JPS6028679B2 - writing instrument nib - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to writing odor pen nibs made of a composite of fibers and resin, ranging from fine print nibs equivalent to ballpoint pens to large font pen nibs similar to calligraphy brushes. It concerns the structure and its manufacturing method.

There is a feltben nib as a pen nib of this kind, '1
'Felt ben made mainly of wool felt treated with thermosetting synthetic resin {2) Thermosetting synthetic resin on the parallel fibers,
Felt Ben for brushes impregnated with a mixture of thermoplastic synthetic resin, rubber, plasticizer, and foaming agent and then foamed with foaming agent (Special Publication No. 38-10664) {3} Thermosetting parallel fibers Felt bene is made by impregnating a mixture of synthetic resin, thermoplastic synthetic resin, and fiber with a solvent and hardening the fiber by applying dry heat treatment while applying tension (Jikosho 40-28058
No.). However, the wool felt bene in '1) has a reduced porosity due to resin processing, and the fiber density is uneven, making it unsuitable for use as a nib for fine writing (the brush pen in '2' is too elastic. It is not sufficiently hard enough to make a fine nib, and even when used for calligraphy, it is difficult to write characters that look like they were written with a calligraphy brush.Feltben {3} is too hard and does not slide well with the paper surface, causing squeaks when writing. Moreover, the common disadvantage of these felt pens is that the tip of the pen tip may crack due to poor adhesion of the fibers, or the abrasion resistance of the fiber material used may deteriorate. The tip of the pen becomes thicker as usage time progresses.
It has the disadvantage that the conical shape of the tip has become blunt, making it impossible to write the original fine print.

In contrast, the present invention is made of a composite structure of fibers and a polymer elastomer having continuous pores, and its purpose is to have continuous and uniform ink passages, and to change the hardness and elasticity of the pen tip. The object of the present invention is to provide a pen nib for small to large characters, which has a wide range, excellent morphological stability, mechanical strength such as a low coefficient of friction with the paper surface, and is easy to use and practical. Specifically, the present invention is a porous composite in which the voids of a nonwoven fabric in which fibrous materials are three-dimensionally entangled are filled with a polymer elastomer having countless fine continuous pores, the surface layer of which is a thermosetting synthetic resin. , a thermoplastic synthetic resin or a polymeric elastomer, and then dried using a nonionic or anionic surfactant. The present invention improves mechanical strength such as abrasion resistance and adhesion by forming a composite in which the intertwined voids of fibrous materials are filled with a polymer elastomer, thereby preventing pen tip cracking and conical shape. The polymer elastomer, which has countless fine continuous pores, acts as a passage hole for ink using capillary tubes, and by adding a surfactant to the inner wall of the pores, it improves ink affinity and prevents ink smearing. Furthermore, the porosity of the layer within the porous composite can be reduced by impregnating the surface layer of the porous composite with a single solution or a mixed solution of a solvent for thermosetting synthetic resin, thermoplastic synthetic resin, or polymer elastomer and heat-treating it. It was completed by imparting hardness (hardening treatment) without changing the pen nibs, and by changing the hardening after heat treatment depending on the impregnated coating density, it was possible to obtain a pen nib with hardening and elasticity for fine to large characters. It is something.

In the present invention, the fibrous material and the entangled nonwoven fabric include paper yarns or composite woven fabrics made of single spun fibers such as known Rayon, Bemberg, acetate, nylon, polyester, acrylic, polypropylene, etc., and a mixture of two or more types of polymeric substances. Fibrous materials include fibers made of yarn, such as mixed woven fibers of nylon, polyester, etc. and polyethylene, polystyrene, polypropylene, etc., and composite yarn fibers, which can be used singly or in combination of two or more types. conduct,
An entangled nonwoven fabric is obtained by forming a three-dimensionally entangled nonwoven fabric from an ordinary carded web through needle punching. The fibrous material used to provide appropriate flexibility as a pen tip, prevent ink from smearing, absorb ink, and provide a smooth writing feel is paper yarn or array paper mixed with two or more types of polymeric substances. Using fibers made from yarn,
Hollow or ultra-fine fibers that have voids inside the fibers by splitting the fibers at any stage through mechanical operations such as curling, or by dissolving one fiber component with a solvent. It is better to Next, filling with a polymer elastomer having countless fine continuous pores means impregnating the voids of the nonwoven fabric with a polymer composition mainly composed of a polymer elastomer having rubber-like elasticity, such as a polyurethane elastomer. It is obtained by wet coagulation, washing with water and drying, and is called a porous composite due to the combination of fibers and porous polymer elastomer.

Polymer elastomers with rubber-like elasticity include known polyurethane rubbers, synthetic rubbers such as acrylonitrile-butadiene rubber, styrene-butadiene rubber, and chloroprene;
A polyacrylic acid-based elastomer alone or a composition containing one of these as a main component, which is impregnated into an entangled nonwoven fabric in the form of a solution or an aqueous dispersion dissolved in an organic solvent. The method is not particularly limited. In addition, the countless fine continuous pores formed in a polymer composition mainly composed of high-molecular elastomer are caused by soaking a polymer solution in a coagulating solution consisting of a poor solvent, extracting the polymer solvent, and forming a polymer. The cross-sectional area of the pores is preferably 10 to 100 F2, especially 30 F2 or less for use as a pen nib, and the pore density is also the same as that of an elastomer that evenly fills the voids of the nonwoven fabric. It is most desirable that the particles be distributed evenly and in as many numbers as possible.

Further, the pore cross-sectional area can be easily adjusted by appropriately selecting coagulation conditions or by using a known coagulation regulator. Before impregnating the entangled nonwoven fabric with a polymer composition mainly composed of polymeric elastomer, an aqueous solution of a water-soluble polymer such as PVA or CMC is impregnated and dried to coat the fiber surface of the entangled nonwoven fabric with the water-soluble polymer. The porous composite obtained by forming a coating on the elastomer, then impregnating it with a high-molecular elastomer polymer and extracting the water-dropping polymer is flexible because the fibers and the high-molecular elastomer are not in close contact with each other, and has an extremely low Young's modulus. In both cases, the brush nib of the present invention has a low resistance to bending stress, and the fibers and the elastic body behave separately against stress and deform by causing a "slip" between them. This is a major factor in obtaining the same writing taste as .

Polymer elastomer impregnated into the voids of the entangled nonwoven fabric
The weight ratio of the fibrous material is preferably 10 to 60% and the polymer elastomer is 40 to 90%, especially the fibrous material is 20 to 60%.
40%, preferably 60-80% of polymer elastomer,
The apparent specific gravity of these porous composites is often in the range of 0.1 to 0.7, preferably 0.2 to 0.4, and if the apparent specific gravity is less than 0.1, the rigidity will be insufficient and the If it is more than 0.7, the porosity becomes small and the ink content of the nib becomes small (the ink absorption rate decreases and so-called "smearing" occurs during writing, which is undesirable). The thickness of the porous composite is between 1.0 and 6.0, especially 2.0
~4. Depending on the purpose of the pen nib, this thickness can be made thinner by dividing the porous composite by slicing, or conversely, it can be made thicker by laminating and applying adhesive. By doing so, a desired thickness can be obtained.

The adhesive used for lamination bonding is preferably a homogeneous polymer elastomer adhesive filled in a porous composite.
The adhesion method is performed by a method that does not obstruct the ink passage hole, for example, a point adhesion method.

The porous composite thus obtained is subjected to the following curing treatment on its surface layer (which means the surface layer when the composite is distinguished from the surface layer and the inner layer, and includes the front and back surfaces of the composite). I will receive it. That is, the curing treatment of the present invention involves impregnating and coating the surface layer of a porous composite with a solution or emulsion of a thermosetting resin or thermoplastic resin, and drying and heat-treating it.
Alternatively, the surface layer of the polymer elastomer filled in the porous composite is impregnated with a solvent and then subjected to dry heat treatment to impart only hardness without substantially changing the porosity of the inner layer of the porous composite. That's true. The thermosetting synthetic resin used in the curing process of the present invention is an initial condensation product of known melamine-based, urea-based, phenol-based, epoxy-based synthetic resins, or other thermosetting synthetic resins. The resin is used to impart hardness and elasticity, and includes acrylic, vinyl acetate, vinyl chloride synthetic resins, and other thermoplastic synthetic resins.
For all of these, it is desirable to use a resin that is inactive as an ink solvent after being cured through a drying and heat treatment process. Furthermore, there are solvents for polymer elastomers as curing agents.
These polymer elastomers are used to dissolve the polymer porosity present in the surface layer of the porous composite and form a film, making it easier to fill with the synthetic resin liquid and increasing the hardness of the surface layer. Those that have swelling and dissolving power are used.

For example, when polyurethane is used as the polymer elastomer, dimethylformamide, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, acetone, toluene, inpropyl alcohol, methanol, etc. are used. The curing treatment in the present invention uses the above-mentioned thermosetting synthetic resin, thermoplastic synthetic resin, and polymer elastomer solvents alone or in combination.In the case of single treatment, they are dissolved in an aqueous solution or Among the dispersed solutions of thermosetting synthetic resin, thermoplastic synthetic resin, and polymeric elastomer solvent, any one solution is treated as a single solution, and different single solutions can be repeatedly treated in layers.

In the case of a mixed solution, it is prepared by dissolving or decomposing a thermosetting synthetic resin and/or thermoplastic synthetic resin in water or a polymer elastomer solvent solution. A catalyst may be added to the solution of these thermosetting synthetic resins and thermoplastic synthetic resins to promote the reaction of the resin and the bond between the resin and the porous composite. Amamine hydrochloride etc. are used.

In order to impregnate and coat the surface layer of the above-mentioned porous composite with the single solution or mixed solution prepared in this way, the composite is immersed in the above-mentioned solution by a method such as dipping, spraying, or brushing to achieve a certain degree of adhesion. 80 to 10,000 after dehydrating
After drying with hot air or infrared rays, 150q
Cure of the thermosetting resin is completed by performing high-temperature heat treatment at a temperature of 0 to 23,000 °C.

The method of impregnating and coating with the above solution involves first impregnating with a low-concentration solution as an undercoat, and after drying, further impregnating and coating with a high-concentration solution as an overcoat to create a density gradient in the amount of resin deposited on the surface layer of the porous composite. Methods can also be added.

The form of the object to be treated is impregnated with the above solution and is in the form of a continuous sheet of the porous composite as described above, or in the form of a string having a rectangular or round cross section obtained by cutting or cutting the composite sheet to a certain size. Alternatively, it is also possible to impregnate, coat, and heat-treat a continuous sheet of the composite, and then cut it to a certain size and reprocess it into a string with a round cross section. There are no restrictions on the form of the post-processed product or the number of times of processing, as long as the pen tip processing and hardening processing can be performed more easily and rationally.

Next, the dried and heat-treated porous composite increases the ability to absorb ink liquid against the inner wall of the continuous pores of the polymer elastomer existing in the inner layer of the composite, so as to prevent so-called ink smudges from occurring during writing. A surfactant treatment is performed to impart ink affinity.

Examples of the surfactant include nonionic surfactants of the polyoxyethylene fatty acid ester type, polyoxyethylene alkyl ether type, polyoxyalkyl amine type, and polyoxyalkylphenol ether type, as well as dialkyl sulfosuccinic acid type, An alkyl phosphate type anionic surfactant is used, and the adhesion amount is preferably 0.01 to 1.5% (purity equivalent) to the porous composite, and as the adhesion amount increases, the ink affinity decreases. However, the practical adhesion amount is preferably 0.2 to 0.8%.

These treatments include immersion in the above-mentioned surfactant solution heated from room temperature to around 70°C for a certain period of time, passing through a squeezing roll in the liquid, and using a vacuum impregnation device. It is obtained by impregnating the inner layer with liquid, dehydrating it, drying it, and heat treating it.In addition to treating the porous composite after heat treatment and hardening in the form of a continuous sheet, the composite is cut into a certain size and made into a pen shape. The treatment may also be performed before the cured resin is impregnated into the porous composite.

The writing odor pen nib obtained in this way has a structure in which the surface layer of a composite of a fibrous material and a polymer elastomer having continuous pores is filled and coated with a cured resin, so it can be used without disturbing the continuous pores in the inner layer. It has the characteristic that hardness and elasticity can be imparted without changing the porosity, and it is possible to obtain a hard, thin writing style similar to that of a ballpoint pen, or a soft, thick writing style similar to a brush. . In addition, the fibers and polymer elastomer at the tip of the pen are exposed, which makes it easy to scribbling on paper.This low frictional resistance with paper means that the pen is highly resistant to scratches. In addition to being made of a composite material, this means that there is very little wear or deformation of the tip of the pen, and the thickness of the tip does not change even after long-term use. When used as a brush pen for large or large characters, the fiber suture and the polymer elastomer exhibit separate behavior and deformation in response to the folds, compression, and elongation that are applied to the pen tip during writing, and this action It exhibits excellent features such as a writing style that is extremely similar to a brush, and the ability to make the appearance of the font similar.

An example of implementing the present invention will be given below. Example 1 Random wafer needle punched nonwoven fabric made of nylon 6/polystyrene and 55/45 mixed paper yarn with 54 ribs. Impregnating and filling the voids with 20% urethane DMF (dimethylformamide) solution. After coagulating in a 30% DMF aqueous solution, it was washed with water, and further immersed in a hot toluene solution of 80 qo to dissolve and remove the polystyrene.
A skin-thick porous composite sheet (in which the general pores of lotus root-shaped hollow fibers are filled with urethane resin having countless fine continuous pores) was obtained.

2. Slice the solidified surface (front and back surfaces) of the sheet.
The sheet was made into a sheet, immersed in the following resin solution at room temperature for 15 minutes to remove the liquid, and then dried by infrared rays at 80 qo to give a resin adhesion of 73% (based on the weight of the composite sheet).

Beccamin PM-N (melamine resin) manufactured by Dainippon Ink Chemical Co., Ltd. 45 parts 0 Catalyst 306 (catalyst) Same as above 4.5 parts Isopropyl alcohol 1 part Water
After curing the impregnated resin by heat treatment for 40.5 parts and 180,005 minutes, the nonionic surfactant Rapizol FC (NOF ■
20 minutes at room temperature in a 1% aqueous solution of (manufactured by)), deliquified at 100% squeezing rate, and dried in a hot air dryer at 120 oo to 0.65
% of activator adhesion.

The cured composite sheet thus obtained is cut to a certain size,
When the treated pen tip was used as a signature ben, it slid well against the paper surface, there was no creaking sound, and the writing felt light, and there was no wear on the tip until an average of 38,000 characters were written. There was no blurring and no ink smearing. On the other hand, in the case of the wool felt pen that has been commonly used, it does not easily slide on the paper surface, makes a constant squeaking sound, and the pen tip wears and frays after an average of 30,000 characters, making it no longer useful as a pen tip. I didn't do it.
Example 2 Two sheets of the porous composite sheet of Example 1 were laminated and bonded together using dot adhesion using a urethane adhesive to give a thickness of 4 skins, and this sheet was immersed in the following resin solution at room temperature for 13 minutes to remove the liquid. 8
Infrared drying was performed at 0 qo to give a resin adhesion of 48% (based on the weight of the composite sheet).

Betsukamin PM-N (melamine resin) 3 Anchor part Catalyst 306 (catalyst) 3 Boncoat R-3380 (polyacrylate ester)
10 methanol
-.

water 47 then 1
After hardening the impregnated resin by heat treatment for 90 minutes, it was immersed in a 0.5% aqueous solution of nonionic surfactant Emarox NX-1100 (manufactured by Yoshimura Yukagaku ■) at room temperature for 20 minutes and squeezed 100%. After removing the liquid at a rate of
The adhesion amount was set as . The thus obtained brush pen, which is made by cutting the 4-way thick sheet into a certain size and processing the tip into a conical shape, has a soft and smooth writing feel and reproduces the same font as a brush without running out of ink or causing smearing. I was able to do it.

Claims (1)

[Scope of Claims] 1. A porous composite in which the voids of a nonwoven fabric in which fibrous materials are three-dimensionally entangled are filled with a polymer elastomer having countless fine continuous through-pores, the porous composite comprising: After the surface layer of the composite is cured with at least one selected from a thermosetting resin, a thermoplastic resin, or a solvent for the polymer elastomer, the entire surface is treated with a nonionic or anionic surfactant. A pen nib for writing instruments. 2. The nib for a writing instrument according to claim 1, wherein the polymer elastomer filled in the voids of the nonwoven fabric has a pore cross-sectional area of mainly 10 to 100 μ^2. 3. A pen nib for a writing instrument according to claim 1 or 2, which uses hollow or microfiber bundle fibers having voids inside the fibers as the fibrous material. 4. The nib for a writing instrument according to claim 1, which uses a porous composite in which the fibrous material and the polymer elastomer are substantially non-adhesive. 5 The ratio of the fibrous material to the polymer elastomer is 10 to 60% by weight of the fibrous material and 40 to 90% by weight of the polymer elastomer.
% by weight, and the apparent specific gravity of the porous composite is in the range of 0.1 to 0.7.