JP2002002158A - Colored paper employing glass long fiber braided matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored paper, hardly allowing fungi to propagate or hardly eaten by worms and hardly developing brittleness even when the same is preserved for a long time while being not discolored by ultraviolet rays and hardly contaminated. SOLUTION: A glass long fiber braided matter is laminated on both sides or one side of the substrate of the colored paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored paper suitable for long-term storage.

[0002]

2. Description of the Related Art Conventionally, various materials such as paper, Japanese paper, hemp or silk have been used as a cover of colored paper. However, such conventional products have disadvantages such as being easily discolored by ultraviolet rays or the like and being easily stained. In addition, cracks and holes were formed due to embrittlement due to mold generation and insect bite. On the other hand, colored paper is used not only for painting, such as drawing a picture on it, but also for writing purposes in commemoration of marriage, farewelling, graduation, etc. There is a great demand for colored paper that is less likely to generate mold and worms.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a colored paper which hardly generates mold and worms and hardly becomes brittle even when stored for a long period of time. Another object of the present invention is to provide a colored paper which is not discolored by ultraviolet rays and is hardly stained.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, when a long glass fiber woven or knitted fabric is used for a cover of colored paper, the colored paper is hardly discolored by ultraviolet rays due to the characteristics of glass fibers. I learned that Woven and knitted fabrics made of long glass fibers are hardly stained, and since glass fibers are inorganic fibers, mold is hardly generated and insects are hardly formed. That is, the present inventors have found that it is useful as colored paper to use a glass long fiber woven or knitted fabric as a cover. Such uses of long glass fiber woven or knitted fabrics are unknown.

[0005] The present inventors have also found that by treating a glass long fiber woven or knitted material with a resin, the glass long fiber woven or knitted material can be easily handled. In particular, in the process of sticking a glass long fiber woven or knitted fabric on one or both sides of a colored paper table in the production of colored paper, the ease of handling of the glass long fiber woven or knitted fabric is important. Further, by adding calcium carbonate, calcium sulfate, talc, titanium oxide, silicon dioxide, or the like to the resin, the inorganic compound plays a role of matting with respect to the gloss unique to glass fiber, and the colored paper exhibits an appropriate white color. I got the knowledge that it would be. In addition, there is an advantage that paint, ink, and the like can be easily applied and a good brush touch can be obtained. In particular, since titanium oxide exhibits an antibacterial effect when activated, it has also been found that addition of titanium oxide to the resin makes it more difficult for mold to be generated during long-term storage.

Further, the present inventors have performed resin treatment on only one surface of a glass long fiber woven or knitted fabric, and used the non-resin-treated surface for the front side or the back side, so that colored paper can be used for painting. I got an unexpected finding that I can use it properly when I use it as. In addition, the front refers to the side on which characters and pictures are drawn, and the back refers to the side to be stacked on a colored paper stand. In other words, when using oil-based paints such as oil paintings or pastel paintings, it is easier to write pictures using colored paper with the surface treated with the solvent-based resin, while using water-based paints such as watercolors or ink paintings In this case, it is easier to write without paint being repelled by using colored paper having a surface treated with a water-soluble resin or a surface not treated with a solvent-based resin. The present inventors have further studied and completed the present invention.

That is, the present invention provides (1) colored paper characterized by laminating a glass long fiber woven or knitted fabric on both sides or one side of a colored paper table, and (2) resin on one or both sides of the glass long fiber woven or knitted fabric. The colored paper according to the above (1), wherein the colored paper is treated, and (3) the resin is selected from the group consisting of calcium carbonate, calcium sulfate, talc, titanium oxide, silicon dioxide, insect repellent, fungicide, and antibacterial agent. 1 to be chosen
(2) characterized in that it contains the above substances.
And (4) the colored paper according to (1) to (3), wherein the woven fabric is plain weave.

[0008] The glass long fiber used in the glass long fiber woven or knitted fabric used in the present invention has a diameter of about 3 µm.
Those having a size of about 13 μm are preferably used. Glass is classified in various ways by inorganic substances contained in addition to silica, for example, boron, aluminum, calcium, magnesium, titanium or sodium. The glass long fiber woven or knitted fabric of the present invention is made of any material. Can be used without any problem.

[0009] The glass filament may be a filament yarn obtained by simply arranging filaments, a twisted filament yarn or a knitted filament yarn. Good. When twisting, single twisting may be applied simply. In this case, the twist is preferably about 0.5 to 4 turns / 25 mm. Also, after the first twist, the first twist may be applied.

[0010] The long glass fiber in the present invention is preferably treated with a sizing agent before weaving or knitting for the purpose of bundling a single yarn. As the sizing agent, for example,
An emulsion or suspension such as starch (starch) or polyvinyl alcohol, or a hardly water-soluble resin such as an acrylic resin, a polyester resin, or an epoxy resin is exemplified. The sizing agent can be appropriately selected depending on the type of loom. For example, when using a water jet loom, it is preferable to use a poorly water-soluble resin as a sizing agent.

The glass fiber thus obtained is woven and knitted. The weaving method includes, for example, plain weave, satin weave, twill weave, horizontal stripe weave,
There are various techniques such as leno weaving and oblique weaving, and any weaving method may be used in the present invention, but plain weaving is preferred as the glass long fiber woven or knitted fabric of the present invention. Also in the knitting method, for example, there are various methods such as flat knitting, flat knitting such as rubber knitting or pearl knitting, vertical knitting such as single denby knitting or single denby knitting, or lace knitting. May be used.

In weaving and knitting, it is also possible to use a blended yarn of glass fibers and fibers other than glass fibers. In such a case, the fibers other than glass fibers include natural fibers and chemical fibers. Examples of natural fibers include plant fibers such as cotton and hemp, and animal fibers such as wool and cashmere and hair or silk. Recycled fiber such as rayon; semi-synthetic fiber such as acetate; polyolefin, polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyurethane or phenol And inorganic fibers such as carbon fibers and metal fibers.
As described above, the use of a blended yarn using a fiber other than the glass fiber also has an advantage that the design becomes versatile and brilliant. Further, the glass long fiber woven or knitted fabric according to the present invention may be a mixed woven fabric of glass fiber and fibers other than the above-described glass fiber. The thickness of the woven or knitted fabric suitable as the long glass fiber woven or knitted fabric of the present invention is about 20 μm to 3 m.
m, preferably about 30 to 150 μm.

The glass long fiber woven or knitted fabric according to the present invention is preferably subjected to a resin treatment. The resin treatment serves as a filler so that the warp and the weft of the glass long fiber woven or knitted fabric do not shift. Examples of the resin treatment include a treatment of applying or impregnating a solvent or a water-soluble resin on one or both sides of a glass long fiber woven or knitted fabric.

As the solvent-based resin, known resins may be used. For example, polyethylene resin, polypropylene resin, polyurethane resin, polyester resin, polyvinyl acetate resin, polyacryl resin, ethylene-vinyl acetate copolymer resin, SBR And conjugated diene polymers such as NBR, polyamide resins (copolymerized nylon soluble in alcohol and graft polymers such as (meth) acrylic acid onto methoxymethylated polyamides), organopolysiloxanes and, for example, dimethylpolysiloxane. Examples include those having different alkyl groups, those having an aryl group introduced therein, and those having a mixture thereof. Among them, a mixture of a polyacryl resin and a polyurethane resin is preferable.
The ratio is preferably about 10: 1 to 1:10, and more preferably about 3: 2. These are appropriately dissolved in an organic solvent or applied as an emulsion polymer, a suspension, or a paste.

As the water-soluble resin, known resins may be used. Examples thereof include polyvinyl alcohols such as polyvinyl alcohol, silyl-modified polyvinyl alcohols such as carboxymethylcellulose, methylcellulose and hydroxymethylcellulose. And polyalkylene glycol-based resins such as polyalkylene glycol-aromatic dicarboxylic acid-alkylene glycol copolymers.

The above resin contains about 60% by weight of an inorganic substance.
Hereinafter, it is preferable to add about 30 to 50% by weight. As the inorganic substance, for example, calcium carbonate, calcium sulfate, glass powder, glass beads,
Inorganic substance powders such as glass flakes, natural mica, artificial mica, oxides such as silicon dioxide, titanium oxide and alumina, and hydroxides such as aluminum hydroxide and magnesium hydroxide are preferred. It is desirable that the inorganic material powder is fine particles having an average particle size of about 10 μm or less, preferably about 0.1 to 5 μm.

In particular, if titanium oxide is added to the resin, the antifouling effect can be further exhibited. That is, active oxygen generated by titanium oxide and light (ultraviolet) energy strongly oxidizes and decomposes components and bacteria that cause dirt or smell. Therefore, organic substances that cause dirt, such as tobacco or oil stains, are strongly oxidatively decomposed, and as a result, inorganic dirt such as dust and dirt accompanying organic dirt can be swapped or dried. Can be easily wiped off. In addition, the strong oxidizing power of active oxygen oxidizes and decomposes bacteria, mold, and the like, thereby exhibiting an antibacterial effect.

[0018] Instead of titanium oxide, a titanium oxide-based compound
The same effect can be obtained by adding to the resin. Oxidized titanium
Examples of the titanium-based compound include, in addition to titanium oxide, titanium
And silicon composite oxide, hydrous titanium oxide, hydrated titanium oxide
, Titanium hydroxide, metatitanic acid or orthotitanic acid
And the like. Also, instead of titanium oxide, a photocatalyst
A semiconductor may be added to the resin. Photocatalytic semiconductors rely on light
And decompose bacteria and mold by oxidation and reduction
As such a substance, for example, TiO 2_Two, Z
nO, SrTiO_Three, CdS, CdO, CaP, In
P, In_TwoO_Three, CaAs, BaTiO_Three, K_TwoNbO_Three,
Fe_TwoO _Three, Ta_TwoO_Five, WO_Three, SbO_Two, Bi_TwoO_Three, Ni
O, Cu_TwoO, SiC, SiO_Two, MoS_Two, MoS_Three, I
nPb, RuO_TwoOr CeO_TwoAnd the like.

When a resin treatment is applied to one side of the glass fiber woven or knitted fabric, the viscosity may be increased depending on the state of the resin used so that the resin does not ooze to the opposite side.
As the thickener to be added when it is necessary to increase the viscosity, for example, a polymer mainly composed of acrylic acid or methacrylic acid is neutralized with ammonia, caustic soda, etc. to make it water-soluble, or polyvinyl alcohol or milk And water-soluble polymer substances such as casein.
On improving the adhesiveness to the glass long fiber woven or knitted fabric, for example, tetramethoxysilane, tetraethoxysilane, phenyltriethoxysilane, butyltritrimethoxysilane, glycidoxypropyltrimethoxyxysilane,
It is effective to add a small amount of a silyl compound such as glycidoxypropylmethyldimethoxyxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

In order to prevent the occurrence of mold and insects on the colored paper, a fungicide, insect repellent or antibacterial agent may be further added to the resin. As the antibacterial agent used in the present invention, known antibacterial agents can be used,
Examples thereof include an inorganic antibacterial agent in which a metal ion is supported on an inorganic compound, an inorganic oxoacid salt having an antibacterial metal ion, tourmaline, or a plant or a processed product thereof.

In the inorganic antibacterial agent in which a metal ion is supported on an inorganic compound, any inorganic compound can be used. For example, activated alumina, inorganic adsorbents such as silica gel, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrous bismuth, hydrous zirconium or inorganic ion exchangers such as hydrotalcite and the like. Can be Examples of the metal ion include silver, copper, zinc, and tin.

As a method for supporting metal ions on these inorganic compounds, a known supporting method may be appropriately employed. For example, a method of supporting by physical adsorption or chemical adsorption, a method of supporting by ion exchange reaction, a method of supporting by a binder, a method of supporting a metal compound by driving a metal compound into an inorganic compound, or a thin film such as vapor deposition, dissolution deposition reaction, or sputtering A method in which a thin metal layer is formed on the surface of an inorganic compound by a forming method so as to be supported, and the like.

Among the above-mentioned inorganic compounds, the inorganic ion exchanger is preferably used because it can strongly support metal ions, and zeolite or zirconium phosphate is particularly preferably used. As the inorganic compound, for example, “Novalon A
Commercial products such as "G-300" (manufactured by Toa Gosei Chemical Co., Ltd., zirconium phosphate carrying silver ions) and "Zeomic AW-10D" (manufactured by Sinanen New Ceramics, zeolite carrying silver ions) can also be used in the present invention.

An antibacterial zeolite as an example of the above is disclosed in JP-A-60-202162, and a part or all of ion-exchangeable ions in a zeolite such as a natural zeolite or a synthetic zeolite is converted to silver nitrate or sulfuric acid. About 0.1 to 15% of silver ions using silver or the like, and about 0.1 to 8%
Antibacterial zeolites substituted by about copper ions and about 0.1 to 8% zinc ions are exemplified, but the antibacterial zeolites may be used in the present invention.

A typical example of the inorganic oxoacid salt having an antibacterial metal ion is one obtained by ion-exchanging a metal ion of an inorganic oxoacid salt with an antibacterial metal ion. Here, examples of the inorganic oxo acid salt include silicate, phosphate, titanate, antimonate and the like. Examples of the silicate include magnesium aluminate metasilicate, calcium silicate and magnesium silicate. Examples of the phosphate include calcium phosphate and zirconium phosphate. Examples of titanates include potassium titanate and calcium titanate. Examples of the antimonate include compounds such as sodium antimonate. As the inorganic oxo acid salt, particularly, apatite mainly composed of magnesium aluminate metasilicate and calcium phosphate is preferable from the viewpoint of safety. Apatite is also called apatite, and is a general term for fluorapatite, chlorapatite, or hydroxyapatite.

As metal ions having antibacterial properties to be ion-exchanged, metal ions usually used as antibacterial agents or bactericides, such as silver, copper, zinc or tin, can be applied.

These metal ions are ion-exchanged with the metal ions of the above-mentioned oxo acid salt by a usual method. For example,
Exchange of ions such as silver, copper, zinc or tin takes place in a region below the pH value at which hydroxides are formed and in which the oxoacid salts do not dissolve. That is, in the case of silver, the pH is about 9 to 4.
About pH 6-4 for copper, about p for zinc
The range of about H9 to 4 is preferable. The ratio of the antibacterial metal ion to be ion-exchanged is preferably about 0.1 to 90 mol% of the ion exchange capacity of the oxoacid salt, and the ion-exchanged ion in the antibacterial agent is Preferably, it is about 0.01 to 40% by weight of the antimicrobial agent. When the metal ion is less than the above minimum value, the antibacterial property is not sufficient, and when the metal ion exceeds the maximum value, the metal ion becomes unstable and the stability and sustainability of the antibacterial effect are lacking.

Examples of the plant or a processed product thereof include an extract of hiba.

In the present invention, fungicide or insect repellent treatment may be performed by performing resin treatment with a resin to which a fungicide or insect repellent is added. Examples of the fungicide and insect repellent include plants such as hiba extract and indigo dye or processed products thereof.

When the active ingredient such as an antibacterial agent used in the above-mentioned antibacterial treatment, antifungal treatment or insect repellent treatment is granular, the particle size of the active ingredient is such as to fill in the entanglement between the fibers of the glass filament woven or knitted fabric. Therefore, it is desirable that the fine particles have an average particle diameter of about 10 μm or less, preferably about 0.1 to 5 μm.

In addition, additives commonly used in the art may be added to the resin, if desired. As the additive,
Pigment, peroxide-based crosslinking agent, coupling agent, for example, a lubricant such as bisamide, for example, a phenolic antioxidant,
For example, hindered amine light stabilizers, ultraviolet absorbers, flame retardants and the like can be mentioned.

The resin treatment in the present invention is usually performed by the following method. That is, first, to the resin, if desired, the above-mentioned inorganic compound, an antibacterial agent, a fungicide or an insect repellent, or a thickener are added, and mixed by a known method such as stirring with a Henschel mixer or a method equivalent thereto,
Then, the resin composition is impregnated or coated by a known method. In the method of impregnating the resin composition, the woven or knitted fabric is immersed in a tub containing the molten resin composition, pulled up to squeeze out an excess amount, and the resin-treated woven or knitted fabric is dried. As a drying method, for example, a method known per se such as a method of hot air, infrared rays, contact with a heating cylinder, or the like may be used. More specifically, the method for applying the resin composition includes, for example, a method such as roll coating, knife coating or coating by spraying. The amount of resin to be deposited by the process is about 20 to 200 g / ^{m 2.} Preferably, it is about 40 to 100 g / m ² .

The above resin treatment may be performed on only one side of the glass fiber woven or knitted fabric, or may be performed on both sides. Alternatively, a treatment may be performed in which one surface is coated or impregnated with a solvent-based resin, and the other surface is coated or impregnated with a water-soluble resin. Depending on the presence or absence of resin treatment or the type of resin,
Different writing tools can be used to create different tastes. In other words, the surface treated with the solvent resin is suitable for writing with an oil paint such as oil paint or pastel. On the other hand, a surface treated with a water-soluble resin or a surface not treated with a resin is suitable for writing with a water-soluble writing instrument such as watercolor paint or black ink. However, it is needless to say that the present invention is not limited to this.

The long glass fiber woven or knitted fabric produced as described above is laminated as a cover on a colored paper board to produce the colored paper according to the present invention. At this time, the glass long fiber woven or knitted fabric may be laminated on only one side of the colored paper table, or may be laminated on both sides. By laminating a glass long fiber woven or knitted fabric having different resin treatments on each side, a colored paper which can be used for various writing instruments is obtained. That is, one surface is laminated with the surface coated or impregnated with the solvent-soluble resin facing up, and the other surface is coated or impregnated with the water-soluble resin or the surface not subjected to the resin treatment. For example, a case where the sheets are laminated in a table is used.

The color paper table used in the present invention may be a known paper material such as paper, wood or synthetic resin. In the present invention,
It is preferred to use cardboard. The shape of the colored paper table is not limited to a square, but may be any shape. Further, the colored paper table according to the present invention may have a known structure. For example, there is a structure in which one or a plurality of small holes are formed in a colored paper table.
By doing so, the decoration is positioned at the position where the decoration of the doll or the like is to be attached, the wire or the needle is pressed against the colored paper, the small hole portion is searched and penetrated, and the decoration of the doll or the like is drawn by the thread passed through the wire or the needle. Can be fixedly attached to colored paper. Further, the display device may have a structure in which a support portion that can be raised to maintain the display posture is provided. Accordingly, there is an advantage that the display can be performed without putting in a frame, and a display such as a wall-mounted display or a table-top display can be selected.

The method for laminating is not particularly limited. For example, the colored paper table and the glass fiber woven or knitted fabric may be stopped by a fastener known per se, or the glass fiber woven or knitted cloth may be attached to the colored paper table using an adhesive. May be adhered, or the glass fiber woven or knitted fabric may be adhered to a colored paper board using an adhesive. Examples of the method of stopping with a stopper include a method of framing with a sheet material coated with an adhesive.

As the adhesive, those known per se can be used, but a hot melt adhesive or an aqueous adhesive is preferable. Known hot melt adhesives can be used, but polyethylene hot melt adhesives are preferred. Further, as the water-based adhesive, a starch-based adhesive or an adhesive composed of polyvinyl acetate is preferable. Specifically, as the starch-based adhesive, an adhesive composed of spray paste 77 (manufactured by Sumitomo 3M Limited) or polyvinyl acetate is used. As the agent, a bond for woodworking (manufactured by Cemedine Co., Ltd.) is preferable. Among them, a polyethylene hot melt adhesive is more preferable.

As the pressure-sensitive adhesive, a known pressure-sensitive adhesive such as a rubber-based or acrylic-based pressure-sensitive adhesive can be used. In addition, by using a re-adhesive adhesive, only the glass long fiber woven or knitted fabric on the cover can be replaced.

The colored paper according to the present invention can be used for various purposes. For example, it may be used for drawing a picture, writing a book, a waka, a haiku, or the like, or may be used for a side note. When used for painting, it can be used for oil painting, acrylic painting, pastel painting, watercolor painting, ink painting, and the like. The writing implement is not particularly limited because it is written on colored paper, and any known implement can be used. Further, it is also possible to directly print on colored paper by an ink jet method or the like.

[0040]

The present invention will be described in detail with reference to the following examples.
This does not limit the present invention.

Example 1 A polyacrylic resin (Chuo Rika Kogyo Co., Ltd.) and a polyurethane resin (Dainippon Ink Chemical Co., Ltd.) were coated on one surface of a plain weave cloth H153 (manufactured by Unitika Glass Fiber Co., Ltd., weight 113 g). 6: 4, and further, a mixture of calcium carbonate and talc in a ratio of 3: 1 was applied to a resin liquid of 40% by weight.
Drying was performed at 140 ° C. in the first step and then at 110 ° C. in the second step to obtain a long glass fiber fabric. The obtained glass long fiber fabric was stuck on one side of a colored paper stand with a polyethylene hot melt adhesive to obtain a colored paper according to the present invention.

[0042]

The colored paper according to the present invention thus obtained is
Since the cover is made of glass fiber woven or knitted fabric, it is hardly discolored by ultraviolet rays and hardly stained. In addition, the occurrence of mold and insect biting are unlikely to occur, and the composition is not easily embrittled even when stored for a long period of time.
In addition, the resin treatment facilitates handling of the long glass fiber woven or knitted fabric in the process of producing colored paper. In addition, various aspects can be obtained by selectively using the surface that has been subjected to the resin treatment or the surface that has not been subjected to the resin treatment depending on the writing implement to be used. Further, by adding various additives to the resin, antibacterial properties, insect repellency and fungicide properties can be enhanced.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yuko Shimizu 1-18-17 Minamisenba, Chuo-ku, Osaka-shi, Osaka Unitika Glass Fiber Co., Ltd. F-term (reference) AC10C AG00B AG00C AK01B AK01C AK04G AK25 AK53 AL05B AL05C BA03 BA06 BA10B BA10C CA12B CA12C CB05 DG10A DG12B DG12C EJ64B EJ64C GB90 HB00A JC00 JL06 JL10A

Claims (4)

[Claims] 1. A colored paper comprising a glass fiber woven or knitted fabric laminated on both sides or one side of a colored paper stand. 2. The colored paper according to claim 1, wherein one or both sides of the glass fiber woven or knitted fabric are resin-treated. 3. The resin according to claim 1, wherein the resin contains at least one substance selected from the group consisting of calcium carbonate, calcium sulfate, talc, titanium oxide, silicon dioxide, insect repellent, fungicide, and antibacterial agent. The colored paper according to claim 2. 4. The colored paper according to claim 1, wherein the woven fabric is a plain weave.