JP2013151770A - Sheet for wallpaper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet for a wallpaper, which can prevent deposition of both of a hydrophilic contaminant and an oleophilic contaminant, has excellent printability, does not need to be bonded with a film and the like and thereby has excellent productivity, and is produced by an environment-friendly production process, in the sheet for the wallpaper, which is used as an interior material in a house and the like.SOLUTION: The sheet for the wallpaper is produced by subjecting a nonwoven fabric containing wood pulp and a synthetic fiber to water repellent and oil repellent treatment. The water repellent and oil repellent treatment is conducted by using an amino siloxane protonated by an acid.

Description

  The present invention relates to a wall paper sheet for interior use used in a house or the like, and more particularly to a wall paper sheet that can prevent adhesion of pollutants, both hydrophilic and lipophilic. .

  Conventional wallpaper mainly includes a base paper for wallpaper provided with a polyvinyl chloride resin layer. However, polyvinyl chloride has been avoided from the viewpoint of waste disposal and the like, and wallpaper using non-woven fabric has come to be used.

  On the other hand, although the wallpaper using a nonwoven fabric has a good texture, there is a problem that surface processing such as printing is difficult. In order to solve this problem, a nonwoven fabric for wallpaper containing synthetic fibers and cellulosic fibers has been proposed (see, for example, Patent Documents 1 and 2). However, there has been a problem that cellulosic fibers are liable to adhere to hydrophilic contaminants and synthetic fibers are liable to adhere to lipophilic contaminants. In addition, in order to prevent adhesion of hydrophilic contaminants, a nonwoven fabric for wallpaper in which a fatty acid sizing agent is internally added has been proposed (for example, see Patent Document 2). However, although the method of Patent Document 2 can prevent the adhesion of hydrophilic contaminants to some extent, the effect is small. In addition, this method cannot prevent the adhesion of lipophilic contaminants.

  In general, wallpaper using nonwoven fabric is more susceptible to contaminants than wallpaper with a polyvinyl chloride resin layer, and depending on the type of contaminants, it can be difficult to remove, and even the interior of the wallpaper can be contaminated. Substances could penetrate.

  In order to solve these problems, a wallpaper sheet in which a wet nonwoven fabric made of polyolefin synthetic pulp is bonded to a dry nonwoven fabric has been proposed (see, for example, Patent Document 3). However, since polyolefin synthetic pulp is highly hydrophobic, adhesion of hydrophilic contaminants can be prevented, but there is a problem that lipophilic contaminants are more likely to adhere. In addition, there has been proposed a wallpaper sheet in which a nonwoven fabric layer made of water-repellent pulp fibers is provided and a surface nonwoven fabric layer having printability is provided (see, for example, Patent Document 4). However, this method can prevent the penetration of liquid to some extent, but cannot prevent the adhesion of contaminants to the surface. In addition, a wallpaper sheet in which a nonwoven fabric layer of water-repellent pulp fibers is provided and a thermoplastic resin film is bonded has been proposed (see, for example, Patent Document 5). Penetration can also be prevented, but productivity is poor because a process of bonding the thermoplastic resin film is required. Moreover, although the sheet | seat for wallpaper which bonded the fluorine-type film is proposed (for example, refer patent document 6), although this method can also prevent adhesion and penetration of a pollutant, the process of bonding a fluorine-type film Productivity is poor because it is necessary. In addition, it is difficult to print on a fluorine-based film.

  In addition to this, a solvent-based coating agent has been proposed that coats wallpaper to impart water and oil repellency and prevent the adhesion of contaminants (see, for example, Patent Document 7). However, solvent-based coatings using volatile organic compounds (VOC) are not preferred from a health and environmental standpoint.

  In order to impart water repellency and oil repellency without using a solvent, an aminosiloxane or the like is added to an oil-in-water (O / W type) emulsion using an emulsifier (for example, see Patent Document 8). The use of organosiloxanes (see, for example, Patent Document 9) has been proposed. However, in an oil-in-water emulsion containing an emulsifier, the hydrophobicity is lowered by the emulsifier, so that sufficient water repellency cannot be obtained, and adhesion of hydrophilic contaminants cannot be sufficiently prevented. In addition, polyorganosiloxane that can be water-solubilized cannot be water-solubilized unless its hydrophobicity is lowered, so that sufficient water repellency cannot be obtained, and adhesion of hydrophilic contaminants can be sufficiently prevented. Can not. In order to solve this problem, an oil-in-water emulsion obtained by protonating aminosiloxane with an acid and use thereof have been proposed (for example, see Patent Document 10). In the emulsion, since the emulsifier is not used or only a small amount is used, it is possible to prevent the hydrophobicity from being lowered by the emulsifier. In Patent Document 10, use as a paper sizing agent and use for hydrophobizing a gypsum board are exemplified, and it is described that water repellency is excellent. However, oil repellency has not been studied at all. Absent.

  In this way, even if the contaminant is hydrophilic or oleophilic, adhesion can be prevented, printing suitability is good, and it is not necessary to attach a film or the like, so that productivity is good, and also in terms of the environment in the manufacturing process. A careful wallpaper sheet has not yet been obtained.

JP-A-2005-29920 JP 2002-61062 A JP 2004-16219 A JP 2005-179813 A Japanese Patent Laying-Open No. 2005-2536 JP-A-8-127975 JP 2000-351933 A JP-A-7-97455 Japanese Patent Laid-Open No. 11-256071 JP 2006-57095 A

  It is an object of the present invention to prevent adhesion of contaminants, whether hydrophilic or oleophilic, in interior wallpaper sheets used in houses and the like, and has good printability and bonding of films and the like. Is to provide a sheet for wallpaper which is good in productivity, has good productivity, and is environmentally friendly in the manufacturing process.

  Specific means for solving this problem is as follows.

  (1) A wallpaper sheet in which a non-woven fabric containing wood pulp and synthetic fiber is subjected to water and oil repellency treatments, which are subjected to water and oil repellency treatments using aminosiloxane protonated with an acid. The sheet for wallpaper characterized by being.

  (2) The wallpaper sheet according to (1), wherein the synthetic fiber is at least one selected from polyester fibers or polyolefin fibers.

  (3) The sheet for wallpaper according to (1) or (2), wherein the nonwoven fabric contains hot water-soluble binder fibers.

  According to the present invention, it is possible to prevent the contaminants from being hydrophilic or oleophilic, to have good printability, to eliminate the need for bonding of films and the like, to improve productivity, and to the environmental aspect in the manufacturing process. Considerable wallpaper sheets can be provided.

  The wallpaper sheet of the present invention is a wallpaper sheet obtained by subjecting a nonwoven fabric containing wood pulp and synthetic fibers to a water and oil repellency treatment, wherein the nonwoven fabric is protonated with an acid (hereinafter referred to as “aminosiloxane”). A sheet for wallpaper which is a non-woven fabric which has been subjected to water and oil repellency treatment using a “protonated aminosiloxane” in some cases.

  First, the reason why the sheet for wallpaper of the present invention is a non-woven fabric that has been subjected to water and oil repellency treatment using protonated aminosiloxane with an acid will be described below.

  Aminosiloxane is a general term for polysiloxanes having aminoalkyl groups. For example, there are those represented by the general formula (I), but the present invention is not limited thereto.

R _a (— (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ ) _b SiO _{(4-ab / 2)} (I)
R ⁴ represents a substituted or unsubstituted alkyl group, alkoxy group, or hydroxyl group.

  In addition, although many aminosiloxanes 1-3 are each known for a and b, this invention is not limited to this. Further, when R is a substituted or unsubstituted alkyl group or alkoxy group, many aminosiloxanes each having 1 to 20 carbon atoms are known, but the present invention is not limited thereto.

  Next, a method for protonating aminosiloxane with an acid will be described by way of example, but the present invention is not limited to this. As a method for protonating aminosiloxane with an acid, for example, aminosiloxane is added to water and suspended using a stirrer or the like. At this time, if it is difficult to suspend, a small amount of an auxiliary solvent such as ethylene glycol monobutyl ether may be added. While continuing stirring, a protonating agent (acid) is added little by little, and water is further added to adjust the concentration to obtain a protonated aminosiloxane emulsion. As the protonating agent, an organic or inorganic proton acid can be used, and examples thereof include acetic acid, citric acid, hydrochloric acid, sulfuric acid, hydrochloric acid, formic acid and the like, but the present invention is not limited thereto. is not.

  In aminosiloxane, an aminoalkyl group is protonated by adding an acid, and an emulsifier is not used, or an oil-in-water emulsion can be obtained with a small amount. Generally, the usage-amount of an emulsifier is 5 mass parts or less with respect to aminosiloxane. Since the protonated aminosiloxane thus obtained does not use an emulsifier or uses only a small amount, it can prevent the hydrophobicity from being lowered by the emulsifier, and has higher repellency than the aminosiloxane using the emulsifier. Since wateriness can be provided, adhesion of hydrophilic contaminants can be prevented. In addition, since polysiloxane such as aminosiloxane has oil repellency, adhesion of lipophilic contaminants can also be prevented. Furthermore, in the present invention, since the aminoalkyl group is protonated, that is, ionized, it repels lipophilic contaminants, and thus lipophilic contaminants are more difficult to adhere.

  Another example in which no emulsifier is used is a method using a soap-free emulsion using a reactive emulsifier having a surfactant function as a monomer. However, in the general soap-free emulsion, although the emulsified component is not separated from the polymer, since the polymer functions as an emulsifier, a decrease in hydrophobicity cannot be avoided as in the case of using an emulsifier. Since the protonated aminosiloxane of the present invention does not contain a reactive emulsifier, the hydrophobicity is not lowered by the emulsifier.

  Next, the reason why the wallpaper sheet of the present invention is a nonwoven fabric containing wood pulp and synthetic fibers will be described below.

  The wallpaper sheet may be used in a solid color, but is generally used by printing a predetermined pattern on the surface by a method such as gravure printing or flexographic printing. A nonwoven fabric using synthetic fibers has a cloth-like texture and is suitable as a sheet for wallpaper. In general, synthetic fibers have poorer printability than wood pulp. On the other hand, wood pulp has good printability even if it is made into a sheet alone. Therefore, by using a nonwoven fabric containing both wood pulp and synthetic fibers, a wallpaper sheet having a cloth-like texture can be obtained without impairing printability.

  The wallpaper sheet of the present invention is a wallpaper sheet in which a nonwoven fabric containing wood pulp and synthetic fibers is subjected to water and oil repellency treatments, and the nonwoven fabric is repelled using a protonated aminosiloxane with an acid. It is a nonwoven fabric that has been subjected to water and oil repellent treatment.

  The aminosiloxane protonated with the acid used in the present invention can be obtained as an oil-in-water emulsion. The surface of the emulsion particles is hydrophilic, but the aminosiloxane protonated with the acid used in the present invention does not use an emulsifier. Therefore, in the nonwoven fabric containing both wood pulp and synthetic fiber, it is less than wood pulp. Are more likely to adhere to the synthetic fiber. Therefore, the non-woven fabric containing both wood pulp and synthetic fibers, when used with the same concentration of protonated aminosiloxane, effectively attaches the protonated aminosiloxane to the non-woven fabric rather than wood pulp alone. Since the water repellency of the nonwoven fabric is increased, adhesion of hydrophilic contaminants can be prevented.

  On the other hand, polysiloxanes such as aminosiloxanes also have oil repellency, so that adhesion of lipophilic contaminants can be prevented, and even when they adhere, they can be easily wiped off. In addition, since protonated aminosiloxane adheres more to synthetic fibers than wood pulp, it does not impair printability under normal printing conditions.

  Water repellent and oil repellent treatment methods using protonated aminosiloxane include applying wet protonated aminosiloxane by impregnation or coating to a non-woven fabric in a wet paper state after paper making or in a dry state after drying, and then drying. Is preferred. The impregnation or coating method is not particularly limited, and examples thereof include a size press method, a tab size press method, a spray method, and a gravure coating method.

The amount of the protonated aminosiloxane used in the present invention applied to the nonwoven fabric is preferably 0.01 to 2.00 g / m ² , more preferably 0.05 to 1.50 g / m ² as the solid content, and 0.10. ˜1.00 g / m ² is particularly preferred. When the amount to be applied is less than 0.01 g / m ² , it may not be possible to sufficiently prevent the adhesion of contaminants. On the other hand, when it exceeds 2.00 g / m < ² >, printability may worsen.

  The ratio of the wood pulp and the synthetic fiber contained in the wallpaper sheet of the present invention is preferably 90:10 to 20:80, more preferably 85:15 to 50:50 in terms of mass ratio. If the content of the synthetic fiber is too small, it may not be possible to obtain a cloth-like texture, or the effects of water and oil repellency may be reduced, and the adhesion of contaminants may not be sufficiently prevented. On the other hand, when the content of the synthetic fiber is too large, printability may be deteriorated. Moreover, when there is too much content of a wood pulp, it may become easy to receive to the influence of humidity, such as a cloth-like texture not being obtained or expansion and contraction by a humidity change. On the other hand, when there is too little content of wood pulp, printability may worsen. Moreover, when manufacturing by a wet papermaking method, the water retention of the sheet before drying becomes poor, and it may be difficult to peel off from the felt.

  The wood pulp used in the present invention may be NBKP, LBKP, NBSP, LBSP, GP, TMP, or any other type of pulp, and is not particularly limited, but NBKP is preferred from the viewpoint of strength. The Canadian standard freeness is preferably in the range of 300 to 600 ml CSF. If the Canadian standard freeness is less than 300 ml CSF, the dimensional stability of the non-woven fabric may be reduced. If the Canadian standard freeness exceeds 600 ml CSF, the strength of the non-woven fabric may be reduced.

  Synthetic fibers used in the present invention include polyolefins, polyesters, polyvinyl acetates, ethylene-vinyl acetate copolymers, polyamides, acrylics, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl ethers, polyvinyl ketones. , Polyether, polyvinyl alcohol, diene, polyurethane, phenol, melamine, furan, urea, aniline, unsaturated polyester, alkyd, fluorine, silicone, polyamideimide, polyphenylene A sulfide system and a polyimide system can be used, but the present invention is not limited to these. The synthetic fiber may be a fiber (single fiber) made of a single resin, or may be a fiber (composite fiber) made of two or more kinds of resins. Examples of the composite fiber include a core-sheath type, an eccentric type, a side-by-side type, a sea-island type, an orange type, and a multiple bimetal type. These synthetic fibers may be used alone or in combination of two or more.

  In addition, when using polyester and polyolefin synthetic fibers, the resulting non-woven fabric not only has a cloth-like texture, but also has an appropriate softness suitable for embossing, etc. It is preferable to use at least one selected from

  The fiber diameter of the synthetic fiber used in the present invention is preferably 4 to 40 μm, more preferably 5 to 25 μm, and even more preferably 7 to 15 μm. If the fiber diameter of the synthetic fiber is less than 4 μm, it may fall off from the paper making wire during paper making. On the other hand, when the fiber diameter of the synthetic fiber exceeds 40 μm, the number of fibers may be relatively reduced, the strength may be lowered, and the smoothness of the sheet surface may be inferior.

  The fiber length of the synthetic fiber is preferably 1 to 20 mm, more preferably 2 to 15 mm, and still more preferably 3 to 10 mm. If the fiber length of the synthetic fiber is less than 1 mm, the fibers are hardly entangled and the strength may be lowered. On the other hand, when the fiber length of the synthetic fiber exceeds 20 mm, it may become easy to generate kinks or clumps during paper making, and the formed nonwoven fabric may become non-uniform.

  The method for producing the nonwoven fabric according to the present invention is not particularly limited, and can be selected and used as needed, such as dry methods such as spunbond, chemical bond, melt blow, and wet papermaking. It is easy to make pulp into a slurry, it is easy to mix and use multiple fibers with different fiber lengths and fineness, if necessary, a filler to increase opacity, and a sizing agent to further increase water repellency Can be added internally, and wet papermaking is particularly preferred. The nonwoven fabric may have a multilayer structure. The multilayer structure can be manufactured by a combination paper machine, or may be manufactured by laminating using a separate processing machine.

  Moreover, in this invention, it is preferable that a nonwoven fabric contains at least 1 sort (s) chosen from polyvinyl alcohol (PVA) type fiber, viscose type fiber, polyester type fiber, and polyolefin type fiber as a binder fiber. Two or more kinds of binder fibers may be used in combination. The binder fiber may be a single fiber or a composite fiber such as a core-sheath fiber or a split fiber.

  In particular, hot water-soluble binder fibers, such as PVA fibers, are hardly dissolved in room temperature water and maintain the fiber form. However, when heated in a state containing moisture after papermaking, they begin to dissolve easily. Once dissolved, when pressed with equipment such as a touch roll, it develops a binder ability that works between synthetic fibers and wood pulp, and then re-solidifies by dehydration and drying, and it can be done easily only in high-temperature water. This is particularly preferable because it is a strong binder fiber that does not dissolve.

  5-50 mass% is preferable with respect to the total fiber content of a nonwoven fabric, 7-40 mass% is more preferable, and, as for content of a binder fiber, 10-30 mass% is further more preferable. When the content of the binder fiber is less than 5% by mass, the tensile strength is weak and the paper may be cut off during wet papermaking. If the content of the binder fiber exceeds 50% by mass, the non-woven fabric becomes hard and the cloth-like texture is impaired, and the printability may be deteriorated due to the relatively decreased content of the wood pulp.

  When the binder fiber used in the present invention is a synthetic fiber, the binder fiber is also included in the synthetic fiber content when calculating the synthetic fiber content.

  The fiber diameter of the binder fiber according to the present invention is preferably 4 to 40 μm, more preferably 6 to 25 μm, and still more preferably 10 to 18 μm. If the fiber diameter of the binder fiber is less than 4 μm, it may fall off from the paper making wire during paper making, and the binder ability may be reduced. On the other hand, when the fiber diameter of the binder fiber exceeds 40 μm, the specific surface area of the fiber is relatively decreased, the binder ability may be decreased, and the smoothness of the sheet surface may be deteriorated. The fiber length of the binder fiber is preferably 1 to 20 mm, more preferably 2 to 15 mm, and still more preferably 3 to 10 mm. When the fiber length of the binder fiber is less than 1 mm, the binder ability may be lowered. On the other hand, when the fiber length of the binder fiber exceeds 20 mm, the paper fabric is likely to be twisted or hardened, and the formed nonwoven fabric may be uneven.

  The nonwoven fabric according to the present invention may contain fibers other than wood pulp, synthetic fibers, and binder fibers as necessary for the purpose of adjusting voids and strength. Examples of such fibers include regenerated fibers such as rayon, cupra, and lyocell fibers, and inorganic fibers such as glass, silica, ceramics, and rock wool. However, the present invention is not limited to these. Absent.

The basis weight of the nonwoven fabric according to the present invention is preferably 15~200g / ^{m 2,} more preferably 20 to 120 g / ^{m 2,} more preferably 30 to 100 g / ^{m 2.} When the basis weight of the nonwoven fabric is less than 15 g / m ² , the strength may be weakened. Moreover, when the basic weight of a nonwoven fabric exceeds 200 g / m < ² >, not only the texture as a wallpaper is bad, but it may become easy to peel from a wall with dead weight. In addition, the basic weight said by this invention means the basic weight based on the method prescribed | regulated to JISP8124 (paper and paperboard-basic weight measuring method). Moreover, 50-500 micrometers is preferable, as for the thickness of a nonwoven fabric, 70-350 micrometers is more preferable, and 100-300 micrometers is more preferable. When the thickness of the nonwoven fabric is less than 50 μm, rigidity may be insufficient or post-processing such as embossing may be difficult. If it exceeds 500 μm, uneven printing may easily occur. In addition, the thickness of the base material said by this invention means the value measured using the outside micrometer by the method prescribed | regulated to JISB7502. The density of the nonwoven fabric is preferably 0.10~0.90g / cm ^3, more preferably 0.20~0.80g / cm ^3, more preferably 0.30~0.70g / cm ^3. When the density of the nonwoven fabric is less than 0.10 g / cm ³ , the inter-fiber adhesion may be poor and dimensional stability may not be ensured. On the other hand, if the density of the nonwoven fabric exceeds 0.90 g / cm ³ , the nonwoven fabric becomes hard and post-processing such as embossing may be difficult.

  Moreover, a sizing agent can be mix | blended with the nonwoven fabric concerning this invention as needed. As the sizing agent, any reinforced rosin sizing agent, rosin emulsion sizing agent, petroleum resin sizing agent, synthetic sizing agent, neutral rosin sizing agent, alkyl ketene dimer (AKD) may be used as long as the desired effect of the present invention is not impaired. Any of known sizing agents such as) can be used. In addition, by blending the sizing agent, the amount of protonated aminosiloxane used can be reduced and the adhesion of hydrophilic pollutants can be further prevented. It is preferable to add a sizing agent internally.

  In addition to these, an anionic, nonionic, cationic or amphoteric retention improver, a filtering agent, a dispersant, a paper strength improver and a sticking agent are appropriately selected and used as necessary. In addition, internal additives for papermaking such as a pH adjuster, an antifoaming agent, a pitch control agent, and a slime control agent can be appropriately added depending on the purpose.

  In addition, if necessary, for example, clay, kaolin, calcined kaolin, talc, calcium carbonate, titanium dioxide, fillers having self-extinguishing properties such as aluminum hydroxide, magnesium hydroxide, etc. It is preferable to make it contain. Further, these fillers may be used by coating on the surface of the nonwoven fabric together with a binder such as a water-soluble resin or latex.

In addition, the wallpaper sheet of the present invention may be directly applied to a wall, used as a cover, and may be used by adhering to a backing paper. When using the backing paper, the basis weight of the backing paper is not particularly limited, but is preferably 40 to 150 g / m ² . As the backing paper, paper, a synthetic resin film, or a sheet bonded with these is preferable because it is easy to handle. Also, backing paper that has been concealed with fillers such as clay, kaolin, calcined kaolin, talc, calcium carbonate, and titanium dioxide, and backing that has reduced dimensional changes when glued using sizing agents and synthetic fibers Paper is particularly preferred.

  The wallpaper sheet of the present invention may be used as it is, but a pattern is printed as necessary. Examples of printing methods include gravure printing, screen printing, flexographic printing, and the like, and these methods can be used alone or in combination. Moreover, you may give the embossing for forming an uneven | corrugated pattern in the sheet | seat for wallpaper of this invention. Further, printing and embossing may be performed after bonding the backing paper.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples. Further, in the examples, unless otherwise indicated, parts and percentages are based on mass.

[Preparation of Protonated Aminosiloxane-A]
90 g of aminosiloxane having a functional group “— (CH ₂ ) ₃ NH (CH ₂ ) NH ₂ ” (amine value: 34 KOH mg / g, kinematic viscosity at 25 ° C .: 800 mm ² / s), ethylene glycol monobutyl ether as an auxiliary solvent 3 g, 30 g of water and 1 g of glacial acetic acid (acid, protonating agent) were added with stirring, and water was added little by little while continuing stirring to make a total of 500 g, and an opaque oil-in-water emulsion was obtained. This was diluted with water so that the aminosiloxane content was 5% to obtain protonated aminosiloxane-A.

[Preparation of Aminosiloxane-B]
90 g of aminosiloxane having a functional group “— (CH ₂ ) ₃ NH (CH ₂ ) NH ₂ ” (amine value: 34 KOH mg / g, kinematic viscosity at 25 ° C .: 800 mm ² / s), 150 g of water, and about 8 as an emulsifier. 30 parts of isotridecyl ethoxylate having 1 ethylene oxide unit and 45 parts of n-butyl ethoxylate having about 2 ethylene oxide units are added with stirring, and water is added little by little while continuing stirring to make a total of 500 g. An opaque oil-in-water emulsion was obtained. This was diluted with water so that the content of aminosiloxane was 5% to obtain aminosiloxane-B emulsified with an emulsifier.

[Preparation of Aminosiloxane-C]
Commercially available water-soluble aminosiloxane (manufactured by Dow Corning Toray Co., Ltd., trade name: BY16-893) is used as aminosiloxane-C, and diluted with water so that the content becomes 5% to obtain an aqueous solution of aminosiloxane-C. It was.

[Preparation of synthetic fiber dispersion]
Synthetic fibers and binder fibers were added to the water in the pulper dispersion tank at the ratio shown in Table 1, and mixed and dispersed for 10 minutes to prepare a synthetic fiber dispersion.

The details of the abbreviations shown in Table 1 are as follows.
F-1: Short polyester fiber. Fineness 0.6 dtex. Fiber length 5 mm.
F-2: Polypropylene / polyethylene core-sheath fiber. Core polypropylene. Sheath high density polyethylene. Fineness 0.9dtex. Fiber length 5 mm.
F-3: Acrylic fiber. Fineness 0.5 dtex. Fiber length 5 mm.
B-1: Thermal fusion type core-sheath binder fiber. Low-melting point copolyester having a core polyester and sheath flow starting temperature of 110 ° C. Fineness 2.2 dtex. Fiber length 5 mm.
B-2: Hot water soluble binder fiber (PVA fiber). Fineness 1.1 dtex. Fiber length 3mm.
P: NBKP (wood pulp).

[Preparation of wood pulp dispersion]
NBKP (wood pulp) beaten in 500 ml CSF was added to the water in the pulper dispersion tank and dispersed for 10 minutes. A wood pulp dispersion was prepared by adding 1% by mass of polyamide epichlorohydrin resin (manufactured by Arakawa Chemical Industries, trade name: Arafix (registered trademark) 100) as a wet paper strength enhancer to the wood pulp.

[Production of non-woven fabrics 1 to 11]
Nonwoven fabrics 1 to 11 were produced using a circular net paper machine. The synthetic fiber dispersion and the wood pulp dispersion were sent to a storage tank and mixed so as to have a mixing ratio shown in Table 1. The mixed dispersion is fed to the paper making head so as to have the basis weight shown in Table 1, and after pressing the wet paper web, it is pressed and dried against the Yankee dryer surface to obtain non-woven fabrics 1 to 11 shown in Table 1. It was.

[Production of non-woven fabric 12]
The nonwoven fabric 12 was manufactured using a combination paper machine in which an inclined wire type paper machine and a circular net paper machine were installed online. Synthetic fiber dispersion and wood pulp dispersion are stored in storage tanks for the first layer (for inclined wire type paper machines) and for the second layer (for circular net paper machines) so that the mixing ratio shown in Table 1 is obtained. Feed mixed. The mixed dispersions are sent to the first paper head (inclined wire type paper machine) and the second paper machine head (circular paper machine), respectively, so that the basis weight shown in Table 1 is reached, and the paper is combined in the wet paper web state. After that, it was pressed and dried so that the surface of the second layer was in contact with the Yankee dryer surface, to obtain a nonwoven fabric 12 consisting of two layers shown in Table 1.

[Production of non-woven fabrics 13 to 14]
Nonwoven fabrics 13 to 14 were produced using a circular net paper machine. The synthetic fiber dispersion and the wood pulp dispersion were sent to the storage tank and mixed so as to have the same mixing ratio as that of the nonwoven fabrics 1 and 6. While stirring the mixed dispersion, 6 parts of aluminum hydroxide (made by Showa Denko, trade name: H-42) and titanium oxide (made by DuPont, trade name: Taipure (registered trademark)) are used as inorganic pigments to increase opacity. ) RPD-2) 4 parts were added, and then 0.05 part of an acrylic amide yield improver was added and stirred for 10 minutes. The obtained dispersion was sent to a papermaking head, a wet paper web was made, and then pressed, and applied to the Yankee dryer surface and dried to obtain nonwoven fabrics 13 to 14.

[Production of non-woven fabric 15]
The nonwoven fabric 15 was prepared in the same manner as the nonwoven fabric 1 except that 1% by mass of an alkyl ketene dimer sizing agent (manufactured by Seiko PMC, trade name: AD1602) was added at the time of preparation of the synthetic fiber dispersion and the wood pulp dispersion. Manufactured.

[Manufacture of wallpaper sheet]
<Examples 1-9>
Protonated aminosiloxane-A was diluted so that the content of aminosiloxane was 0.2%. The diluted solution is impregnated with non-woven fabrics 1-9, and after excess liquid is squeezed out between two rollers, it is dried with a hot air drying dryer at 120 ° C. to obtain wallpaper sheets of Examples 1-9. It was.

<Examples 10 to 13>
The sheet | seat for wallpaper of Examples 10-13 was obtained like Example 1-9 except having used the nonwoven fabrics 12-15 instead of the nonwoven fabrics 1-9 in Examples 1-9.

<Comparative Examples 1-2>
Wallpaper sheets of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1 except that aminosiloxane-B and aminosiloxane-C were used in place of protonated aminosiloxane-A in Example 1, respectively.

<Comparative Examples 3-4>
Non-woven fabrics 1 and 15 were used as they were to obtain wallpaper sheets of Comparative Examples 3-4.

<Comparative Examples 5-6>
Instead of the nonwoven fabrics 1-9 in Examples 1-9, the wallpaper sheet of Comparative Examples 5-6 was obtained like Example 1-9 except having used the nonwoven fabrics 10-11.

[Evaluation]
The wallpaper sheet was subjected to the following evaluation on the surface side unless otherwise specified, with the nonwoven fabric Yankee dryer surface side as the surface.
[Measurement of Amount of Aminosiloxane Adhesion]
The amount of silicon present per unit area was measured with fluorescent X-rays, and based on this, the amount of aminosiloxane deposited (g / m ² ) was calculated. The results are shown in Table 2.

[Pollution Resistance 1: Lipophilic Pollutant]
Carbon black (0.2 g) was mixed with liquid paraffin (0.8 g) and diluted with 100 ml of automobile engine oil to prepare a lipophilic contaminant for evaluation. 0.1 ml of this lipophilic contaminant was hung with a dropper on the wallpaper sheets obtained in Examples 1 to 13 and Comparative Examples 1 to 6, and wiped with a white cloth 60 seconds later. Using the gray scale for contamination of JIS L 0805, the level of contamination of the part where the contaminant was wiped off was evaluated on a 1-9 scale. The evaluation was 9 when no contaminants remained, and the contamination resistance against lipophilic contaminants was determined according to the following criteria. The results are shown in Table 2.
○: Level 8 or more and 9 or less. There is almost no contamination.
Δ: Level 7 or more and less than 8. Slight contamination is observed.
X: Less than level 7. Contamination is significant.
In addition, (circle) or (triangle | delta) is a level which does not have a problem.

[Contamination resistance 2: hydrophilic contaminants]
0.1 ml of water colored with a dye was dropped on the wallpaper sheets obtained in Examples 1 to 13 and Comparative Examples 1 to 6 with a dropper, and the time until water penetrated was measured. In addition, 10 minutes after dripping water, it was wiped off with paper, the coloring state with the dye was confirmed, and the contamination state of the surface was confirmed according to the following criteria. The results are shown in Table 2.
○: It takes 10 minutes or more until water penetrates. Moreover, coloring with dye is not recognized.
Δ: It takes 10 minutes or more for water to permeate, but a slight coloring by the dye is observed.
X: Time until water permeates is 5 minutes or more and less than 10 minutes, and coloring with a dye is observed.
XX: Time until water permeates is less than 5 minutes, and coloring with a dye is observed.
In addition, (circle) or (triangle | delta) is a level which does not have a problem.

[Printability 1]
Flexographic printing was performed on the nonwoven fabrics 1-15. Among these, what was printed on the nonwoven fabric 1 was used as a standard sample. Moreover, the same printing was performed to the wallpaper sheet obtained in Examples 1-13 and Comparative Examples 1-6, and it compared with the printability of the used nonwoven fabric. The printability was determined according to the following criteria. The results are shown in Table 2.
A: Almost the same as the standard sample. And almost the same as the corresponding non-woven fabric.
○: Printing unevenness is partially observed and slightly inferior to the standard sample, but there is no problem in use. It is almost equivalent to the corresponding non-woven fabric.
Δ: Printing unevenness is partially observed, slightly inferior to the standard sample, slightly inferior to the corresponding non-woven fabric, but no problem in use.
X: It is far inferior to a standard sample and cannot be used.

[Printability 2]
In the printability 1, the wallpaper sheet for which the printability was determined to be “◯” or “Δ” was continuously printed at 1000 m, and the flexographic printing plate was visually checked for stains. The results are shown in Table 2.
A: Almost no dirt is observed.
Δ: Slight dirt is observed, but printing is not hindered.
In the evaluated wallpaper sheets, none of the flexographic printing plates was so soiled as to interfere with printing.

[Opacity]
The opacity (%) was measured according to JIS P 8149 using a spectroscopic color difference meter PF-10 manufactured by Nippon Denshoku. A larger opacity value is preferable because the concealability becomes higher, and the opacity is particularly preferably 80% or more.

[Processability: Embossing]
The wall paper sheets obtained in Examples 1 to 13 and Comparative Examples 1 to 6 were bonded to a backing paper having a basis weight of 100 g / m ² and a vinyl acetate emulsion, and then heated to 120 ° C., depth of 300 μm, size. The embossing was performed by passing between a 0.4 mm square engraving roll and a paper roll at a speed of 1 m, pressurizing with a pressure of 200 MPa, and then passing through a cooling roll and cooling. The thickness before and after the embossing was measured with a dial gauge thickness gauge (PURICOCK PURIHT DIAL GAUGE (0.001 × 2 mm), No. 25, measuring element 5 mmφ flat type), and the embossing rate was obtained by the following formula. . Moreover, the same measurement was performed 5 times about the same sample and the average value of the obtained embossing rate was made into the embossing rate of the said sample. The embossing rate is preferably 10% or more.

Embossing rate (%): {(d−d0) / 300} × 100
d: Thickness after embossing (μm)
d0: Thickness before embossing (μm)
Engraving depth: 300 μm

  From the comparison between Example 1 and Comparative Examples 1 to 3 and the comparison between Example 13 and Comparative Example 4, the nonwoven fabric was subjected to water and oil repellency treatment using aminosiloxane protonated with an acid, thereby making it hydrophilic. It is possible to obtain a wallpaper sheet that is prevented from adhering to any lipophilic contaminant. Further, from the comparison between Example 1 and Comparative Examples 5 to 6, the nonwoven fabric was a nonwoven fabric containing wood pulp and synthetic fibers, so that the nonwoven fabric was water-repellent using aminosiloxane protonated with an acid. When the oil repellent treatment is performed, adhesion of both hydrophilic and oleophilic contaminants can be prevented, and a wallpaper sheet having good printability can be obtained.

  Further, by comparing polyester fibers or polyolefin fibers as synthetic fibers in the nonwoven fabric, a wallpaper sheet having excellent printability and excellent processability can be obtained by comparing Examples 7 to 8 and Example 9. Can do.

  In addition, the comparison between Examples 3 to 4 and 7 to 10 and Examples 1 to 2, 5 to 6, and 11 to 13 indicates that the nonwoven fabric contains hot water-soluble binder fibers, so that the printing plate is stained. Is prevented, and a sheet for wallpaper having better printability can be obtained.

  Further, from the comparison between Example 1 and Example 11 and Example 6 and Example 12, the inclusion of an inorganic pigment can increase the opacity and increase the concealability. Further, from the comparison between Example 1 and Example 13, hydrophilic contaminants can be further prevented by internally adding a sizing agent to the nonwoven fabric.

  The wallpaper sheet of the present invention can be suitably used as an interior member used in a house or the like.

Claims (3)

  A wallpaper sheet in which a non-woven fabric containing wood pulp and synthetic fiber has been subjected to water and oil repellency treatments, and has been subjected to water and oil repellency treatments using aminosiloxane protonated with acid. Characteristic sheet for wallpaper.   The wallpaper sheet according to claim 1, wherein the synthetic fiber is at least one selected from polyester fibers or polyolefin fibers.   The wallpaper sheet according to claim 1 or 2, wherein the nonwoven fabric contains hot water-soluble binder fibers.