CN1874902A

CN1874902A - Coating tool

Info

Publication number: CN1874902A
Application number: CN 200480032689
Authority: CN
Inventors: 米田茂树; 尾松武志
Original assignee: Sakura Color Products Corp
Current assignee: Sakura Color Products Corp
Priority date: 2003-11-07
Filing date: 2004-11-04
Publication date: 2006-12-06
Anticipated expiration: 2024-11-04
Also published as: CN100391751C

Abstract

A coating tool which comprises an ink reservoir tube and, contained therein, an oil-based ink and a backflow preventive which is in contact with the ink, wherein the ink reservoir tube has an interface which is in contact with the oil-based ink and the backflow preventive, the ink reservoir tube contains polyvinyl alcohol and a fluorochemical surfactant at the interface, the oil-based ink comprises a colorant, a resin, an organic solvent, and a gallant, the organic solvent comprises at least one of aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents, the gallant comprises a metal soap, the backflow preventive comprises a gel composition comprising polyacrylic acid and a base ingredient comprising at least one member selected from the group consisting of diglycerol/ethylene oxide adducts and diglycerol/propylene oxide adducts, and the polyacrylic acid is contained in an amount of 0.1 to 3 wt.% based on the whole backflow preventive.

Description

Spreading implement

Technical field

The present invention relates to contain the spreading implement of oiliness China ink, the spreading implement that the wall that relate in particular to the correction pen that can be suitable for containing the oil-base gel China ink, prevents oiliness China ink in the Chu Moguan and anti-reverse fluid when using adheres to is residual, the self-cleaning voltinism has been improved.

Background technology

In the past, under known use diglycerol ethylene oxide adduct, the situation of diglycerol propylene oxide adduct, add silica particle and carry out viscosity adjustment (patent documentation 1, patent documentation 2) as the base material component of the contained anti-reverse fluid of the storage China ink pipe of spreading implement.

Patent documentation 1: the Japan Patent spy opens 2000-343875

Patent documentation 2: the Japan Patent spy opens 2003-34098

But, therefore this anti-reverse fluid is difficult to obtain enough elasticity as a whole, when existing in nib and upwards preserving, can take place in time in the Chu Moguan that anti-reverse fluid hangs and the ink leak that causes, with the consumption of inking, produce the residual problem of adhering to of many anti-reverse fluids on the wall of Chu Moguan.In addition, not shock-resistant, anti-reverse fluid is yielding in the Chu Moguan, easily ink leak.

This is owing under the situation of above-mentioned base material component, be difficult to give structural viscosity (gelation) by silica particle.Think it to be, and be the high material of polarity, thereby hindered gel formation because above-mentioned base material component itself has very strong surface-active.

On the other hand, provide performance self-cleaning voltinism all the time, make oiliness China ink such as opaquing fluid when using, be not attached to Chu Moguan, can use all amounts of being filled, and can confirm the truing tool (for example patent documentation 3) of residual amount when using transparent or opaque containers.

Disclosed following truing tool in this patent documentation 3: have the coating part of coating as the opaquing fluid of content liquid at front end, the interior aforementioned coating part side of container of accommodating aforementioned opaquing fluid is equipped with at least by screening agent, boiling point is at 40～150 ℃ the varsol and the opaquing fluid of the film forming agent formation that dissolves in this solvent, accommodate and disposed the anti-reverse fluid that contacts with the interface, rear of this opaquing fluid, described anti-reverse fluid is at least by insoluble or be insoluble in the organic solvent and/or the water of the varsol of aforementioned opaquing fluid, viscosity modifier and surfactant constitute, and contain fluorine class surfactant as aforementioned surfactants.

Patent documentation 3: the Japan Patent spy opens 2002-103884

But a little less than the in fact aforementioned self-cleaning voltinism of this truing tool, anti-reverse fluid in the China ink (black follower) invades in the opaquing fluid easily in time.

In addition, the truing tool that patent documentation 4 provides has following feature: have the coating part of coating as the opaquing fluid of content liquid at front end, the interior aforementioned coating part side of container of accommodating aforementioned opaquing fluid is equipped with at least by screening agent, boiling point is at 40～150 ℃ the varsol and the opaquing fluid of the film forming agent formation that dissolves in this solvent, disposed the anti-reverse fluid that contacts with the interface, rear of this opaquing fluid, described anti-reverse fluid is made of viscosity modifier and organic solvent and/or water insoluble or that be insoluble in the varsol of aforementioned opaquing fluid at least, has been coated with insoluble at least or is insoluble in the organic solvent and/or the water of the varsol of aforementioned opaquing fluid at the inwall of the container of accommodating aforementioned opaquing fluid.

Patent documentation 4: the Japan Patent spy opens 2002-127680

But owing to just be coated with insoluble at least or be insoluble in the organic solvent and/or the water of the varsol of aforementioned opaquing fluid at the inwall of accepting container, the organic solvent and/or the water of coating die down in time, and described truing tool is also lost aforementioned self-cleaning voltinism.

Problem of the present invention be to provide possess the elasticity that keeps enough, prevent in Chu Moguan in time hang and follow China ink consumption wall adhere to residual, be subjected to impacting the also spreading implements such as truing tool of on-deformable anti-reverse fluid.In addition, problem of the present invention also is to provide in addition, and anti-reverse fluid is difficult for invading in the China ink, for the good spreading implements such as truing tool of continuation of the self-cleaning voltinism effect of China ink and anti-reverse fluid.

The announcement of invention

Solve the method for problem

Spreading implement of the present invention be in Chu Moguan, be equipped with oiliness China ink with contact this oiliness China ink, can be with the spreading implement of the anti-reverse fluid that moves of this oiliness China ink,

Above-mentioned anti-reverse fluid constitutes by containing the base material component more than a kind and the polyacrylic gel combination that are selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct at least,

The above-mentioned polyacrylic acid that contains 0.1～3 weight % with respect to the total amount of aforementioned anti-reverse fluid.

Aforementioned polyacrylic acid better is to contain mean molecule quantity at the polyacrylic acid more than 1000000, is more preferably aforementioned polyacrylic mean molecule quantity more than 1000000.

As the aforementioned substrates composition, better be that the total amount with respect to aforementioned anti-reverse fluid contains 87～99.9 weight %.

In addition, aforementioned anti-reverse fluid better is also to contain silica particle.Good especially is that the total amount that also contains with respect to aforementioned anti-reverse fluid is the silica particle of 1～10 weight %.

The gel combination of aforementioned anti-reverse fluid contains under the situation of silica particle, as aforementioned polyacrylic acid, better be to constitute by multiple polyacrylic acid with different mean molecule quantities, contain mean molecule quantity more than 1000000, better be more than 1500000, be more preferably more than 2000000, good especially be polyacrylic acid more than 3000000, and contain mean molecule quantity below 2000000, better be polyacrylic acid below 1500000.The gel combination of anti-reverse fluid is good especially be contain mean molecule quantity at the polyacrylic acid more than 2000000 and mean molecule quantity at the polyacrylic acid below 1500000.

In addition, the viscosity of aforementioned oiliness China ink better be shear rate when being 0.1 (1/s) more than 700mPas, when shear rate is 100 (1/s) below 500mPas.

In addition, aforementioned oiliness China ink better is to contain in aliphatic hydrocarbon kind solvent, the clicyclic hydrocarbon kind solvent any one organic solvent at least.

Therefore, as anti-reverse fluid, better be to constitute at the polyacrylic gel combination more than 1000000 by containing the base material component more than at least a kind and the mean molecule quantity that are selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct,

The anti-reverse fluid of above-mentioned polyacrylic oiliness China ink that contains 0.1～3 weight % with respect to the total amount of aforementioned anti-reverse fluid.

In addition, as the resin of accommodating pipe that is suitable for revising China ink, can exemplify nylon, PETG, but because these resins are good with the wellability of revising oiliness China inks such as China ink, be difficult to produce auto purification effect based on anti-reverse fluid (black follower or China ink are followed body), so in order to solve this point, need make the oiliness China ink poor with the wellability of Chu Moguan, wellability between anti-reverse fluid and the pipe is good, find by adding polyvinyl alcohol resin as polar resin for the black wellability difference of hanging down polarity, again in order further to make wellability difference selectivity append the material of fluorine class surfactant gained, be formed at the interface that contacts with aforementioned oiliness China ink at least, can solve above-mentioned problem.

The preferred spreading implement of the present invention is that except aforesaid structure, aforementioned storage China ink pipe has the interface that contacts with aforementioned anti-reverse fluid with aforementioned oiliness China ink, contains the spreading implement of polyvinyl alcohol in the aforementioned interface in polyvinyl alcohol and fluorine class surfactant at least.

In addition, the preferred spreading implement of the present invention is that aforementioned interface constitutes with the coating on the internal face that is formed at the black pipe of aforementioned storage, contains the spreading implement of polyvinyl alcohol in this coating in aforementioned polyvinyl alcohol and fluorine class surfactant at least.

Aforementioned interface better is to contain polyvinyl alcohol and fluorine class surfactant.Good especially is that polyvinyl alcohol and fluorine class surfactant are contained in aforementioned interface, contain ionic fluorine class surfactant as aforementioned fluorine class surfactant, contain the spreading implement of the modified polyvinylalcohol opposite as aforementioned polyvinyl alcohol with the aforementioned surfactants ionic.

Among the present invention, owing to as aforementioned anti-reverse fluid, serve as reasons and contain base material component more than at least a kind and the polyacrylic gel combination formation that is selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct,

The above-mentioned polyacrylic anti-reverse fluid that contains 0.1～3 weight % with respect to the total amount of aforementioned anti-reverse fluid, therefore if this anti-reverse fluid, then can provide possess the elasticity that keeps enough, prevent in Chu Moguan in time hang and follow black consumption wall adhere to residual, be subjected to impacting the also spreading implements such as truing tool of on-deformable anti-reverse fluid.

In addition, because the present invention is containing the spreading implement of polyvinyl alcohol and fluorine class surfactant with the interface that aforementioned oiliness China ink contacts with aforementioned anti-reverse fluid, anti-reverse fluid is difficult for invading in the China ink, the good spreading implements such as truing tool of continuation of aforementioned self-cleaning voltinism effect so can provide.Especially, contain polyvinyl alcohol and fluorine class surfactant at aforementioned interface, and contain ionic fluorine class surfactant as aforementioned fluorine class surfactant, contain under the situation of modified polyvinylalcohol as aforementioned polyvinyl alcohol of the ionic opposite with the aforementioned surfactants ionic, can make the interaction that has ion between aforementioned polyvinyl alcohol and the aforementioned fluorine class surfactant, surpassing under the temperature environment of normal temperature (20 ℃), also can keep the auto purification effect more fully specifically under the hot environment more than 40 ℃, storage stability is good.

The best mode that carries out an invention

(anti-reverse fluid)

As anti-reverse fluid, can make the anti-reverse fluid of use (the water-based adverse current prevents composition etc.).Specifically, can use with in diglycerol ethylene oxide adduct and the diglycerol propylene oxide adduct at least any one known follower or adverse current as base material etc. prevent composition, better be with any one contains the polyacrylic acid of 0.1～3 weight % as base material with respect to anti-reverse fluid total volume at least in diglycerol ethylene oxide adduct and the diglycerol propylene oxide adduct in addition.

As aforementioned polyacrylic acid, can use mean molecule quantity more than 1000000, better be more than 1250000, be more preferably more than 2000000, the polyacrylic acid more than 3000000 preferably.In addition, can use maximum as mean molecule quantity better to be below 10000000, be more preferably the polyacrylic acid below 4000000.Mean molecule quantity is less than under 1000000 the situation, and the formation of gel is low, and the elasticity of anti-reverse fluid is low, is easy to generate to hang, and is subjected to impacting also easy deformation.In addition,, also can use mean molecule quantity, because hardening easily better is below 10000000, to be more preferably below 4000000 though surpassing 10000000.

The above-mentioned polyacrylic acid that importantly contains 0.1～3 weight % with respect to the total amount of aforementioned anti-reverse fluid.Under the situation of total amount less than 0.1 weight % of above-mentioned polyacrylic acid with respect to aforementioned anti-reverse fluid, be difficult to form gel, the elasticity of anti-reverse fluid is insufficient, easily hangs, and is subjected to impacting also easy deformation.In addition, above-mentioned polyacrylic acid surpasses under the situation of 3 weight % with respect to the total amount of aforementioned anti-reverse fluid, and then hardening is low with the performance of the black anti-reverse fluid that moves of oiliness.

As above-mentioned polyacrylic acid, better be the cross-linking type polyacrylic acid.Specifically, can use trade name カ one ボ Port, one Le 941 (mean molecule quantity 1250000), カ one ボ Port, one Le 934 (mean molecule quantity 3000000), カ one ボ Port, one Le 940 (mean molecule quantity 4000000) of BF グ Star De リ Star チ corporate system.

As the base material component of aforementioned anti-reverse fluid, can exemplify diglycerol ethylene oxide adduct, diglycerol propylene oxide adduct.As the diglycerol ethylene oxide adduct, can use for example PEO (n) diglycerol ether, as preferred example, can use trade name SC-E2000 (40 moles of addition products of oxirane), the SC-E1500 (30 moles of addition products of oxirane) of this pharmaceutical industries of slope corporate system.

In addition, as aforementioned diglycerol propylene oxide adduct, can use for example PPOX (n) diglycerol ether, as preferred example, can use trade name SC-P1000 (14 moles of addition products of expoxy propane), the SC-P750 (9 moles of addition products of expoxy propane) of this pharmaceutical industries of slope corporate system.

Aforementioned diglycerol ethylene oxide adduct and aforementioned diglycerol propylene oxide adduct can be distinguished optionally use, also can mix use.Total amount with respect to aforementioned anti-reverse fluid better is the described base material component that contains 87～99.9 weight %.Under the situation of total amount less than 87 weight % of this base material component with respect to aforementioned anti-reverse fluid, then hardening, low with the performance of the anti-reverse fluid that moves of oiliness China ink.This base material component surpasses under the situation of 99.9 weight % with respect to the total amount of aforementioned anti-reverse fluid, and then polyacrylic addition reduces, and the elasticity of anti-reverse fluid is insufficient, easily hangs, and is subjected to impacting also easy deformation.

(silica particle)

Among the present invention, for the relation of diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct, importantly use aforementioned polyacrylic acid to replace silica particle.That is,, as mentioned above, under the situation of above-mentioned base material component, be difficult to give structural viscosity (gelation) by silica particle if silica particle and diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct are used simultaneously.Think because above-mentioned base material component itself has very strong surface-active, and be the high material of polarity, thereby hindered gel formation.Opposite with it, for diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct, if use aforementioned polyacrylic acid to replace silica particle, then because used polyacrylic mean molecule quantity is big, the viscosity of aforementioned substrates is significantly increased, and make its gelation, therefore anti-reverse fluid keeps enough elasticity, prevent in Chu Moguan in time hang and follow China ink consumption wall adhere to residually, be subjected to impacting also not yielding.

By this point, better be to use aforementioned polyacrylic acid to replace silica particle separately, but by silica particle and aforementioned polyacrylic acid and aforementioned substrates composition being used simultaneously with certain content, discovery is as anti-reverse fluid, not only have enough elasticity, and can at random control viscoplasticity.Thus, can obtain meeting the anti-reverse fluid of black viscosity, desired black discharge.Specifically, it better is the above-mentioned polyacrylic acid that contains 0.1～3 weight % with respect to the total amount of aforementioned anti-reverse fluid, contain the described base material component of 87～99.9 weight % with respect to the total amount of aforementioned anti-reverse fluid, contain the silica particle of 1～10 weight % with respect to the total amount of aforementioned anti-reverse fluid.

As spendable silica particle among the present invention, can use hydrophily silica arbitrarily, hydrophobic silica, specifically can exemplify trade name " アエロジ Le #380 " (the hydrophily silica of Japanese アエロジ Le corporate system, 1 grade of average particle size 7 μ m), " アエロジ Le #200 " (hydrophily silica, 1 grade of average particle size 12 μ m), " アエロジ Le R-972 " (hydrophobic silica, surface treatment based on dimethyldichlorosilane, 1 grade of average particle size 16 μ m), " hydrophobic silica; アエロジ Le R-976 " (hydrophobic silica, surface treatment based on dimethyldichlorosilane, 1 grade of average particle size 7 μ m), " アエロジ Le R-812 " (hydrophobic silica, based on the surface treatment of HMDS, 1 grade of average particle size 7 μ m).

Contain in the gel combination under the situation of aforementioned anti-reverse fluid of described silica particle, as aforementioned polyacrylic acid used in the present invention, better be to constitute by multiple polyacrylic acid with different mean molecule quantities, contain mean molecule quantity more than 1000000, better be more than 1500000, be more preferably more than 2000000, polyacrylic while more than 3000000 preferably, contain its low polyacrylic acid of molecular weight ratio with respect to these different polyacrylic acid.Specifically, better be contain mean molecule quantity 2000000, better be below 1500000, be more preferably below 1250000, good especially be polyacrylic acid below 1000000.In the combination of such mean molecule quantity, if use polyacrylic acid with multiple mean molecule quantity, constitute anti-reverse fluid with the polyacrylic acid that shows molecular weight distribution, then can prevent gel combination (anti-reverse fluid composition) syneresis (phenomenon that base material in time from anti-reverse fluid composition ooze out) of base material aforementioned or described later from the anti-reverse fluid of the present invention stated with a plurality of peaks or synthetic 1 peak.If syneresis takes place, then under the state that nib makes progress, anti-reverse fluid contraction and China ink is overflowed, or viscosity rises and causes servo-actuated together not good.Described base material is considered to occur in this anti-reverse fluid (composition) from the syneresis of anti-reverse fluid composition and contains under the situation of silica particle, supposition may be by adding aforesaid low-molecular-weight polyacrylic acid again, this polyacrylic acid is as the dispersant onset, prevent the aggegation of silica particle, suppressed the generation of above-mentioned syneresis.

Preferably aforementioned polyacrylic acid is made of the multiple polyacrylic acid with different mean molecule quantities, contain mean molecule quantity at the polyacrylic acid more than 2000000 and mean molecule quantity at the polyacrylic gel combination below 1500000 (anti-reverse fluid composition).

As other adding ingredient, can at random mix surfactant, antioxidant, anticorrisive agent, mould inhibitor etc. as required in the anti-reverse fluid.

As the manufacture method of anti-reverse fluid, for example each composition of above-mentioned appointment can be disperseed to obtain anti-reverse fluid of the present invention by mill.

(oiliness China ink)

Better be to contain the spreading implement of colouring agent, resin, organic solvent and gelating agent, but be not limited thereto as aforementioned oiliness China ink.

Under the situation of truing tools such as correction pen, better being to contain titanium oxide in the oiliness China ink as colouring agent (sheltering material), also better is to contain in aliphatic hydrocarbon kind solvent, the clicyclic hydrocarbon kind solvent any one organic solvent at least in the oiliness China ink.

In addition, as above-mentioned gelating agent, better be that solubility (20 ℃) for above-mentioned organic solvent is the dissolubility gelating agent of 0.1～20 weight %, the viscosity of China ink better be shear rate when being 0.1 (1/s) more than 700mPas, when shear rate is 100 (1/s) below 500mPas, as concrete gelating agent, better be to contain metallic soap.Good especially is to contain 2 ethyl hexanoic acid aluminium.

The condition determination of this viscosity is, uses front end to have the correction pen of nib that the ball that makes diameter 1.0mm keeps the gap of 60 μ m, and the viscosity (mPas) when with the rotation by ball China ink being imposed shearing force is as standard.The viscosity of the oiliness China ink shown in the present invention is for using HAAKE corporate system current meter (reometer) RS-75,20 ℃ of values of measuring with the Z20DIN rotor.

The combination of the viscosity of the structural viscosity by aforementioned anti-reverse fluid and this oiliness China ink (revising China ink) can obtain containing the outflow that keeps China ink and to its flexible spreading implement that carries out the better anti-reverse fluid of servo-actuated simultaneously.

(Chu Moguan)

As storage China ink pipe used in the present invention, importantly do not invaded (not imbibition), and do not prevented base material (polar substances) intrusion by adverse current by the contained aliphatic of oiliness China ink, clicyclic hydrocarbon kind solvent.

The Chu Moguan that satisfies these requirements is made of the resin that is selected from nylon resin, pet resin and polybutylene terephthalate (PBT) resin.Specifically can exemplify 4,6-nylon, 6-nylon, 6,6-nylon, 6,10-nylon, 6,12-nylon, 11-nylon, 12-nylon, PET (PETG), PBT (polybutylene terephthalate (PBT)).By the angle that can confirm residual amount from the outside, better be nylon resin and PET (PETG).As described later, interface at the Chu Moguan that contacts with the oiliness China ink is at least contained under the situation of polyvinyl alcohol and fluorine class surfactant, by constituting Chu Moguan by nylon resin and PET (PETG) or PBT (polybutylene terephthalate (PBT)), can prevent the circuit (passage) of formation China ink in Chu Moguan in time, prevent that China ink from draining to outside or solvent minimizing and the keeping quality of China ink is lost from this black circuit (passage).Based on this point, aforementioned storage China ink pipe better is to be made of the resin that is selected from nylon resin, pet resin and polybutylene terephthalate (PBT) resin.

The present invention better is that the black pipe of aforementioned storage has the interface that contacts with aforementioned anti-reverse fluid with aforementioned oiliness China ink, contains the spreading implement of polyvinyl alcohol in the aforementioned interface in polyvinyl alcohol (PVA) and fluorine class surfactant at least.Be more preferably the spreading implement that contains polyvinyl alcohol and fluorine class surfactant in the aforementioned interface.

As aforementioned PVA (polyvinyl alcohol), better be the PVA that contains a large amount of-OH base (hydroxyl), polarity quite high (water-soluble).Therefore, be more preferably complete gelation type or the approaching PVA of gelation type fully, also can use the PVA of partial gel type.Comparatively ideal PVA is a complete gelation type or near the complete PVA of gelation type, better be for example jelly grade more than 98.0.Specifically, better be the goods of complete gelation, can use PVA-102, PVA-103, PVA-104A, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-135, the PVA-HC of trade name " the Network ラレ Port バ one Le " series of Network ラレ corporate system.Wherein, better be the trade name " Network ラレ Port バ one Le PVA-105 " (jelly grade 98～99mol%, the degree of polymerization 500) of Network ラレ corporate system.In addition, better be Japanese synthetic chemistry corporate system, NH-26, NH-20, NH-18, N-300, NM-14, NM-11, the NL-05 of the trade name of NH-" go one セノ one Le N type Port バ one Le " series.In addition, can use VC-20, V, the VC-10 of the trade name " V series " of Japanese vinegar PVC Port バ one Le corporate system, JC-25, JF-20, JF-17, JF-17L, JF-10, JF-05, the JF-04 of " J series ".

If the coating that will constitute the interface that contacts with the oiliness China ink is as benchmark, PVA is 0.05wt%～20wt% with respect to this coating liquid total amount, better is 0.5wt%～10wt%.PVA is with respect under the situation of this coating liquid total amount less than 0.05wt%, and is low for aforementioned oiliness China ink self-cleaning voltinism.On the other hand, PVA surpasses under the situation of 20wt% with respect to this coating liquid total amount, and viscosity is too high, applies difficulty.

In addition, among the present invention, except unmodified PVA (unmodified polyvinyl alcohol), in order to ensure surpassing the storage stability that under the hot environment more than 40 ℃, also can keep the auto purification effect under the temperature environment of normal temperature, specifically more fully, can use modified PVA (polyvinyl alcohol) with cationic or anionic property.Promptly, better be the PVA that contains a large amount of-OH base (hydroxyl), polarity quite high (water-soluble), better being complete gelation type or the approaching cation-modified or anion-modified PVA (polyvinyl alcohol) of gelation type fully, for example better is that jelly grade is more than 86.0.As comparatively ideal PVA, specifically can exemplify trade name " Network ラレ Port バ one Le KL-118 " (the anion-modified polyvinyl alcohol of Network ラレ corporate system, jelly grade 95～99mol%), with trade name " Network ラレ Port バ one Le CM-318 " (the cation-modified polyvinyl alcohol of corporate system, the quaternary ammonium modified PVA, the trade name of jelly grade 86～91mol%), Japanese synthetic chemistry corporate system " go one セ Off アイマ one K210 " (cation-modified polyvinyl alcohol) plasma modified polyvinylalcohol.

If the coating that will constitute the interface that contacts with the oiliness China ink is as benchmark, these ion modifications PVA is 0.05wt%～10wt% (amounting to below 20wt% with unmodified PVA) with respect to this coating liquid total amount, better is 0.1wt%～5wt%.PVA is with respect under the situation of this coating liquid total amount less than 0.05wt%, and is low for aforementioned oiliness China ink self-cleaning voltinism.On the other hand, PVA surpasses under the situation of 20wt% with respect to this coating liquid total amount, and viscosity is too high, applies difficulty.

As fluorine class surfactant used in the present invention, importantly have dissolubility, and be insoluble to the solvent (the alicyclic hydro carbons organic solvent of aliphatic) of China ink water, have the effect that the surface tension of making significantly descends.It better is ionic fluorine class surfactant.Specifically can exemplify the S-111,112,113,121,131,132,141,145 of the trade name サ one Off ロ Application series of セイミケミカ Le corporate system.In addition, can exemplify ネオス corporate system trade name " Off one ジエ Application ト " series 100,150,300,400S, the EF-101,102,104,105,112 of trade name " the エ Off ト Star プ " series of the マテリア of Mitsubishi Le corporate system.

If the coating that will constitute the interface that contacts with the oiliness China ink is as benchmark, aforementioned fluorine class surfactant contains 0.005wt%～1wt% with respect to this coating liquid total amount, better is 0.03wt%～0.5wt%.Aforementioned fluorine class surfactant is difficult to make surface tension to descend with respect under the situation of this coating liquid total amount less than 0.005wt%; On the other hand, if surpass 1wt%, then aforementioned fluorine class surfactant is easily from interface stripping to the oiliness China ink of coating.

Coating liquid as forming above-mentioned coating importantly contains polyvinyl alcohol at least in PVA and fluorine class surfactant, better be to make the coating aqueous solution that contains water to use.Therefore, better be to make with respect to this coating liquid total amount to contain the aforementioned PVA of 0.05wt%～20wt%, the coating aqueous solution that the content of this surfactant is 0.005wt%～1wt% with respect to this coating liquid total amount when adding aforementioned fluorine class surfactant again.Can add defoamer, surface tension adjustment agent, anticorrisive agent etc. in the coating liquid.

Spreading implement of the present invention can obtain by for example following manufacture method.That is, the pipe of accommodating that has been shaped is immersed in the aqueous solution of PVA and fluorine class surfactant, forms the coating of the aqueous solution of PVA and fluorine class surfactant at aforementioned internal face of accommodating pipe.Then, carried out drying in 1 day with stove or by the normal temperature placement.Then, accommodate filling oiliness China ink in the pipe, filling anti-reverse fluid at this.Thus, obtain the spreading implement of one embodiment of the present invention.

In the spreading implement of the present invention, in order to form the interface of accommodating pipe internal surface, except forming coating by above-mentioned dipping or directly accommodating above-mentioned that application forms the coating in the pipe, can also be by known manufacturing process such as extrusion molding or injection moldeds, when Chu Moguan is shaped, has the internal layer that in PVA and fluorine class surfactant, contains the interface of polyvinyl alcohol at least in the inner surface formation of accommodating pipe.In addition, can also be after Chu Moguan be shaped, side will have the internal layer that contains the interface of polyvinyl alcohol in PVA and fluorine class surfactant at least and form as formed body within it, after the internal layer that perhaps will have an interface of containing polyvinyl alcohol in PVA and fluorine class surfactant at least was shaped as formed body, the main body in its outside with Chu Moguan formed as formed body.

Perhaps, also can make in the resin of the Chu Moguan that is selected from nylon resin, pet resin and polybutylene terephthalate (PBT) resin, in PVA and fluorine class surfactant, contain polyvinyl alcohol at least, make the interface that contacts with anti-reverse fluid with the oiliness China ink become the interface of in PVA and fluorine class surfactant, containing polyvinyl alcohol at least and constitute.

As the concrete form of the present invention, can exemplify oiliness China ink and the anti-reverse fluid that contacts this China ink are housed in Chu Moguan,

Above-mentioned storage China ink pipe has the interface that contacts with aforementioned anti-reverse fluid with aforementioned oiliness China ink,

The spreading implement that in polyvinyl alcohol and fluorine class surfactant, contains polyvinyl alcohol in the aforementioned interface at least.

The black pipe of aforementioned storage is not particularly limited, and better is to constitute with the resin that is selected from nylon resin, pet resin and polybutylene terephthalate (PBT) resin as previously mentioned.These never are subjected to, and aliphatic or clicyclic hydrocarbon kind solvent are invaded, the angle of not imbibition is desirable, and never are subjected to prevent that as the adverse current of polar substances the angle that base material (anti-reverse fluid) is invaded from also being desirable.Specifically, better be 4,6-nylon, 6-nylon, 6,6-nylon, 6,10-nylon, 6,12-nylon, 11-nylon, 12-nylon, PET (PETG), PBT (polybutylene terephthalate (PBT)).By the angle that can confirm residual amount from the outside, all nylon and PET are desirable.

The aforementioned storage Mo Guanzhong that in the interface, contains polyvinyl alcohol at least, better be to adopt foregoing anti-reverse fluid, promptly constitute, contain the above-mentioned polyacrylic anti-reverse fluid of 0.1～3 weight %, but be not particularly limited with respect to the total amount of aforementioned anti-reverse fluid by containing the base material component more than at least a kind and the polyacrylic gel combination that are selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct.Even the oiliness China ink is housed in Chu Moguan at least, above-mentioned storage China ink pipe has the interface that contacts with aforementioned oiliness China ink at least, at least the spreading implement that contains polyvinyl alcohol in the aforementioned interface in polyvinyl alcohol and fluorine class surfactant also can be as the spreading implement that at least the oiliness China ink is had the self-cleaning voltinism.

Most preferred spreading implement is following spreading implement: oiliness China ink and the anti-reverse fluid that contacts this China ink are housed in Chu Moguan,

The resin that above-mentioned storage Mo Guanyou is selected from nylon resin, pet resin and polybutylene terephthalate (PBT) resin constitutes,

Contain polyvinyl alcohol and fluorine class surfactant in the aforementioned interface,

Contain ionic fluorine class surfactant as aforementioned fluorine class surfactant, contain the modified polyvinylalcohol opposite as aforementioned polyvinyl alcohol with the aforementioned surfactants ionic,

Aforementioned oiliness China ink contains colouring agent, resin, organic solvent and gelating agent,

As aforementioned organic solvent, contain in aliphatic hydrocarbon kind solvent, the clicyclic hydrocarbon kind solvent any one organic solvent at least,

Contain metallic soap as gelating agent,

Aforementioned anti-reverse fluid constitutes by containing the base material component more than a kind and the polyacrylic gel combination that are selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct at least,

As spreading implement, except in urceolus, equip Chu Moguan, the distolateral spreading implement that possesses nib, one-sided refilling structure of Chu Moguan, can also use at one of the black pipe of aforementioned storage distolaterally have nib, at another distolateral spreading implement that has at least the pressue device that the oiliness China ink in this storage China ink pipe of packing into is pressurizeed.

Embodiment

The nib of ball diameter 1mm is installed at an end of the black pipe of transparent storage of bore (internal diameter) 4mm that is shaped with the 11-nylon resin, then, fill the oiliness China ink that contains 50 weight % titanium oxide, 4 weight % abietic resins, 40 weight % aliphatic hydrocarbon kind solvents and 1.5 weight % gelating agents (2 ethyl hexanoic acid aluminium) with respect to oiliness China ink total amount in the China ink pipe aforementioned the storage, follow composition again from the described anti-reverse fluid of forming shown in the top of the aforementioned oiliness China ink ST Stuffing Table 1 of embodiment.For relatively, also with above-mentioned operation similarly, the composition shown in the composition substitution list 1 of the described anti-reverse fluid of forming shown in the ST Stuffing Table 2 of comparative example.Store up the aftermentioned coating processing that black Guan Wei contains PVA and fluorine class surfactant at this.

Then, for the correction ball pen that contains shown in table 1 and the table 2 each anti-reverse fluid of forming, with regard to nib make progress under the state keeping quality and when on paper, writing anti-reverse fluid the servo-actuated of oiliness China ink is estimated.The results are shown in each table.

Have good keeping qualities and represent with zero, keeping quality difference and usefulness * expression of hanging represent the usefulness zero that the servo-actuated of China ink is good, to the usefulness * expression of the servo-actuated difference of China ink.All all are based on outward appearance and observe.

Above-mentioned keeping quality is estimated the state after 50 ℃, 1 month.

[table 1]

(weight %)

Anti-reverse fluid is formed (trade name)		Embodiment
		Embodiment											1	2	3	4	5	6	7	8	9	10	11
		SC-E2000		98.0	97.0				95.0		94.5		1	2	3	4	5	6	7	8	9	10	11
SC-E1500		SC-E2000		98.0	97.0				95.0		94.5				98.5				95.0			92.5
SC-E1500		SC-P1000					98.5					94.5			98.5				95.0			92.5
SC-P750		SC-P1000					98.5					94.5					99.9						92.9
SC-P750		カ one ボ Port one Le 940		2.0	3.0			0.1	1.0	1.0	0.5	0.5					99.9						92.9	0.5	0.1
カ one ボ Port one Le 934		カ one ボ Port one Le 940		2.0	3.0			0.1	1.0	1.0	0.5	0.5			1.5	1.5								0.5	0.1
カ one ボ Port one Le 934		アエロジルR-972							4.0		5.0				1.5	1.5								7.0
アエロジル#380		アエロジルR-972							4.0		5.0								4.0		5.0		7.0	7.0
アエロジル#380		Estimate	The keeping quality of anti-reverse fluid (whether hanging)	○	○	○	○	○	○	○	○	○							4.0		5.0		7.0	○	○
Servo-actuated to the oiliness China ink	○		The keeping quality of anti-reverse fluid (whether hanging)	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○		○	○

(remarks)

SC-E2000: diglycerol ethylene oxide adduct, this pharmaceutical industries of slope corporate system, 40 moles of addition products of oxirane

SC-E1500: diglycerol ethylene oxide adduct, this pharmaceutical industries of slope corporate system, 30 moles of addition products of oxirane

SC-P1000: diglycerol propylene oxide adduct, this pharmaceutical industries of slope corporate system, 14 moles of addition products of expoxy propane

SC-P750: diglycerol propylene oxide adduct, this pharmaceutical industries of slope corporate system, 9 moles of addition products of oxirane

カ one ボ Port one Le 940: cross-linking type polyacrylic acid, BF グ Star De リ Star チ corporate system, mean molecule quantity 4000000

カ one ボ Port one Le 934: cross-linking type polyacrylic acid, BF グ Star De リ Star チ corporate system, mean molecule quantity 3000000

アエロジ Le R-972: hydrophobic silica, Japanese アエロジ Le corporate system, 1 grade of average particle size is 16 μ m

アエロジ Le #380: hydrophily silica, Japanese アエロジ Le corporate system, 1 grade of average particle size is 7 μ m

[table 2]

(weight %)

Anti-reverse fluid is formed (trade name)		Comparative example
		Comparative example									1	2	3	4	5	6	7	8	9
		SC-E2000		95.0	96.0						1	2	3	4	5	6	7	8	9
SC-E1500		SC-E2000		95.0	96.0								96.0		93.0		90.0	85.0
SC-E1500		SC-P1000					95.0						96.0		93.0		90.0	85.0
SC-P750		SC-P1000					95.0									93.0			85.0
SC-P750		カ one ボ Port one Le 940		5.0												93.0			85.0
カ one ボ Port one Le 934		カ one ボ Port one Le 940		5.0
カ one ボ Port one Le 934		アエロジルR-972			4.0			7.0												15.0
アエロジル#380		アエロジルR-972			4.0			7.0					4.0	5.0		7.0	10.0		15.0	15.0
アエロジル#380		Estimate	The keeping quality of anti-reverse fluid (whether hanging)	○	×	×	×	×	×	×			4.0	5.0		7.0	10.0		15.0	×	×
Servo-actuated to the oiliness China ink	×		The keeping quality of anti-reverse fluid (whether hanging)	○	×	×	×	×	×	×	○	○	○	○	○	○	○	○		×	×

(remarks)

By table 1 and table 2 as can be known, constitute if possess by containing the base material component more than at least a kind and the polyacrylic gel combination of mean molecule quantity more than 1000000 that are selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct,

Contain the spreading implement of the anti-reverse fluid of above-mentioned polyacrylic acid of 0.1～3 weight % with respect to the total amount of aforementioned anti-reverse fluid, then anti-reverse fluid can not produce in time and hang, have good keeping qualities, and also also good for the servo-actuated of the outflow of the oiliness China ink in the Chu Moguan.

The spreading implement of present embodiment possesses the elasticity that keeps enough, prevent in Chu Moguan in time hang and follow China ink consumption wall adhere to residual, be subjected to impacting also on-deformable anti-reverse fluid.

Therefore, the ink leak that has prevented to take place in time in the Chu Moguan anti-reverse fluid to hang and caused and with the residual problem of adhering to that produces many anti-reverse fluids on the wall in the consumption storage China ink pipe of inking, also has resistance to impact, anti-reverse fluid is not yielding in Chu Moguan, so can prevent ink leak on this point yet.

Then, except adding silica particle again, adopt outside the composition shown in the table 3, with previous embodiment similarly, adjust anti-reverse fluid, make to revise and use ball pen, make progress keeping quality under the state, syneresis when anti-reverse fluid is to the servo-actuated of oiliness China ink and preservation when writing on paper of nib estimated.Hanging is the phenomenon that anti-reverse fluid is out of shape in time, identical with the evaluation of the embodiment that has stated to the conservatory evaluation that nib makes progress under the state.Syneresis by anti-reverse fluid in time from base material ooze out with * expression, do not ooze out with zero the expression estimate.It the results are shown in table 3.Above-mentioned keeping quality and the syneresis when preserving are estimated the state after 50 ℃, 1 month.The anti-reverse fluid that spreading implement had in the table 3 contains silica particle, and contain multiple polyacrylic acid with different mean molecule quantities, contain the polyacrylic acid of mean molecule quantity more than 2000000, and contain mean molecule quantity and be lower than the polyacrylic acid of aforementioned polyacrylic mean molecule quantity below 2000000, below 1500000, below 1250000, below 1000000.Spreading implement in the table 4 contains the polyacrylic acid of mean molecule quantity more than 2000000.

[table 3]

(weight %)

Anti-reverse fluid is formed (trade name)		Molecular weight (ten thousand)	Embodiment
			Embodiment									12	13	14	15	16	17	18	19	20	21
			SC-E2000	-	93.0	92.5	92.0	93.5	93.0	93.0	93.0	12	13	14	15	16	17	18	19	20	21	93.0	93.0	93.0
カ one ボ Port one Le 940		400	SC-E2000	-	93.0	92.5	92.0	93.5	93.0	93.0	93.0	1.0	1.0	1.0	0.5	1.0	1.0	1.0	1.0			93.0	93.0	93.0
カ one ボ Port one Le 940		400	カ one ボ Port one Le 934	300								1.0	1.0	1.0	0.5	1.0	1.0	1.0	1.0				1.0
カ one ボ Port one Le 941		125	カ one ボ Port one Le 934	300								1.0	1.5	2.0	1.0					1.0			1.0
カ one ボ Port one Le 941		125	ジユンロンPW-110	100					1.0			1.0	1.5	2.0	1.0					1.0
ジユンロンPW-111		10	ジユンロンPW-110	100					1.0								1.0
ジユンロンPW-111		10	ジユンロンPW-150	200							1.0						1.0							1.0
アクペツクHV-501E		150	ジユンロンPW-150	200							1.0								1.0		1.0			1.0
アクペツクHV-501E		150	アエロジルR-972		5.0	5.0	5.0	5.0	5.0	5.0	5.0								1.0		1.0	5.0	5.0	5.0
Estimate	The keeping quality of anti-reverse fluid (whether hanging)		アエロジルR-972		5.0	5.0	5.0	5.0	5.0	5.0	5.0	○	○	○	○	○	○	○	○	○	○	5.0	5.0	5.0
	The keeping quality of anti-reverse fluid (whether hanging)		Servo-actuated to the oiliness China ink	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○
	Syneresis when anti-reverse fluid is preserved		Servo-actuated to the oiliness China ink	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○

(remarks)

カ one ボ Port one Le 941: cross-linking type polyacrylic acid, BF グ Star De リ Star チ corporate system, mean molecule quantity 1250000

ジユ Application ロ Application PW-110: cross-linking type polyacrylic acid, Japanese pure medicine corporate system, mean molecule quantity 1000000

ジユ Application ロ Application PW-111: cross-linking type polyacrylic acid, Japanese pure medicine corporate system, mean molecule quantity 100000

ジユ Application ロ Application PW-150: cross-linking type polyacrylic acid, Japanese pure medicine corporate system, mean molecule quantity 2000000

ア Network ペ Star Network HV-501E: cross-linking type polyacrylic acid, the Sumitomo corporate system of refining, mean molecule quantity 1500000

[table 4]

(weight %)

Anti-reverse fluid is formed (trade name)		Molecular weight (ten thousand)	Comparative example
			Comparative example	10	11
			SC-E2000	10	11	-	94.0	93.0
カ one ボ Port one Le 940		400	SC-E2000	1.0	2.0	-	94.0	93.0
カ one ボ Port one Le 940		400	カ one ボ Port one Le 934	1.0	2.0	300
カ one ボ Port one Le 941		125	カ one ボ Port one Le 934			300
カ one ボ Port one Le 941		125	ジユンロンPW-110			100
ジユンロンPW-111		10	ジユンロンPW-110			100
ジユンロンPW-111		10	ジユンロンPW-150			200
アクペツクHV-501E		150	ジユンロンPW-150			200
アクペツクHV-501E		150	アエロジルR-972			5.0	5.0
Estimate	The keeping quality of anti-reverse fluid (whether hanging)		アエロジルR-972		○	5.0	5.0	○
	The keeping quality of anti-reverse fluid (whether hanging)		Servo-actuated to the oiliness China ink	○	○	○		○
	Syneresis when anti-reverse fluid is preserved		Servo-actuated to the oiliness China ink	○	×	○	×

(remarks)

ア Network ペ Star Network HV 501E: cross-linking type polyacrylic acid, the Sumitomo corporate system of refining, mean molecule quantity 1500000

By table 3, table 4 as can be known, contain under the situation of anti-reverse fluid of silica particle, have and contain multiple polyacrylic acid with different mean molecule quantities, contain the polyacrylic acid of mean molecule quantity more than 2000000, and contain spreading implement that mean molecule quantity is lower than the polyacrylic anti-reverse fluid of aforementioned polyacrylic mean molecule quantity below 2000000, below 1500000, below 1250000, below 1000000 keep nib make progress under the state keeping quality and when on paper, writing in the servo-actuated of anti-reverse fluid to the oiliness China ink, prevent the syneresis of base material.

Then, respectively applying shown in the black Guan Zaibiao 5 of transparent storage of bore (internal diameter) 4mm that will be shaped with the 11-nylon resin carried out dip-coating in the aqueous solution.Apply the aqueous solution and form formation, for example in the spreading implement of embodiment 22, contain the condition preparation of the aforementioned fluorine class surfactant of 0.15wt% according to the PVA that contains 5wt% with respect to the coating liquid total amount, with solid component meter with the treatment fluid of table 5.Then, respectively store up black pipe and from the described aqueous solution, take out respectively, air-dry at normal temperatures 1 day, form the coating that contains PVA and fluorine class surfactant at the aforementioned internal face that respectively stores up black pipe with aforementioned.Other embodiment, comparative example are operated similarly, form above-mentioned coating at each internal face that stores up black pipe.

[table 5]

(weight %)

Ionic			Embodiment
			Embodiment																	22	23	24	25	26	27	28	29	30	31	32	33	34	35	36	37	38
			Treatment fluid is formed	Polyvinyl alcohol																22	23	24	25	26	27	28	29	30	31	32	33	34	35	36	37	38
PVA-105	Nonionic	5.0		Polyvinyl alcohol																5.0	2.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	10.0		5.0	5.0	5.0		5.0
PVA-105	Nonionic	5.0		CM-318		Cationic			0.1	0.1	0.01	0.1	1.0	50	0.1	0.1	0.1	10.0	0.1	5.0	2.0	5.0	5.0	5.0	5.0	5.0	5.0	5.0	10.0		5.0	5.0	5.0		5.0
KL-118	Anionic			CM-318		Cationic			0.1	0.1	0.01	0.1	1.0	50	0.1	0.1	0.1	10.0	0.1													0.1	5.0	10.0	0.1
KL-118	Anionic			Fluorine class surfactant																												0.1	5.0	10.0	0.1
サ one Off ロ Application S-111N	Anionic	0.15		Fluorine class surfactant																0.45	0.15	0.03	0.15	0.15	0.15	0.15	0.3	0.45	0.15	0.15					0.15
サ one Off ロ Application S-111N	Anionic	0.15		サ one Off ロ Application S-121N		Cationic													0.15	0.45	0.15	0.03	0.15	0.15	0.15	0.15	0.3	0.45	0.15	0.15					0.15	0.15	0.15	0.15
Water		94.85		サ one Off ロ Application S-121N		Cationic													0.15	94.55	97.75	94.87	94.84	94.75	93.85	89.85	94.6	94.45	89.75	89.85	94.75	94.75	89.85	89.85	94.75	0.15	0.15	0.15
Water		94.85		Add up to (coating liquid total amount)			100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	94.55	97.75	94.87	94.84	94.75	93.85	89.85	94.6	94.45	89.75	89.85	94.75	94.75	89.85	89.85	94.75	100.0	100.0	100.0	100.0
Self-cleaning voltinism after pipe is handled	Initially			Add up to (coating liquid total amount)			100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	100.0	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	100.0	100.0	100.0	100.0	○
	Initially		20℃	Preserved 3 days	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○			○
	50℃	Preserved 3 days	20℃	Preserved 3 days	○	○	○	○	○	○	○	○	○	○	○	○	○	○	○	×	×	○	○	○	○	○	○	○	×	○	○	×	○	○	○	○	○	×

(remarks)

PVA-105: the trade name of Network ラレ corporate system " Network ラレ Port バ one Le PVA105 " (jelly grade 98～99mol%, the degree of polymerization 500)

CM-318: Network ラレ corporate system, trade name " Network ラレ Port バ one Le CM-318 " (cation-modified polyvinyl alcohol, quaternary ammonium modified PVA, jelly grade 86～91mol%)

KL118: Network ラレ corporate system, trade name " Network ラレ Port バ one Le KL118 " (anion-modified polyvinyl alcohol, jelly grade 95～99mol%)

サ one Off ロ Application S-111N: セイミケミカ Le corporate system, trade name " サ one Off ロ Application S-111N " (anionic fluorine class surfactant, concentration 30%), the numerical value in the table is the weight % of solid constituent

サ one Off ロ Application S-121N: セイミケミカ Le corporate system, trade name " サ one Off ロ Application S-121N " (cationic fluorine class surfactant, concentration 30%), the numerical value in the table is the weight % of solid constituent

Then, the nib of ball diameter 1mm is installed at this end that stores up black pipe, then, in aforementioned storage China ink pipe, fill and contain 50 weight % titanium oxide with respect to oiliness China ink total amount, 4 weight % abietic resins, the oiliness China ink of 40 weight % aliphatic hydrocarbon kind solvents and 1.5 weight % gelating agents (2 ethyl hexanoic acid aluminium), then fill following anti-reverse fluid again: diglycerol ethylene oxide adduct (this drug company of the slope system that contains 98.5 weight % with respect to anti-reverse fluid total volume from the top of aforementioned oiliness China ink, trade name " SC-E2000 ") as base material, the polyacrylic acid (BF グ Star De リ Star チ corporate system, trade name " カ one ボ Port one Le 940 ") of molecular weight more than 1000000 that contains 0.1～3 weight % with respect to anti-reverse fluid total volume.

If use the above-mentioned storage China ink pipe coating paper that this oiliness China ink and anti-reverse fluid are housed, then anti-reverse fluid is difficult for invading in the China ink, and oiliness China inks such as opaquing fluid can not continue performance self-cleaning voltinism attached on the Chu Moguan in use, and, can clearly confirm residual amount owing to be transparent Chu Moguan.In addition, if use the spreading implement of the Chu Moguan of coating aqueous solution processing, even then under 50 ℃ hot environment, also bring into play the self-cleaning voltinism sustainably through containing ionic fluorine class surfactant and the modified polyvinylalcohol opposite with this surface active agent ion type.In the table 5, in the evaluation of self-cleaning voltinism, " initially " is meant that " preserving 3 days " was meant the state of the self-cleaning voltinism when the ball pen assembling was coated with on paper after 3 days when ball pen assembling back was coated with China ink on paper at first.

The possibility of utilizing on the industry

Spreading implement of the present invention can be used for truing tool and other spreading implements such as correction pen.

Claims

1. spreading implement, it is the oiliness China ink to be housed in Chu Moguan and to contact this oiliness China ink, can it is characterized in that with the spreading implement of the anti-reverse fluid that moves of this oiliness China ink,

Described anti-reverse fluid constitutes by containing the base material component more than a kind and the polyacrylic gel combination that are selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct at least,

The described polyacrylic acid that contains 0.1～3 weight % with respect to the total amount of described anti-reverse fluid.

2. spreading implement as claimed in claim 1, its feature are that also described polyacrylic acid contains mean molecule quantity at the polyacrylic acid more than 1000000.

3. spreading implement as claimed in claim 2, its feature also are, also contain silica particle, and described polyacrylic acid is made of the multiple polyacrylic acid with different mean molecule quantities, contain mean molecule quantity at the polyacrylic acid below 2000000.

4. spreading implement as claimed in claim 2, its feature also is, also contain silica particle, and described polyacrylic acid is made of the multiple polyacrylic acid with different mean molecule quantities, contain mean molecule quantity at the polyacrylic acid more than 2000000 and mean molecule quantity at the polyacrylic acid below 1500000.

5. spreading implement as claimed in claim 1, its feature also are, contain the described base material component of 87～99.9 weight % with respect to the total amount of described anti-reverse fluid.

6. spreading implement as claimed in claim 1, its feature are that also the total amount that described anti-reverse fluid contains with respect to described anti-reverse fluid is the silica particle of 1～10 weight %.

7. spreading implement as claimed in claim 1, its feature also be, the viscosity of described oiliness China ink when shear rate is 0.1 (l/s) more than 700mPas, when shear rate is 100 (l/s) below 500mPas.

8. spreading implement as claimed in claim 1, its feature also be, described oiliness China ink contains in aliphatic hydrocarbon kind solvent, the clicyclic hydrocarbon kind solvent any one organic solvent at least.

9. spreading implement as claimed in claim 1, its feature are that also the black pipe of described storage has the interface that contacts with described anti-reverse fluid with described oiliness China ink,

In polyvinyl alcohol and fluorine class surfactant, contain polyvinyl alcohol at least in the described interface.

10. spreading implement as claimed in claim 9, its feature are that also described interface is made of the coating on the internal face that is formed at the black pipe of described storage, contain polyvinyl alcohol at least in this coating in described polyvinyl alcohol and fluorine class surfactant.

11. spreading implement as claimed in claim 9, its feature are that also polyvinyl alcohol and fluorine class surfactant are contained in described interface.

12. spreading implement as claimed in claim 9, its feature also be, described polyvinyl alcohol contains the ionic polyvinyl more than a kind or 2 kinds that is selected from nonionic, cationic and anionic.

13. spreading implement as claimed in claim 9, its feature also be, described fluorine class surfactant contains the ionic fluorine class surfactant more than a kind or 2 kinds that is selected from nonionic, cationic and anionic.

14. spreading implement as claimed in claim 9, its feature are that also described fluorine class surfactant contains ionic fluorine class surfactant, described polyvinyl alcohol contains and the opposite modified polyvinylalcohol of described surface active agent ion type.

15. spreading implement as claimed in claim 14, its feature are that also described polyvinyl alcohol is cationic modified polyvinyl alcohol, described fluorine class surfactant is an anionic fluorine class surfactant; Perhaps described polyvinyl alcohol is the anionic modified polyvinylalcohol, and described fluorine class surfactant is cationic fluorine class surfactant.

16. spreading implement as claimed in claim 9, its feature are that also the resin that described storage Mo Guanyou is selected from nylon resin, pet resin and polybutylene terephthalate (PBT) resin constitutes.

17. spreading implement as claimed in claim 9, its feature are that also described oiliness China ink contains colouring agent, resin, organic solvent and gelating agent.

18. spreading implement as claimed in claim 17, its feature are that also described colouring agent contains titanium oxide.

19. spreading implement as claimed in claim 9, its feature also be, the oiliness China ink contains in aliphatic hydrocarbon kind solvent, the clicyclic hydrocarbon kind solvent any one organic solvent at least.

20. spreading implement as claimed in claim 17, its feature also is, described gelating agent is the dissolubility gelating agent of 0.1～20 weight % for the solubility (20 ℃) for described organic solvent, the China ink viscosity when shear rate is 0.1 (l/s) more than 700mPas, when shear rate is 100 (l/s) below 500mPas.

21. spreading implement as claimed in claim 17, its feature are that also the oiliness China ink contains metallic soap as gelating agent, contain in aliphatic hydrocarbon kind solvent, the clicyclic hydrocarbon kind solvent at least any one as organic solvent.

22. spreading implement, it is the spreading implement that oiliness China ink and the anti-reverse fluid that contacts this China ink are housed in Chu Moguan, it is characterized in that,

The resin that described storage Mo Guanyou is selected from nylon resin, pet resin and polybutylene terephthalate (PBT) resin constitutes,

The black pipe of described storage has the interface that contacts with described anti-reverse fluid with described oiliness China ink,

Contain polyvinyl alcohol and fluorine class surfactant in the described interface,

Contain ionic fluorine class surfactant as described fluorine class surfactant, contain the modified polyvinylalcohol opposite as described polyvinyl alcohol with described surface active agent ion type,

Described oiliness China ink contains colouring agent, resin, organic solvent and gelating agent,

As described organic solvent, contain in aliphatic hydrocarbon kind solvent, the clicyclic hydrocarbon kind solvent any one organic solvent at least,

Contain metallic soap as gelating agent,

23. spreading implement, it is the spreading implement that the oiliness China ink is housed in Chu Moguan at least, it is characterized in that,

The black pipe of described storage has the interface that contacts with described oiliness China ink at least,

24. spreading implement as claimed in claim 1, its feature also be, distolaterally has a nib at one of the black pipe of described storage, distolaterally has a pressue device that at least the oiliness China ink in this storage China ink pipe of packing into is pressurizeed at another.

25. spreading implement as claimed in claim 21, its feature are that also described metallic soap is a 2 ethyl hexanoic acid aluminium.

26. spreading implement as claimed in claim 22, its feature are that also described metallic soap is a 2 ethyl hexanoic acid aluminium.

27. the anti-reverse fluid of oiliness China ink, it is characterized in that, constitute at the polyacrylic gel combination more than 1000000 by containing the base material component more than at least a kind and the mean molecule quantity that are selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct

28. the anti-reverse fluid of oiliness China ink, it is characterized in that, constitute at the polyacrylic gel combination below 1500000 at polyacrylic acid more than 2000000 and mean molecule quantity by containing the base material component more than at least a kind, silica particle, the mean molecule quantity that are selected from diglycerol ethylene oxide adduct and diglycerol propylene oxide adduct, contain the described polyacrylic acid of 0.1～3 weight % with respect to the total amount of described anti-reverse fluid.

29. storage China ink pipe is characterized in that, has the interface that contacts with the oiliness China ink at least,