JP2002129091A - Water-based whiteout - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based whiteout excellent in masking characteristic, and even if it is kept for a long time, there is little separation of liquid, and also capable of using in good masking condition whenever using, and excellent in rewriting. SOLUTION: The water-based whiteout containing at least a titanium oxide, an aluminosilicate, a polypeptide whose average molecular weight is 3,000-6,000, an acrylic resin emulsion whose average particle size is below 0.1 μ, and water, and whose viscosity is 100-180 mPa.S is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous correction liquid, and more particularly, to an aqueous correction liquid which is excellent in concealment of a coated surface,
The present invention relates to a correction liquid that has little separation over time and is excellent in rewriting properties.

[0002]

2. Description of the Related Art Conventionally, a correction liquid has been used to conceal and correct handwriting of a writing instrument, a printing mark of a typewriter, a copy image by a dry copying machine, and the like. In this correction fluid,
There are an oil-based correction liquid using an organic solvent as a solvent and an aqueous correction liquid using water. In recent years, there has been a growing demand in the market for aqueous correction liquids due to the problem of odor of organic solvents and the like. The aqueous correction liquid is used for concealing and correcting handwriting of oil-based ink, printing marks of a typewriter or the like, a copy image by a dry copying machine, and the like, and a concealing material such as titanium oxide, water, and water-soluble. Organic solvent and water-soluble acrylic resin (ammonium salt, amine salt, sodium salt)
Or, those containing an acrylic resin emulsion are known.

[0003]

The concealing material is dispersed in fine particles in the correction fluid. Therefore, when stored for a long period of time, they tend to settle. In particular, titanium oxide is
Due to its high specific gravity, it sediments over time. Therefore, usually, a metal stirring ball or the like is filled in the container together with the correction liquid, and the concealing material that has settled by shaking the container is redispersed and used.

[0004] For time-dependent separation, surface treatment of titanium oxide, flocculation using a polymer flocculant or an inorganic salt electrolyte, clay minerals or water-soluble thickeners are used. Attempts have been made to suppress separation over time by using agents and the like.

However, particularly in the case of titanium oxide,
Even if the specific gravity is large and the method of reducing the separation over time is adopted, the effect is not enough, and the separation liquid is generated at the upper part of the liquid, so that the handwriting is corrected in a thin state, and it is difficult to conceal the handwriting. Occurs.

[0006] In addition, after the correction of characters and the like, the color of the rewritten handwriting becomes light, and it is not satisfactory at present. The present invention is excellent in concealing properties, and furthermore, even when stored for a long time, there is little separation of the liquid, any time of use, it can be used in a state of high concealing properties, and further, it provides an aqueous correction liquid excellent in rewriting properties. That is the task.

[0007]

According to the present invention, titanium oxide, aluminosilicate and an average molecular weight of 3,000 to 6,
000, and an acrylic resin emulsion having an average particle size of 0.1 μ or less, and at least water.
The gist is an aqueous correction fluid having a viscosity of 100 to 180 mPa · S.

Hereinafter, the present invention will be described. Titanium oxide imparts concealing properties, and various types of titanium oxide such as rutile type and anatase type can be used. Commercially available products include titon SR-1, R-650 and R-650.
-3L, R-310, A-110, A-150,
R-5N (all manufactured by Sakai Chemical Industry Co., Ltd.), TYPE R-550, R-580, R-930, A-10
0, A-220 (all manufactured by Ishihara Sangyo Co., Ltd.), Kronos KR-310, KR-380, KR-480, KA-10, KA-20, KA-30 (all, titanium Untreated titanium oxide such as manufactured by Kogyo Co., Ltd., Bayer R-FD-1, R-FD-2, R-FB-1, R
-FB-3, R-KB-3, R-CK-20 (manufactured by Bayer AG, Germany), Typek R-63
0, R-615, R-830 (all manufactured by Ishihara Sangyo Co., Ltd.), Typure R-900, and R-901 (all manufactured by Dupont Japan Limited) No. These titanium oxides can be used alone or as a mixture of two or more kinds, and the amount of the titanium oxide is preferably 20 to 50% by weight based on the total amount of the aqueous correction fluid.

The aluminosilicate imparts concealing properties. Rather, when used in combination with titanium oxide, the concealing properties can be improved as compared with the case of using titanium oxide alone. Used as a material. General silica powder has a small particle size, low concealing property, high oil absorption, high viscosity as an aqueous correction liquid, and has no effect as much as aluminosilicate. On the other hand, the aluminosilicate has a relatively high concealing property and a relatively small oil absorption. When used in combination with titanium oxide, the concealing property is improved. Specific examples of aluminosilicates include cypernate 820 and 8
20A (Degussa, Germany). The amount used can be 1 to 10% by weight, preferably 5 to 8% by weight, based on the total amount of the aqueous correction fluid.

Polypeptides are used as fixing agents and pigment dispersion stabilizers and have an average molecular weight of 3,0.
It is necessary to use those having a size of 00 to 6,000. This means that when the average molecular weight is less than 3,000,
Separation with time or the strength of the coating film is weakened, rewriting causes a problem that the coating film is broken, and when the average molecular weight exceeds 6,000, the viscosity of the aqueous correction liquid increases, This is because problems such as fraying and uneven coating occur. Polypeptides can be obtained by hydrolyzing gelatin, which is obtained by purifying and extracting cattle hide and bovine bone with an acid or an alkali, with an acid or an enzyme. The amount of the polypeptide to be used can be 2 to 10% by weight, preferably 3 to 8% by weight, based on the total amount of the aqueous correction fluid. Here, the average molecular weight will be described. Strictly speaking, a high molecular compound does not consist of a single molecule, but is a mixture of molecules having various molecular weights. It is. There are three methods for determining the number average molecular weight, the weight average molecular weight, the Z average molecular weight, and the viscosity average molecular weight. In the present invention, the number average molecular weight is used.

An acrylic resin emulsion has a fixing property,
It is used to improve the strength of the coating film, but is an important factor for improving rewriting. When a normal acrylic resin emulsion is mixed with an aqueous correction liquid, that is, an aqueous pigment dispersion, the strength of the coating film increases, but the viscosity of the liquid increases and the fluidity deteriorates. Instead, the re-writability deteriorates. Further, there is a problem that the viscosity of the liquid increases with time. Therefore, even if they are mixed, the fluidity of the liquid is maintained, and as a result of intensive investigation of a liquid that does not change with time, the average particle diameter is smaller than that of the conventional liquid (0.
(1 μm or less) An acrylic resin emulsion of fine particles could be found. As specific examples, Joncryl emulsion J-450 (average particle size 0.06 μ), J-74J
(Average particle size: 0.08 μm) and J-741 (average particle size: 0.
1μ), J-775 (average particle size 0.08μ), J-775
7001 (average particle size 0.08 μ) (manufactured by Johnson Polymer Co., Ltd.), Movinyl DM772 (average particle size 0.06)
μ), DM774 (average particle size 0.06 μ), Movinyl 727 (average particle size 0.06 μ) (Hoechst Gosei Co., Ltd.)
Manufactured). Here, the average particle size will be described. Strictly speaking, the particle size of the produced resin emulsion does not consist of a single particle size but a mixture of different particle sizes. Therefore, when indicating the particle size, it is indicated by the average particle size. The method of obtaining the arithmetic mean particle size measurement method, the weight average particle size measurement method, the average volume diameter measurement method, the mode diameter measurement method, the median diameter measurement method and the like, but in the present invention, the arithmetic average particle size measurement method Using. The used amount can be 5 to 15% by weight, preferably 7 to 10% by weight based on the total amount of the aqueous correction liquid.
It is.

Incidentally, in addition to the above-mentioned components, various additives conventionally used can also be used. For example, in order to match the color tone with a writing surface such as paper,
An extender such as silica powder, aluminum silicate or calcium carbonate may be used in combination to improve the hiding power.
Further, glycols, glycol ethers and polyhydric alcohols may be used in combination for freeze stability. Furthermore, dispersants and anti-settling agents for dispersion stability of the concealing material and pigment,
Thickeners for adjusting viscosity, plasticizers for adjusting hardness of coating films, and flow improvers and leveling agents for improving coating performance can also be appropriately added.

The correction liquid of the present invention can be obtained by dispersing and mixing the above components using a stirring and dispersing machine such as a Dyno mill, a ball mill, an attritor, and a sand grinder.

[0014] The correction fluid of the present invention has a viscosity of 100 to
It is necessary to be 180 mPa · S. 100mP
If less than a · S, the pigment tends to settle over time,
Temporal separation is likely to occur. Also, 180mPa · S
When the value exceeds the above, the spread when applying with a brush is deteriorated, the ink is blurred, and the leveling of the coated surface is deteriorated. Further, when the ink is filled in the pen-type raw ink structure, there is a problem that the liquid hardly comes out.

[0015]

It is not clear why the aqueous correction liquid of the present invention is excellent in the concealing property of the coated surface and the separation is small with time, but it is presumed as follows. Concealment is because the particles and particle diameter resulting from the composition of titanium oxide and aluminosilicate suppress the approach effect of titanium oxide and enhance concealment. Note that the approach effect is a phenomenon in which, as the amount of titanium oxide used is increased, the titanium oxides approach each other at a certain amount, the light scattering region is reduced, and the concealment property is reduced. As for the separation with time, the circumference of the titanium oxide and the aluminosilicate is covered with a polypeptide to suppress the approach of the respective powders and prevent the aggregation with time. or,
The aluminosilicate is interposed between titanium oxides having a large specific gravity, thereby reducing the apparent specific gravity of the titanium oxide. Furthermore, the protective colloid of the polypeptide stabilizes the dispersion of the pigment, and since the polypeptide has a structural viscosity, it has the property of immobilizing a weak structure when the whole liquid is left unattended. Of sedimentation. Regarding the rewriting property, due to the synergistic effect of the film properties of each of the polypeptide and the acrylic resin emulsion, that is, when the hardness of the film of the polypeptide and the flexibility of the film of the acrylic resin emulsion and the appropriate adhesiveness were written, the coating was rewritten. Is considered to have excellent rewriteability, without breaking, not slipping, and suppressing ink penetration.

[0016]

EXAMPLES Example 1 Tytone R-5N (rutile type titanium oxide, manufactured by Sakai Chemical Industry Co., Ltd.) 46.0 parts by weight Cypernate 820 (aluminosilicate, Degussa, Germany) 7.5 parts by weight Poly Peptide AFD (25% by weight aqueous solution, average molecular weight 3,500, manufactured by Nippi Co., Ltd.) 17.0 parts by weight Joncryl J-450 (acrylic resin emulsion, average particle size 0.06μ, manufactured by Johnson Polymer Co., Ltd.) 9.0 parts by weight DISCOAT N-14 (anionic surfactant, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.3 parts by weight Glycerin 2.0 parts by weight Proxel GXL (preservative, manufactured by Zeneca Corporation) 0.2 parts by weight Water 18.0 parts by weight Each of the above components was subjected to dispersion treatment in a ball mill for 24 hours to obtain a correction liquid.

Example 2 Bayer R-FD-1 (rutile type organically treated titanium oxide, manufactured by Bayer AG, Germany) 43.0 parts by weight Sipernate 820A (aluminosilicate, manufactured by Degussa, Germany) 7.0 weight percent Part Aerosil 200 (amorphous silica, manufactured by Nippon Aerosil Co., Ltd.) 1.0 part by weight Polypeptide AFD (25% by weight aqueous solution, average molecular weight 3,500, manufactured by Nippi Corporation) 13.0 parts by weight Movinyl DM772 ( Acrylic resin emulsion, average particle size 0.06μ, manufactured by Hoechst Gosei Co., Ltd. 8.0 parts by weight Poise 530 (anionic surfactant, manufactured by Kao Atlas Co., Ltd.) 0.2 parts by weight Proxel GXL (described above) 0.2 parts by weight water 27.6 parts by weight Each of the above components was made in the same manner as in Example 1 to obtain an aqueous correction liquid.

Example 3 Thai Pure R900 (rutile type titanium oxide, manufactured by Dupont Japan Limited) 45.0 parts by weight Sipernate 820 (aluminosilicate, manufactured by Degussa, Germany) 7.0 parts by weight Polypeptide PE50 ( 25 wt% aqueous solution, average molecular weight 5,500, manufactured by Nippi Corporation 14.0 parts by weight John Krill J-74J (acrylic resin emulsion, average particle size 0.08 μm, manufactured by Johnson Polymer Co., Ltd.) 7.0 weight Parts Discoat N-14 (anionic surfactant, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.3 parts by weight Propylene glycol 2.0 parts by weight Proxel GXL (described above) 0.2 parts by weight Water 24.5 parts by weight The above components were made in the same manner as in Example 1 to obtain an aqueous correction fluid.

Example 4 Bayer R-FD-1 (rutile-type organically treated titanium oxide, manufactured by Bayer AG, Germany) 44.0 parts by weight Sipernate 820A (aluminosilicate, manufactured by Degussa, Germany) 6.0 weight percent Part Polypeptide (25% by weight aqueous solution, average molecular weight 5,500, manufactured by Nippi Co., Ltd.) 15.0 parts by weight Joncryl J-741 (acrylic resin emulsion, average particle diameter 0.1 μm, manufactured by Jonson Polymer Co., Ltd.) 8.0 parts by weight Poise 530 (anionic surfactant, manufactured by Kao Atlas Co., Ltd.) 0.2 parts by weight Proxel GXL (described above) 0.2 parts by weight Water 26.6 parts by weight Similarly, an aqueous correction liquid was obtained.

Comparative Example 1 An aqueous correction liquid was obtained in the same manner as in Example 1 except that polypeptide AFD (25% by weight aqueous solution) was used instead of Joncryl J-450.

Comparative Example 2 The procedure of Example 1 was repeated, except that in place of Joncryl J-450, Movinyl 700 (acrylic resin emulsion, manufactured by Hoechst Synthetic Co., Ltd., average particle size: 0.3 μm) was used. Similarly, an aqueous correction liquid was obtained.

Comparative Example 3 In Example 1, the polypeptide AFD (25% by weight)
An aqueous correction liquid was obtained in the same manner as in Example 1 except that an ammonium salt of an acrylic resin (25% by weight aqueous solution) was used instead of the aqueous solution (average molecular weight 3,500).

Comparative Example 4 Toxir U in Example 2 was replaced with Cypernat 820A (aluminosilicate, Degussa, Germany)
An aqueous correction fluid was obtained in the same manner as in Example 2 except that (amorphous silica, manufactured by Tokuyama Soda Co., Ltd.) was used.

Comparative Example 5 Polypeptide PE20 (25% by weight aqueous solution) (average molecular weight 2,75) was used instead of polypeptide AFD (25% by weight aqueous solution, average molecular weight 3,500) in Example 1.
0, manufactured by Nippi Co., Ltd.), and an aqueous correction liquid was obtained in the same manner as in Example 1.

Comparative Example 6 In Example 3, the polypeptide PE50 (25% by weight)
Instead of aqueous solution, average molecular weight 5,500, polypeptide PA100 (25% by weight aqueous solution, average molecular weight 12,
Aqueous correction fluid was obtained in the same manner as in Example 3 except that 500 (manufactured by Nippi Corporation) was used.

Comparative Example 7 In Example 2, cypernate 820A was reduced by 2% by weight, and further, polypeptide AFD (25% by weight aqueous solution)
(Average molecular weight: 3,500) was reduced by 5% by weight and water was added by 7% by weight in the same manner as in Example 2 to obtain an aqueous correction liquid.

Comparative Example 8 In Example 4, 1.5% by weight of cypernate 820A was added.
The aqueous correction liquid was prepared in the same manner as in Example 4 except that the amount of water was increased by 1% by weight, and the amount of water was reduced by 2.5% by weight. Obtained

As described above, the aqueous correction solutions obtained in Examples 1 to 4 and Comparative Examples 1 to 8 were tested for concealing properties, separation with time, and rewriting properties. Table 1 shows the results.

Hiding test: The above-mentioned aqueous correction liquid was applied to a hiding test paper using a 50-micron applicator, and after drying, the Y value was measured with a color computer. Ask.

[0030]

(Equation 1)

Separation test over time: The above-mentioned correction liquid is placed in a screw vial, and the height of the liquid surface is measured from the bottom of the bottle. After leaving at room temperature for one month, the height of the separated solution was measured and
Calculate the separation rate over time based on the formula

[0032]

(Equation 2)

Rewriteability test: Strength of coating film: After drying on the surface coated in the concealment test, letters are written with an oil-based ballpoint pen and the state of occurrence of cracks on the coated surface is visually observed. Handwriting density: Write letters with a water-based pigment ballpoint pen, and visually observe the handwriting density immediately after writing and after drying.

Viscosity measuring method: Measured with a B-type viscometer (manufactured by Tokyo Keiki Seisakusho). The liquid temperature is 25 ° C.

[0035]

[Table 1]

[0036]

As described in detail above, the aqueous correction liquid of the present invention is an aqueous correction liquid that is excellent in concealing properties of the coated surface, has little separation over time, and is excellent in rewriting properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C09D 5/02 C09D 5/02 10/00 10/00 189/00 189/00

Claims (1)

[Claims] 1. A titanium oxide, an aluminosilicate, and a polypeptide having an average molecular weight of 3,000 to 6,000,
An acrylic resin emulsion having an average particle size of 0.1 μ or less and at least water, and having a viscosity of 100 to 180 mP
An aqueous correction fluid that is a · S.