JP2000044850A - Correction liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a correction liquid having excellent hiding property and overwriting property with rapid drying and formable a smooth coated film surface by at least including a specific titanium dioxide, a bonding material and a solvent. SOLUTION: This correction liquid contains at least (A) titanium dioxide in which the surface is treated with a coupling agent (e.g. a silane coupling agent such as γ-aminopropyltriethoxysilane, etc.), (B) a bonding material such as a styrene-acrylic emulsion and (C) a solvent such as water. A using amount of each component is preferably 20-50 wt.% of the component A, 5-20 wt.% of the component B and 30-60 wt.% of the component C. The component A is obtained by, e.g. dropping or spraying the coupling agent directly or dissolved in a small amount of water, etc., to a being stirred titanium dioxide and drying.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a correction fluid.

[0002]

2. Description of the Related Art A correction fluid is used to cover and conceal erroneous characters written on paper, film or the like so that erroneous characters or the like are not visible. In addition, typographical errors are corrected by writing on the coated film.

[0003] Conventionally, correction fluids have a concealing material, a binder, and a solvent as main components. The concealing material is for concealing typographical errors and the like, and a high concealing pigment having a high refractive index of 2.0 or more is used as a main concealing material. The binder is used to fix the concealing material on paper or film to form a coating film,
Various resins and elastomers are used. The solvent is used for dispersing the concealing material, dissolving or dispersing the binder, and adjusting the viscosity of the correction liquid, and water and / or an organic solvent is used.

In the case of a correction liquid for correcting handwriting of water-based ink such as a fountain pen and a water-based felt pen, an organic solvent such as toluene, xylene, 1,1,1-trichloroethane, and trichloroethylene is used as a main solvent. Handwriting with oil-based ink such as oil-based ballpoint pens and oil-based markers,
In the case of a correction liquid for correcting printing by a typewriter, a copy image by a dry copying machine, etc., water is used as a main solvent. Further, in recent years, naphthenic solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, and cyclopentane, and normal hexane, isohexane, and normal heptane have been used to eliminate the complexity of using different correction solvents having different main solvents depending on the type of handwriting to be corrected. A correction liquid containing a paraffinic solvent as a main solvent is used.

[0005]

The correction liquid is applied to the paper or film surface with a brush, a resin member, a metal member, or the like so as to be spread on the surface of the coating film.
Since the drying is quick, the coating film is dried while the surface is uneven. The correction fluid not only conceals typographical errors, but also often writes on the coating film at the concealed location.Therefore, if the coating surface is uneven, it will not be possible to write cleanly when writing on the coating film. Occurs. Since writing is performed after the coating film is dried, the earlier the coating film is dried, the better the correction liquid, and it was difficult to obtain a smooth coating film surface with the quick drying correction liquid. An object of the present invention is to provide a correction liquid that can be dried quickly and can obtain a smooth coating film surface.

[0006]

According to the present invention, there is provided a correction solution containing at least titanium dioxide, a binder and a solvent, wherein the titanium dioxide has a surface treated with a coupling agent. The gist is a correction fluid.

The details will be described below. Titanium dioxide is
Various titanium dioxides such as rutile type and anatase type can be used. Commercially available products include Tytone SR-1,
R-650, R-3L, A-110, A-15
0, R-5N (all manufactured by Sakai Chemical Industry Co., Ltd.), TYPAKE R-580, R-550, R-930, A-
100, A-220, CR-58 (all manufactured by Ishihara Sangyo Co., Ltd.), Kronos KR-310, KR-380,
KR-480, KA-10, KA-20, KA
-30 (manufactured by Titanium Industry Co., Ltd.), Thai Pure R-
900, R-931, (Dupon Japan
Ltd.), TITANIX JR-300, JR-800, JR-602 (above, Teika Corporation)
Manufactured). The amount used is 2 with respect to the total amount of correction fluid.
0 to 50% by weight is preferred. It is necessary to use titanium dioxide whose surface has been treated with a coupling agent as the titanium dioxide used in the correction fluid of the present invention. This is because a smooth coating surface is obtained by using titanium dioxide whose surface is treated with a coupling agent.

The coupling agent includes a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.

The silane coupling agent chemically bonds to a functional group (an amino group, a mercapto group, an epoxy group, a vinyl group, a methacryl group, a chloro group, etc.) or an affinity part which chemically bonds to an organic substance in the molecule and an inorganic substance. Organic silicon having a functional group (methoxy group, ethoxy group, cellosolve group, etc.). Specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminomethyl) aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-anilinopropyl Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl ) Ethyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxytriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltri Methoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ
-Ureidopropyltriethoxysilane, alkyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltrisec-octyloxysilane, methyltriphenoxysilane, Phenyltrimethoxysilane,
Examples include phenyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane. Commercially available products include Toray Silicone SH6020, SZ6023, and SH602
6, SZ6030, SZ6032, SH604
0, SZ6050, SH6062, SZ607
0, SZ6072, SH6075, SH607
6, SZ6079, SZ6083, SZ6300
(The above are manufactured by Toray Silicone Co., Ltd.), Shin-Etsu Silicone KA1003, KBC1003, and KBE100
3, the same KBM1003, the same KBM503, the same KBM30
3, same KBM403, same KBE402, same KBE40
3, the same KBM502, the same KBE502, the same KBE50
3, same KBE603, same KBE903, same KBM40
2, same KBM603, same KBM602, same KBM90
3, the same KBM573, the same KBM803, the same KBM703
(Shin-Etsu Chemical Co., Ltd.), NUC Silicone A
-143, A-150, A-151, A-17
2, A-174, A-186, A-187, A
-189, A-1100, A-1120, A-1
160 (manufactured by Nippon Unicar Co., Ltd.), Sila Ace S210, S220, S230, S310, S
311, S320, S321, S330, S5
10, S520, S530, S610, S62
0, the same S710, the same S810 (Chisso Corporation)
Manufactured), RT-168E, MTS-31, MTS-32,
MTS-33, MTS-34, MTS-38 (S), M
TS-3PH, PTS-31, and PTS-32 (all manufactured by Daihachi Chemical Co., Ltd.).

The titanate-based coupling agent is an organic titanium having, in its molecule, a functional group which chemically bonds to an inorganic substance and a portion which is compatible with an organic substance. Specifically, isopropyl triisostyaroyl titanate, isopropyl trinormal stearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphite) titanate Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, Isopropyl dimethacryloyl isostearyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl iso Thearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl diisostearoyl cumyl phenyl titanate, isopropyl distearoyl methacryl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl diisostearoyl acrylic titanate, isopropyl iso Stearoyl diacryl titanate, isopropyl 4-aminobenzenesulfonyl di (dodecylbenzenesulfonyl) titanate, isopropyl trimethacryl titanate, isopropyl triacryl titanate, isopropyl tri (N, N-dimethyl-ethylamino) titanate, isopropyl tri (N-ethylamino) -Ethylamino) titanate Isopropyl di (4-aminobenzoyl) isostearoyl titanate, isopropyl trianthranil titanate, isopropyl octyl, butyl pyrophosphate titanate, isopropyl di (butyl, methyl pyrophosphate) titanate, tetraisopropyl di (dilauryl phosphite) titanate,
Tetraisopropyl di (dioctyl phosphite) titanate, tetraoctyl di (ditridecyl phosphite) titanate, tris (dioctyl pyrophosphate) ethylene titanate, diisostearoyl oxyacetate titanate, isostearyl methacryloxy acetate titanate, isostearyl acryloxy acetate titanate , Di (dioctyl phosphate) oxyacetate titanate, 4-aminobenzenesulfonyldodecylbenzenesulfonyloxytitanate, dimethacryloxyacetate titanate, diacryloxyacetate titanate, dicumylphenolate oxyacetate titanate, 4-aminobenzoylisostearoyloxyacetate Titanate, di (octyl, Tyl pyrophosphate) oxyacetate titanate, diisostearoylethylene titanate, isostearylmethacrylethylene titanate, di (dioctylphosphate) ethylene titanate, 4-aminobenzenesulfonyldodecylbenzenesulfonylethylene titanate, dimethacrylethylene titanate, 4-aminobenzoylisostearoyl Ethylene titanate, di (dioctyl pyrophosphate)
Ethylene titanate Diacrylethylene titanate, dianthranyl ethylene titanate, di (butyl methyl pyrophosphate) ethylene titanate, and the like. Commercially available KR-TTS, KR-TTS
-B, KR-5, KR-6, KR-7, KR-9S, K
R-10, KR-11, KR-12, KR-15, KR
-26S, KR-33CS, KR-34S, KR-37
BS, KR-38S, KR-39CS, KR-43, K
R-44, KR-52, KR-58CS, KR-62
S, KR-36B, KR-41B, KR-46, KR-
55, KR-101, KR-106, KR-110S,
KR-112S, KR-126S, KR-133CS,
KR-134S, KR-137BS, KR-138S,
KR-139CS, KR-158DS, KR-201,
KR-206, KR-212, KR-226, KR-2
33, KR-237, KR-238S, KR-239,
KR-252, KR-262S (above, US KENR
ICH PETROCHEMICALS, INC.
Manufactured), Prenact KR TTS, KR 38S, KR 46B, KR 55, KR 138S, K
R238S, KR9S, KR41B (all manufactured by Ajinomoto Co., Inc.), Titacoat S-151, S-15
2, S-152P, S-153, S-181, S
-581, S-582, P-151P, R-16
1, R-291, C-151, and C-231 (all manufactured by Nippon Soda Co., Ltd.).

The aluminum-based coupling agent is an organoaluminum having a functional group chemically bonding to an inorganic substance in a molecule thereof and a portion having an affinity for an organic substance. In particular,
There is acetoalkoxyaluminum diisopropylate, and commercially available products are Plenact AL-M (Ajinomoto Co., Inc.)
Made).

In order to treat titanium dioxide with a coupling agent, it is necessary to chemically bond the titanium dioxide and the coupling agent. In the silane coupling agent, a functional group (methoxy group, ethoxy group,
Cellosolve group) hydrolyzes to form a silanol portion, and the silanol portion and the hydroxyl group on the surface of titanium dioxide are chemically bonded by a dehydration reaction. The mechanism by which the titanate-based coupling agent and the aluminum-based coupling agent chemically bond to titanium dioxide is not clear as in the case of the silane coupling agent, but seems to be chemically bonded by a dealcoholization reaction. For this reason, complete surface treatment is performed by drying in the treatment process. The method of treating titanium dioxide with a coupling agent includes a dry method and a wet method. In the dry method, a solution in which the coupling agent is dissolved directly or in a small amount of water and / or an appropriate organic solvent is dropped or sprayed on the stirred titanium dioxide, and then dried. The dry method is easy to dry because a small amount of water and / or organic solvent dissolves the coupling agent.
Less aggregation of titanium dioxide due to drying. As a wet method, the coupling agent is dissolved in a large amount of water or an appropriate organic solvent, and after stirring and mixing with titanium dioxide,
The water or organic solvent is distilled off or filtered, pressed and dried as appropriate. With the wet method, it takes time to dry,
Since agglomeration due to drying is likely to occur, it is necessary to dry while preventing agglomeration or re-grind after drying. For this reason,
The wet method requires more time than the dry method, but after treating with a large amount of the coupling agent, the excess coupling agent can be removed by distillation, filtration, or pressing, so that there is an advantage that sufficient surface treatment can be easily performed.

[0013] The titanium dioxide may be used after its entirety has been treated with a coupling agent, but may be used in combination with untreated titanium dioxide for cost reduction and the like. One or two or more coupling agents can be used in combination. When two or more types of coupling agents are used in combination, a method of simultaneously treating with two or more types of coupling agents or a method of sequentially performing treatment with one type of coupling agent can be considered. The method of using titanium dioxide treated with a ring agent together facilitates treatment management.

As the binder, those which can be dissolved or dispersed in a solvent can be used. When water is used as the main solvent, a (meth) acrylate resin emulsion, a styrene-butadiene copolymer resin emulsion, an ethylene vinyl acetate resin emulsion, or the like can be used.
When using an organic solvent as the main solvent, acrylic resin,
An alkyd resin, a vinyl resin, a polyester resin, a vinyl alkyl ether resin, a cyclized rubber, a styrene-butadiene-based elastomer, or the like can be used. The amount used is preferably 5 to 20% by weight based on the total amount of the correction fluid.

As the solvent, water and / or an organic solvent can be used. When water is used as the main solvent, a water-soluble volatile solvent can be mixed and used. Examples of the water-soluble volatile solvent include lower alcohols such as methyl alcohol, ethyl alcohol, normal propyl alcohol, and isopropyl alcohol. One or more water-soluble volatile solvents can be used in combination with water. Examples of the organic solvent include paraffinic solvents such as normal hexane, isohexane, normal heptane, and normal octane; naphthenic solvents such as cyclohexane, methylcyclohexane, cyclopentane, and methylcyclopentane; 1,1,1-trichloroethane; One or a mixture of two or more chlorine-based solvents such as 1-trichloroethylene can be used. The amount of the solvent used is preferably 30 to 60% by weight based on the total amount of the correction liquid.

In addition, in addition to the above-mentioned components, the correction fluid according to the present invention may contain a colorant such as carbon black, an organic pigment, or an inorganic pigment for adjusting the color tone with paper or the like, if necessary, silica, calcium carbonate, or the like. Extender, dispersant,
It is a matter of course that a conventionally known additive for a correction liquid such as a stabilizer, a viscosity modifier and a polymer flocculant can be used.

[0017]

Although it is not clear why the coating film surface becomes smooth when titanium dioxide surface-treated with a coupling agent is contained in the present invention, it is presumed that the reason is as follows.

In order for the coating surface of the applied correction liquid to be smooth from an uneven state, the correction liquid in the convex portion must flow into the concave portion by gravity. However, since the correction liquid has a higher content of the concealing material than the paint or the like, and particularly has a high content of titanium dioxide, the correction liquid does not easily flow by gravity and the coating film surface is hard to be smooth. Further, in the case of a paint, a sufficient time is required for drying, so that it is easy to obtain a smooth coating film surface even if it is difficult to flow, but the correction liquid dries quickly because the coating film surface is uneven due to rapid drying. Also, the surface of titanium dioxide is rather hydrophilic, but does not have very high affinity for water. For this reason, not only in the case of a correction liquid containing an organic solvent as a main solvent, but also in a correction liquid containing water as a main solvent, titanium dioxide flows under a slight stress due to gravity on a coating film surface because the titanium dioxide is not easily wetted by the solvent. Hard to do. However, when titanium dioxide is treated with a coupling agent, the outermost surface of the titanium dioxide is composed of a portion that chemically bonds or has an affinity with an organic substance of the coupling agent. The part of the coupling agent that is chemically bonded to or compatible with the organic substance is lipophilic or hydrophilic, so if the coupling agent is selected according to the main solvent used, the wetting of the titanium dioxide in the solvent is better than that of the untreated one. Become. In addition, since the coupling agent is chemically bonded to the titanium dioxide, the surface of the titanium dioxide is surely and sufficiently modified, even under a slight stress due to gravity, as compared with a dispersant added to a conventionally known correction liquid. The fluidity is improved.

[0019]

Example 1 <Silane Coupling Treatment of Titanium Dioxide> Kronos KR-380 (titanium dioxide, manufactured by Titanium Industry Co., Ltd.) 100 parts by weight γ-aminopropyltriethoxysilane 1 part by weight Water 10 parts by weight In water The silane coupling agent was added and dissolved with stirring. The water in which the silane coupling agent was dissolved was sprayed on the stirred titanium dioxide, and then dried while stirring to obtain a titanium dioxide treated with the coupling agent. <Manufacture of Correction Solution> 30 parts by weight of the above-mentioned coupling agent-treated titanium dioxide Joncryl J450 (styrene-acrylic emulsion having a nonvolatile content of 43% by weight, manufactured by Johnson Polymer Co., Ltd.) 16 parts by weight Water 43 parts by weight Nikkor BC- 40 TX (polyoxyethylene (40) cetyl ether, manufactured by Nikko Chemicals Co., Ltd.) 1 part by weight The above composition is dispersed in a ball mill for 24 hours. To this dispersion was added 10 parts by weight of an aqueous solution containing 6% by weight of Kelzan AR (Xanthan gum, manufactured by Sansei Corporation), and the mixture was stirred and dissolved to obtain a correction liquid.

Example 2 <Silane Coupling Treatment of Titanium Dioxide> TIRANIX JR-300 (titanium dioxide, manufactured by Teica Co., Ltd.) 100 parts by weight N-phenyl-γ-aminopropyltrimethoxysilane 2 parts by weight The pH was adjusted with acetic acid. 300 parts by weight of water adjusted to 4 A silane coupling agent was added to the pH adjusted acetic acid water and dissolved with stirring. The titanium dioxide was added little by little to the stirred acetic acid aqueous solution in which the silane coupling agent was dissolved, and after the entire amount was added, stirring was continued for 1 hour. After completion of the stirring, the above mixture was subjected to suction filtration to filter titanium dioxide, and dried while stirring to obtain titanium dioxide treated with a coupling agent. <Manufacture of correction liquid> 45 parts by weight of titanium dioxide treated with the coupling agent Paraloid B66 (methyl methacryloid-butyl methacryloid copolymer, manufactured by Rohm and Haas Japan KK) 8 parts by weight Methyl cyclohexane 48 parts by weight Part homogenol L-18 (special polycarboxylic acid type polymer surfactant, manufactured by Kao Corporation) 1 part by weight Mitsubishi carbon black MA100 (carbon black, manufactured by Mitsubishi Chemical Corporation) 0.05 part by weight The dispersion was dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 3 <Titanium dioxide-based coupling agent treatment of titanium dioxide> TITANIX JR-602 (titanium dioxide, manufactured by Teica Corporation) 100 parts by weight Bis (dioctyl pyrophosphate) oxyacetate titanate 3 parts by weight Normal hexane 250 parts by weight Part The above titanate coupling agent is added to normal hexane and dissolved by stirring. The titanium dioxide was added little by little to normal hexane in which the above-mentioned coupling agent was dissolved, and after the whole amount was added, stirring was continued for 1 hour. After completion of the stirring, the mixture was filtered to remove titanium dioxide, and dried while stirring to obtain titanium dioxide treated with a coupling agent. <Manufacture of Correction Solution> 40 parts by weight of the above-mentioned coupling-treated titanium dioxide Joncryl J450 (described above) 16 parts by weight Water 33 parts by weight Nikkor TL-10 (polyoxyethylene (20) sorbitan monolaurate, manufactured by Nikko Chemicals Co., Ltd.) 1 part by weight EM BLUE 2G (blue water-dispersed pigment, manufactured by Toyo Ink Co., Ltd.) 3 parts by weight The above composition was dispersed in a ball mill for 24 hours to obtain a correction liquid.

Example 4 <Treatment of Titanium Dioxide with Titanate Coupling Agent> Chronos KR380 100 parts by weight Isopropyl tris (dioctylpyrophosphate) titanate 2 parts by weight Normal hexane 20 parts by weight The above titanate coupling agent was added to the above normal hexane. To dissolve while stirring. The normal hexane in which the titanate-based coupling agent was dissolved was sprayed onto the above-mentioned stirred titanium dioxide, and then dried while stirring to obtain a titanium dioxide treated with the coupling agent. <Manufacture of Correction Liquid> The above-mentioned coupling-treated titanium dioxide 45 parts by weight Paralyroid B66 8 parts by weight Methylcyclohexane 46 parts by weight Homogenol L-18 1 part by weight The above-mentioned composition was dispersed in a ball mill for 24 hours to obtain a correction liquid.

Comparative Example 1 A correction fluid was obtained in the same mixing ratio and method as in Example 1 except that untreated titanium dioxide (Kronos KR-380) was used.

Comparative Example 2 Untreated titanium dioxide (TITANIX JR-30)
A correction fluid was obtained in the same mixing ratio and method as in Example 2 except that 0) was used.

Comparative Example 3 Untreated titanium dioxide (TITANIX JR-60)
A correction fluid was obtained in the same mixing ratio and method as in Example 3 except that 2) was used.

Comparative Example 4 A correction fluid was obtained in the same mixing ratio and method as in Example 4 except that untreated titanium dioxide (Kronos KR380) was used.

The correction liquids obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were filled in a container of Pentel's correction liquid XZL7F1C (manufactured by Pentel Co., Ltd.) and applied on the following object to be coated. The surface smoothness was visually evaluated. The object to be applied is a hybrid K1 with a 5 mm square on high-quality paper
05-GA (Black ink ballpoint pen, Pentel Co., Ltd.)
) Was used. Evaluation criteria are 1 to
It was grade 3. Grade 1 is a streak-like depression with a deep trace of the surface of the coating film rubbed at the application portion of the container tip. Grade 2 shows a shallow streak-like depression rubbed on the coating surface of the coating at the coating portion of the container tip.
In grade 3, the surface of the coating film is smooth and no streak-like dents are observed.

Further, writing was performed on the dried coating film using Pentel Hybrid K105-GA, and the written character was visually evaluated. The evaluation criteria were grades 1-3. 1
A class cannot write legible characters. In the second grade, the written characters are legible, but many of the written characters lack writing lines or become zigzag, and the characters are dirty compared to writing on paper. Class 3 is capable of writing characters with the same cleanliness as writing on paper. Table 1 shows the results.

[0029]

[Table 1]

[0030]

As described in detail above, the correction liquid of the present invention can provide a smooth coating film surface.
It has the characteristics of being excellent in concealing properties and rewriting properties, and has the same drying properties as conventional correction liquids.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4J038 CC041 CD021 CE051 CF031 CG031 CG141 DD001 DD121 HA216 KA06 MA07 MA08 MA09 MA10 PB12 PC08 PC10

Claims (1)

[Claims] 1. A correction liquid containing at least titanium dioxide, a binder, and a solvent, wherein the titanium dioxide has a surface treated with a coupling agent.