JP3207131B2 - Flexible paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible paper, and more particularly to a novel flexible paper having useful properties suitable for use as an interior material for furniture and building materials.

[0002]

2. Description of the Related Art As interior materials for furniture and building materials, soft vinyl chloride resin films occupy the mainstream, and printing,
A method of performing processing such as embossing and bonding to a board or plywood has been adopted. A soft vinyl chloride resin film is rich in flexibility, has various excellent properties such as printability, chemical resistance, and processability, and is used without problems in quality. However, processed furniture and interior materials for building materials based on vinyl chloride resin film, like vinyl wallpaper, originated from environmental changes such as the enforcement of the PL Law and deregulation, and the conversion to environmentally friendly products was avoided. No new proposals have been made, such as the amendment of fire protection material certification standards. With regard to environmental issues, in particular, the current trend is to respond to the global trend, which is being affected by Europe, which is leading the way.Hazardous substances such as hydrogen chloride and dioxin, including waste, are at present. We are at a turning point due to environmental problems that occur.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned environmental problems, and has a very high practicality which is clear in terms of quality and function which can be replaced with a conventional soft vinyl chloride resin film. The purpose is to provide pollution-free flexible paper.

[0004]

Means for Solving the Problems As a result of various studies to achieve the above object, the present inventor has found that paper made of mixed pulp containing cotton linter pulp as a main component and wood pulp or recycled pulp as an auxiliary component. After highly impregnating with an impregnating agent mainly composed of rubber latex or thermoplastic non-chlorine resin emulsion, after drying, a resin layer is provided on the surface, and pressure is applied while heating and melting to cause a layered floating movement of the impregnated resin,
For this purpose, flexible paper with extensibility that enhances printability by forming a film while strengthening the intermolecular bonds of the resin, and at the same time performing surface modification such as promoting crystallization and thermal curing of the surface resin layer. It was found that they matched, and the present invention was accomplished.

That is, the present invention relates to (A) cotton linter pulp 5
Highly water-absorbing and highly water-retaining paper made from mixed pulp of 0 to 80% by weight and (B) at least one of wood pulp and recycled pulp is used as a base paper, and rubber latex Alternatively, a flexible paper material having spreadability obtained by impregnating various impregnating agents mainly composed of a thermoplastic non-chlorinated resin emulsion at a solid content weight ratio of 40 to 100%, and applying a resin layer on the surface thereof, followed by heating. This is flexible paper formed by applying pressure and cooling to form a resin film.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

[0007] In the present invention, cotton linter pulp 50 ~
80% by weight and wood pulp and / or recycled pulp 50-2
The base paper mixed with 0% by weight ensures high water absorption and high water retention, and the impregnating liquid is promptly impregnated in the next step of impregnating a thermoplastic non-chlorinated resin emulsion (including rubber latex; the same applies hereinafter). It is used for the purpose of uniformly penetrating a large amount into the base paper. When the blending ratio of the cotton linter pulp in the mixed pulp during papermaking is less than 50% by weight, no remarkable effects are obtained in formation of the formation, flexibility, impregnation ratio and the like. On the other hand, when the blending ratio of cotton linter pulp is 8
When it exceeds 0% by weight, it has advantages in formation, flexibility, impregnation rate, etc., but on the other hand, it has problems such as a decrease in paper strength, surface smoothness, wet strength, etc., and is preferred as a base paper for flexible paper. Absent.

By mainly using cotton linter pulp, the water-based thermoplastic non-chlorine-based resin emulsion has a high water absorption rate, the production speed is increased, and the process can be shortened. Taking advantage of the good aspects of cotton linter pulp and the strength of wood pulp, the significance of mixed papermaking is fully exhibited.

NBKP, LBKP, N as wood pulp
BSP or the like is used.

[0010] Wet paper such as melamine resin, urea resin, polyamide, epichlorohydrin resin, polyacrylamide resin and the like in a mixed pulp prepared by mixing (A) cotton linter pulp and (B) wood pulp and / or recycled pulp at a predetermined ratio. The resin emulsion is impregnated effectively by adding a force enhancer or a fixing agent, and is formed into a non-sized paper in order to impart flexibility and texture to the obtained impregnated paper. At this time, if necessary, other papermaking auxiliary materials such as other papermaking fibers, fillers, and coloring agents can be appropriately added and mixed.

[0011] The wet strength agent is usually 0.05 to pulp.
To 2.0% by weight, and the base paper is 35 to 80 g /
m ² , preferably 40 to 60 g / m ² .

The base paper thus formed is impregnated with a resin emulsion in an impregnation vat, and thereafter, according to a conventional method.
The desired resin-impregnated paper flexible paper material is manufactured by passing through the drying device.

The resin emulsion to be impregnated includes, for example, butadiene-based copolymer, isoprene-based copolymer, vinyl acetate-based copolymer, acrylate-based copolymer, styrene-based copolymer, ethylene-based copolymer and the like. A rubber latex or a resin emulsion is used alone or in combination. At this time, if necessary, dyes, pigment coloring agents,
A wax, a dispersant, a water-proofing agent, an antifoaming agent, a softening agent, a sizing agent, and the like can be appropriately added. As the impregnation amount of the resin emulsion, the solid content is 40 to 10 with respect to the weight of the base paper.
By penetrating 0% by weight into the base paper, strength,
A characteristic resin-impregnated paper having improved characteristics such as flexibility, water resistance, processability, workability, and spreadability can be obtained.

Specific examples of the resin include the following. (1) Butadiene-based copolymer Styrene-butadiene copolymer Methyl methacrylate-butadiene copolymer (2) Isoprene-based polymer (3) Vinyl acetate-based copolymer Vinyl acetate-methyl acrylate copolymer Vinyl acetate-acrylic Ethyl acrylate copolymer Vinyl acetate-butyl acrylate copolymer Vinyl acetate-acrylic acid-2-ethylhexyl copolymer Vinyl acetate-dibutyl maleate copolymer Vinyl acetate-ethylene copolymer (4) Acrylate ester-based polymer Copolymer Methyl acrylate copolymer Ethyl acrylate copolymer Butyl acrylate copolymer 2-Ethylhexyl acrylate polymer Butyl acrylate-styrene copolymer Acrylate-2-ethylhexyl-styrene copolymer (5) Styrene Polymer (6) Ethylene polymer Ethylene homopolymer Ethylene-vinegar Vinyl copolymer ethylene - acrylic copolymer

[0015] A flexible paper material impregnated with a resin emulsion has a remarkable improvement in extensibility (elongation rate). However, since the surface is further provided with surface characteristics and printability according to the purpose of use, further resistance is obtained. A resin layer can be provided for application, and the coating composition of flexible paper that can be adapted to the purpose is a blade coater, an air knife coater, a roll coater, a brush coater, which is used in general coated paper production. The coating is performed on the impregnated paper by an off-machine coater provided with a coating device such as a curtain coater, a gravure coater, a comma coater, or a bar coater.
The solid content concentration of the coating composition at that time is 10 to 50% by weight,
Considering the operability, the range of 20 to 35% by weight is preferable. The coating amount of the coating composition on the impregnated paper is 5 to 2 by dry weight.
0 g / m ² approximately, it is adjusted preferably in the range from the surface of the coated paper quality 10~17g / m ² obtained. Specific examples of resins to be provided for coating include the following.

(1) Polyurethane resin (2) Polyester resin (3) Acrylic copolymer (4) Vinyl acetate copolymer (5) Styrene copolymer (6) Synthetic rubber latex (7) Polyolefin resin ( 8) Colloidal silica-acrylic composite particle emulsion Either a single resin or a mixture of two or more resins and a crosslinking agent for each (melamine resin, epoxy resin, polyamidoamine)
Or wax emulsion, zirconium ammonium carbonate or the like can be used in combination to improve the physical properties.

The thermoplastic non-chlorine emulsion resin impregnated inside and the impregnated paper provided with a resin layer on the surface are suitable for printing,
Although it has excellent resistance to building materials such as chemical resistance and heat resistance, it is further heated and pressurized to melt and cool and solidify the resin. Bonding is strengthened and a film is formed. The surface resin is also promoted for crystallization and thermosetting.

The heating / pressurizing / cooling process is a combination of a cylindrical pressure roll having a mirror surface in multiple stages (for example, 2 to 24 stages).
A large amount of resin impregnating liquid penetrates into a mixed papermaking mainly composed of cotton linter pulp as a (base material), and is further processed into a material having a resin layer on the surface of the impregnated paper. The passage of the roll causes the layered floating movement of the impregnated resin, thereby distributing a large amount of resin impregnation on the base paper surface side, and promoting crystallization and thermosetting of the surface resin to improve the surface modification, printability, heat resistance, and heat resistance. Improves chemical properties. The resin film is formed by the upper layer movement of the impregnated resin and the strengthening of intermolecular bonds due to melting, and as shown in Table 3, the extensibility and the flexibility are almost doubled. As a result, the flexible paper is completed, and the following advantages are obtained. Can be.

(1) Excess moisture is removed from the resin-impregnated paper to provide a flexible impregnated paper as an intermediate between the paper and the plastic film. (2) Cross-linking of the resin proceeds, and the strength of the coating film is improved. (3) It becomes a high-density paper, and its temperature dependency and humidity dependency are reduced. (4) The surface smoothness is greatly improved, and the printability is improved.

Various apparatuses can be considered for performing the heating and pressurizing treatments. Effective means include a method in which the number of rolls is combined in multiple stages.

The heating, pressurizing and cooling conditions are carried out in the following ranges. Velocity 30 to 200 m / min line pressure 50 to 400 kg / cm ² roll temperature

As shown in Examples below, the flexible paper according to the present invention is not inferior to conventional soft vinyl chloride resin films in physical properties and can be suitably used as an interior material for furniture and building materials. Applications similar to ordinary resin-impregnated paper, such as poster paper, map paper, packaging paper, display paper, label paper, book cover and return paper, album and file lining paper, industrial base paper (abrasive paper, artificial leather) Paper, process paper), base paper for tapes, stationery, cases, masking tape base paper, gasket paper, etc.

[0023]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 A wet paper strength enhancer (trade name "Epinoc P-130", manufactured by Dick Hercules) was added to a mixed pulp of cotton linter pulp: NBKP: LBKP: recycled pulp (70: 0: 25: 5). 0.8% by weight, a non-sized base paper having a basis weight of 50 g / m ² , and a paper making width of 1.3 according to an ordinary method using a fourdrinier paper machine.
Paper was made at 20 mm. Physical properties of the obtained paper were as shown in Table 1.

Example 2 Cotton linter pulp: NBKP: LBKP: recycled pulp
(40: 30: 30: 0) mixed pulp was internally added with 0.8% by weight of a wet paper strength enhancer (trade name “Epinoc P-130”, manufactured by Dick Hercules), and was constantly added to a fourdrinier paper machine. According to the method, a non-sized base paper is weighed 50 g / m ² and the papermaking width is 1.3.
Paper was made at 20 mm. The physical properties of the obtained paper are as shown in Table 1.

For comparison, cotton linter pulp 100
% And physical properties of non-sized paper made from only wood pulp NBKP: LBKP (60:40) are also shown in the table.

[0027]

[Table 1]

As apparent from the physical properties shown in Table 1,
The cotton linter pulp-wood pulp mixed papermaking of the present invention has a very high water absorption and water retention as compared with a non-sized paper made of only wood pulp, and has a tensile strength enough to withstand high-speed production and a base paper for flexible paper. It will be appreciated that it has both the preferred elongation as paper.

Next, in Examples 3 and 4, the base paper prepared in Example 1 was used as a base paper to prepare a resin emulsion for impregnation.

Example 3 MBR synthetic rubber latex 48% (trade name “Crosslen 2M33A”, manufactured by Takeda Pharmaceutical Co., Ltd.) 20.0% by weight Acrylic ester copolymer 50% (trade name “Polysol SUM-2000”) , Manufactured by Showa Polymer Co., Ltd.) 60.0% by weight Titanium dioxide 60% (trade name "Taipeku Titanium R-550", manufactured by Ishihara Sangyo Co., Ltd.) 15.0% by weight Soft calcium carbonate 65% (product) Name “Tamapearl 222H”, manufactured by Okutama Industry Co., Ltd.) 5.0% by weight

Example 4 Acrylic ester copolymer 50% (trade name “Polysol SUM-2000”, manufactured by Showa Polymer Co., Ltd.) 45.0% by weight Acrylic ester copolymer 45% (trade name “Movinyl” DC-620 ", manufactured by Hoechst Gosei Co., Ltd.) 35.0% by weight titanium dioxide (trade name" Taipeku Titanium R-550 ", manufactured by Ishihara Sangyo Co., Ltd.) 15.0% by weight soft calcium carbonate (trade name) "Tamapearl 222H", manufactured by Okutama Industry Co., Ltd.) 5.0% by weight

The resin emulsions prepared in Examples 3 and 4 were impregnated into a base paper at a solid content of 80% by weight and dried. As a result, an impregnated paper was obtained, which was entirely colored white and had extremely high whiteness and concealing properties. As shown in Table 2, the results of the physical property tests show that the tensile strength and the elongation were greatly improved.

[0033]

[Table 2]

Next, a resin coating on the surface resin layer of the impregnated papers obtained in Examples 3 and 4 was prepared based on Examples 5 to 7 described below.

Example 5 Styrene / acrylic copolymer resin 40% (trade name “Polysol AM-200”, manufactured by Showa Polymer Co., Ltd.) 10.0% by weight Acrylic copolymer resin 46% (trade name “Cybinol EC” -657B ", manufactured by Seiden Chemical Co., Ltd.) 15.0% by weight Acrylic copolymer resin 31% (trade name" Licabond SA-13 ", manufactured by Chuo Rika Kogyo Co., Ltd.) 73.0% by weight Epoxy resin 98% ( Product name “Licabond EX-8”, manufactured by Chuo Rika Kogyo Co., Ltd.) 2.0% by weight

Example 6 Acrylic copolymer resin 40% (trade name “Cybinol EK-35”, manufactured by Seiden Chemical Co., Ltd.) 30.0% by weight Styrene / acrylic copolymer resin 40% (trade name “Movinyl DC-9000” , Hoechst Synthetic Co., Ltd.) 50.0% by weight Acrylic copolymer resin 46% (trade name "Newcoat # 4000", Shin-Nakamura Chemical Co., Ltd.) 15.0% by weight Melamine resin 80% (product) Name "SUMIREZ Resin 613", manufactured by Sumitomo Chemical Co., Ltd.) 5.0% by weight

Example 7 Polyurethane resin 30% (trade name “Superflex-160”, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 80.0% by weight Acrylic resin 38% (trade name “Joncryl SCX-1695”, Johnson) Polymer Co., Ltd.) 10.0% by weight Polyethylene wax 30% (trade name "Johnson Wax", Johnson Polymer Co., Ltd.) 2.0% by weight

In each of Examples 5 to 7, the coating amount was adjusted to 15 g / m ² . The coating thickness averaged 12 microns.

The following items were evaluated for quality as a criterion for determining a resistant resin layer. The results are shown in Table 3.

Test items Test conditions Class Immersion peeling Drying in boiling water for 4 hours, 60 ° C. for 20 hours, and further boiling water for 4 hours, drying for 2 hours Plane tension A 20 mm square metal plate is adhered to the surface, cut in the periphery, and cut vertically. Stab cold repeated 2 hours of heating at 80 ° C for 2 hours and cooling at -20 ° C for 2 hours water resistance test immersed in 60 ° C warm water for 1 hour, dried for 2 hours at 60 ° C and repeated twice Wet heat test After dripping of boiling water, Leave a 1 liter container containing 0.5 liter of boiling water for 20 minutes. Abrasion resistance test Using a Taber abrasion tester, load 500 g of S-33 abrasion wheel. Discoloration test. Apply to sample and wipe off with solvent after 2 hours Alkali resistance test 0.5, caustic soda, 6 hours Acid resistance test 5%, hydrochloric acid aqueous solution, 6 hours Solvent resistance test Toluene, 6 hours

[0041]

[Table 3]

The impregnated paper obtained in Example 3 was provided with a surface resin layer in accordance with Examples 5 to 7, the coating film was dried at 80 to 200 ° C., and subsequently subjected to heating and pressurizing and cooling treatment under the following conditions. As shown in Table 4, the physical property test results are comparable to the soft vinyl chloride resin (PVC) film of the comparative product, and the flexibility, spreadability, surface smoothness and heat resistance are higher than those of the flexible paper material (Table 2). It is a flexible paper with good water resistance, water resistance, chemical resistance and printability.

[0043]

[Table 4]

[Heating / Pressing / Cooling Treatment Conditions] 18 stages; Roll heating temperature: chilled roll 100-1
30 ° C. linear pressure; 250-300 kg / cm ^{2 at} pressurization; 100 m / min Cooling temperature: 8-20 ° C

[0045]

The effects of the present invention are as follows. Since no harmful gas is generated during waste incineration, it is extremely useful as a pollution-free flexible paper. It is possible to substitute a soft vinyl chloride resin film for furniture and building materials. If the paper has high flexibility, resin-impregnated paper with excellent texture can be manufactured, and it has curved surface application and V-cut suitability. Since the paper quality becomes stronger, the paper itself can be made thinner, which contributes to weight reduction. It is possible to produce small lots of your favorite color. Because of the high smoothness, a very excellent printing effect can be expected. Utilizing characteristics such as durability, flexibility, printability, and toughness of a coating film, it can be used as a substitute for synthetic paper.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) D21H 11/00-27/42

Claims (6)

(57) [Claims] 1. Highly water-absorbing and high-maintenance paper-mixed pulp comprising (A) 50-80% by weight of cotton linter pulp and (B) 50-20% by weight of at least one of wood pulp and recycled pulp. Construction paper base paper made of water-based paper 2. High water absorbency and high preservation obtained by papermaking a mixed pulp comprising (A) 50 to 80% by weight of cotton linter pulp and (B) at least one of wood pulp and recycled pulp. Extensible flexible paper material obtained by impregnating a base paper made of water-based paper with an impregnating agent mainly composed of rubber latex or a thermoplastic non-chlorinated resin emulsion at a solid content weight ratio of 40 to 100%. 3. The flexible paper material according to claim 2, wherein the rubber latex is at least one of a butadiene-based copolymer latex, an isoprene-based polymer, and a natural rubber latex. 4. The thermoplastic non-chlorine resin emulsion is at least one of a vinyl acetate-based copolymer, an acrylate-based polymer, a styrene-based polymer, and an ethylene-based polymer. Flexible paper material 5. A flexible paper obtained by providing a resin layer on the surface of the flexible paper material according to claim 2. 6. A flexible paper obtained by providing a resin layer on the surface of the flexible paper material according to claim 2 and then subjecting the flexible paper material to a heating and pressurizing and cooling treatment to form a resin film.