JP2021017560A - Film forming composition, and plastisol composition - Google Patents

Abstract

To intend to enhance antifouling property in various kinds of moldings such as decorative paper, wall paper and leather paper.SOLUTION: The present invention provides a film forming composition, a plastisol composition, and a polyvinyl chloride-based resin composition, which contains a polyvinyl chloride-based polymer, and one or more kinds selected from the group consisting of a cellulose fiber, a chitin fiber, and a chitosan fiber. The composition may contain a plasticizer. The plasticizer may be one or more kinds selected from the group consisting of DINP, DOP, DOTP, DINA, ATBC, TOTM and DINCH. The composition may contain a surfactant. The surfactant may be a nonionic surfactant and/or a cationic surfactant. The surfactant may be a nonionic surfactant. The HLB of the nonionic surfactant may be 8 to 19. Furthermore, the present invention also provides a cured material of the composition.SELECTED DRAWING: None

Description

The present invention relates to a film-forming composition, a plastisol composition, and the like.

In various molded products such as decorative paper used for interior building materials or furniture, wallpaper used for interior of buildings, and leather used for bags or furniture, dust, tobacco tar, oil, food, cosmetics, writing utensils or When dirt such as mold adheres, it is required that it can be easily wiped off with water, detergent, solvent or the like. Such ease of wiping off dirt on the surface of various molded products is also called "antifouling property".

As a technique for imparting antifouling property to various molded products, for example, Patent Document 1 describes a synthetic resin emulsion (A), a wax (B) having a melting point in the range of 40 to 110 ° C., and an average particle size of 1 to 1. It is an antifouling processing agent composed of polyolefin (C) having a drip point in the range of 100 μm and a drip point in the range of 50 to 170 ° C., and is a solid of wax (B) with respect to 100 parts by weight of solid content of synthetic resin emulsion (A). Disclosed is an antifouling agent characterized in that the amount is in the range of 3 to 50 parts by mass and the solid content of the polyolefin (C) is in the range of 5 to 200 parts by weight. Further, Patent Document 2 discloses a wallpaper coating agent containing an anionic polyester resin, wax, and silicone.

Japanese Unexamined Patent Publication No. 2004-0597774 JP-A-2017-014430

Further improvement of antifouling property is required for various molded products such as decorative paper, wallpaper and leather. Therefore, an object of the present invention is to improve the antifouling property of various molded products such as decorative paper, wallpaper and leather.

The present inventors have found that a specific polyvinyl chloride-based resin composition can enhance antifouling properties in various molded products such as decorative paper, wallpaper and leather.

That is, the present invention provides a film-forming composition containing a polyvinyl chloride-based polymer and one or more selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers.
According to one embodiment of the present invention, the film-forming composition may contain a plasticizer.
The plasticizer may be a polyvalent carboxylic acid ester plasticizer.
The plasticizer may be one or more selected from the group consisting of DINP, DOP, DOTP, ATBC, TOTM, and DINA.
According to another embodiment of the present invention, the film-forming composition may contain a surfactant.
The surfactant can be a nonionic surfactant and / or a cationic surfactant.
The present invention also provides a film which is a cured product of the film-forming composition.
The present invention also provides a laminate containing a film, which is a cured product of the film-forming composition, as at least one surface layer.

The present invention provides a plastisol composition comprising a polyvinyl chloride polymer and one or more selected from the group consisting of cellulosic fibers, chitin fibers, and chitosan fibers.
According to one embodiment of the invention, the plastisol composition may include a plasticizer.
The plasticizer may be a polyvalent carboxylic acid ester plasticizer.
The plasticizer may be one or more selected from the group consisting of DINP, DOP, DOTP, DINA, TOTM, and DINCH.
According to other embodiments of the present invention, the plastisol composition may comprise a surfactant.
The surfactant can be a nonionic surfactant and / or a cationic surfactant.
The surfactant may be a nonionic surfactant, and the HLB of the nonionic surfactant may be 8 to 19.
The present invention also provides a cured product of the plastisol composition.

The present invention provides a polyvinyl chloride-based resin composition containing a polyvinyl chloride-based polymer and one or more selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers.

The film-forming composition of the present invention, the plastisol composition, and the like can enhance the antifouling property of various molded products such as decorative paper, wallpaper, and leather.
The effect of the present invention is not necessarily limited to the effects described here, and may be any of the effects described in the present specification.

Hereinafter, embodiments for carrying out the present invention will be described in detail. The embodiments described below are examples of typical embodiments of the present invention, and the present invention is not limited to these embodiments. In this specification, the percentage is expressed by mass unless otherwise specified. Further, the upper limit value and the lower limit value of each numerical value range can be arbitrarily combined as desired.

1. 1. Film-forming composition The film-forming composition of the present invention contains at least one or more selected from the group consisting of polyvinyl chloride-based polymers, cellulosic fibers, chitin fibers, and chitosan fibers. The cured product of the film-forming composition of the present invention is suitable for enhancing antifouling properties in various molded products such as decorative paper, wallpaper and leather.

1-1. Each component of the film-forming composition Each component will be described below.
1-1 (1) Resin

The film-forming composition of the present invention contains at least a polyvinyl chloride-based polymer. For example, the film-forming composition may contain a resin containing a polyvinyl chloride-based polymer as a main component.

The polyvinyl chloride polymer _is a polymer having a group represented by -CH 2 -CHCl-. Examples of the polyvinyl chloride-based polymer include a homopolymer of vinyl chloride; a copolymer of a vinyl chloride monomer and another monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer. One or more selected from the group consisting of these can be used.

As a copolymer of the vinyl chloride monomer and another monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer, for example, vinyl chloride / vinyl acetate copolymer and vinyl chloride / (meth) acrylic acid can be used. Polymer, vinyl chloride / methyl (meth) acrylate copolymer, vinyl chloride / ethyl (meth) acrylate copolymer, vinyl chloride / maleic acid ester copolymer, vinyl chloride / ethylene copolymer, vinyl chloride / Propropylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride ternary copolymer, vinyl chloride / styrene / acrylonitrile Three-way copolymer, vinyl chloride / butadiene copolymer, vinyl chloride / isoprene copolymer, vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride / vinyl acetate ternary copolymer, vinyl chloride / acrylonitrile Examples thereof include copolymers and vinyl chloride / various vinyl ether copolymers.

The method for producing the polyvinyl chloride polymer is not particularly limited. As the polyvinyl chloride-based polymer, for example, those produced by various polymerization methods such as an emulsion polymerization method, a suspension polymerization method or a massive polymerization method can be used. As the polyvinyl chloride polymer, a commercially available product may be used.

The polyvinyl chloride-based polymer may be crosslinked. Examples of the method for cross-linking the polyvinyl chloride-based polymer include a method of adding a cross-linking agent and a peroxide, a method of irradiating an electron beam, and a method of using a water-crosslinkable material.

The polyvinyl chloride-based polymer may be a polymer blend. As the polymer blend, for example, a blend of a polyvinyl chloride polymer and a polyolefin may be used. Examples of the polyolefin include linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer, ethylene-propylene copolymer, polypropylene, and the like. Examples thereof include propylene-α-olefin copolymer, polybutene, polypentene, chloropolyethylene, chloropolypropylene and the like, and one or more selected from the group consisting of these can be used.

The polyvinyl chloride-based polymer may be further chlorinated. Examples of the chlorination method for the polyvinyl chloride-based polymer include a thermal chlorination method and a photochlorination method.

In the film-forming composition of the present invention, the average degree of polymerization of the polyvinyl chloride-based polymer is preferably 300 to 5000, more preferably 500 to 3000, from the viewpoint of improving the antifouling property. , 500 to 2500, more preferably 600 to 2500, further preferably 600 to 2000, and even more preferably 600 to 1300. Here, the average degree of polymerization is the average degree of polymerization measured in accordance with JIS K-6720-2.

In the film-forming composition of the present invention, the K value of the polyvinyl chloride-based polymer is preferably 40 to 90, more preferably 50 to 90, from the viewpoint of improving the antifouling property. More preferably, it is 60 to 80. Here, the K value is a value measured in accordance with ISO1628-2 (JIS K7376-2 plastic-how to determine the viscosity of a polymer diluted solution using a capillary viscometer-Part 2: vinyl chloride resin). is there.

The polyvinyl chloride-based polymer can be generally classified into suspension vinyl chloride-based polymer, paste vinyl chloride-based polymer, and blended vinyl chloride-based polymer according to the shape, particle size, characteristics, and the like of the particles (. For example, Toshiro Igarashi, PVC Paste Processing Features and Applications, Section 1 PVC Paste Features (p12-23), Section 5 Other Combinations (p93-107), Paste Resin Rubber Digest, 1998.11).
The "particle diameter" of the "polychlorinated polymer" in the present specification is the "particle diameter (D50)". The particle size (D50) is a volume-based median diameter (D50) weighted by volume and is measured according to JIS Z8825. The particle size can be measured according to a laser diffraction type particle size analysis measurement method, and can be measured using, for example, a particle size analysis measuring device (SALD-2200, Shimadzu Corporation).

The film-forming composition of the present invention is one or more selected from the group consisting of a suspension vinyl chloride polymer, a paste vinyl chloride polymer, and a blended vinyl chloride polymer as a polyvinyl chloride polymer. Can be used.
The film-forming composition of the present invention preferably contains at least a suspension vinyl chloride-based polymer as a polyvinyl chloride-based polymer from the viewpoint of improving antifouling properties.
Further, the film-forming composition of the present invention may contain, as a polyvinyl chloride-based polymer, a suspension vinyl chloride-based polymer and a paste vinyl chloride-based polymer and / or a blended vinyl chloride-based polymer in combination. , It is more preferable from the viewpoint of improving the antifouling property. It is preferable to further contain the paste vinyl chloride polymer in the film-forming composition of the present invention from the viewpoint of improving the dispersibility of the fibers when the raw materials are mixed.

The suspension vinyl chloride-based polymer is preferably particles having a porous structure, and more specifically, particles having an indefinite shape with many voids inside the particles. The particle size (D50) of the suspension vinyl chloride polymer is preferably 50 to 200 μm, more preferably 100 to 150 μm. Since the suspension vinyl chloride polymer is particles having a porous structure, it can absorb a liquid such as a plasticizer inside the particles, so that it is generally difficult to form a paste. Generally, suspension vinyl chloride-based polymers are sometimes called "general-purpose PVC". The suspension vinyl chloride-based polymer can be obtained by a known production method, and as an example, it can be obtained by suspension polymerization or the like. The form of the vinyl chloride polymer may be a slurry state in which the particles are suspended in water, or a dry powder state.

The paste vinyl chloride polymer is preferably spherical particles, and more specifically, it is preferably true spherical particles having few voids inside and on the surface. The particle size (D50) of the paste vinyl chloride polymer is preferably 0.01 μm or more, more preferably 0.02 μm or more as a suitable lower limit value, and preferably 10 μm or less, more preferably 5 μm as a suitable upper limit value. The preferred numerical range is preferably 0.01 to 10 μm, more preferably 0.02 to 5 μm. Paste Vinyl chloride-based polymers are generally characterized in that they become a paste when a plasticizer is added. Paste vinyl chloride-based polymers are also commonly referred to as "special PVC". The paste vinyl chloride-based polymer can be produced by emulsion polymerization, microsuspension polymerization, or the like, and may be a latex in which the polymer particles are emulsified in water.

The blended vinyl chloride polymer is preferably spherical particles, and more specifically, it is not spherical like the paste vinyl chloride polymer, but has a deformed but relatively smooth surface, and is more appropriate. It is preferable that the particles have an affinity for plasticity. The particle size (D50) of the blended vinyl chloride polymer is preferably 20 to 100 μm, more preferably 20 to 80 μm, and even more preferably 20 to 60 μm. The general feature of the blended vinyl chloride polymer is that the viscosity of the paste vinyl chloride polymer can be lowered and that the surface of the formed product can be matted by forming minute protrusions. The blended vinyl chloride-based polymer can be obtained by a known production method. As an example, suspension polymerization is carried out by finely dispersing vinyl chloride monomer droplets and using a suspending agent in combination with a small amount of emulsifier. Can be obtained by

The content of the suspension vinyl chloride-based polymer in the film-forming composition of the present invention with respect to the total mass of the polyvinyl chloride-based polymer is not particularly limited, but is preferably 40% by mass or more as a suitable lower limit value. , More preferably 50% by mass or more, further preferably 60% by mass or more, still more preferably 70% by mass or more, and the suitable upper limit value is not particularly limited, for example, 100% by mass or less, 90% by mass or less. , Or 80% by mass or less. The preferred numerical range is more preferably 50 to 100% by mass, still more preferably 50 to 90% by mass, from the viewpoint of improving antifouling property.

The content of the paste vinyl chloride polymer and / or the blended vinyl chloride polymer with respect to the total mass of the polyvinyl chloride polymer in the film-forming composition of the present invention is not particularly limited, but is suitable. The lower limit is preferably 0% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more, from the viewpoint of improving the dispersibility of the fibers when the raw materials are mixed and improving the antifouling property. It is preferably 15% by mass or more, more preferably 20% by mass or more, and the suitable upper limit value is not particularly limited, and may be, for example, 100% by mass or less, 80% by mass or less, but from the viewpoint of improving antifouling property. Therefore, it is more preferably 70% by mass or less, further preferably 60% by mass or less, more preferably 50% by mass or less, or 40% by mass or less. The preferable numerical range is more preferably 0 to 50% by mass, still more preferably 20 to 50% by mass from the viewpoint of improving antifouling property.

The mass content ratio of the suspension vinyl chloride polymer to the total mass of the polyvinyl chloride polymer in the film-forming composition of the present invention is not particularly limited, but is not particularly limited. It is preferably 50 to 100:50 to 0, more preferably 60 to 95:40 to 5, and even more preferably 70 to 90:30 to 10, from the viewpoint of improving the antifouling property. As the other vinyl chloride-based polymer, the paste vinyl chloride-based polymer and / or the blended vinyl chloride-based polymer is preferable.

From the viewpoint of improving the antifouling property, the film-forming composition contains, for example, the resin of the polyvinyl chloride-based polymer in an amount of preferably 50% by mass or more, based on the total mass of the film-forming composition. It can be preferably contained in a proportion of 60% by mass or more. Further, from the viewpoint of improving the antifouling property, the film-forming composition preferably contains, for example, the polyvinyl chloride polymer in an amount of 60% by mass or more, more preferably 70% by mass or more, based on the total mass of the resin. It can be contained in a proportion of 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 99 to 100% by mass.

The resin may contain a resin other than the polyvinyl chloride polymer. Examples of the resin other than the polyvinyl chloride polymer include acrylic resin, polystyrene resin, polyethylene resin, polyimide resin, fluororesin, phenol resin, epoxy resin, urethane resin and the like, and are selected from the group consisting of these. One or more types can be used. From the viewpoint of improving the antifouling property, the resin is, for example, a resin other than the polyvinyl chloride polymer, preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the resin. It can be contained in a proportion of 20% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less.
In the film-forming composition of the present invention, the K value of the resin is preferably 40 to 90, more preferably 50 to 90, and more preferably 60 to 80, from the viewpoint of improving the antifouling property. Is more preferable.

1-1 (2) Cellulose fiber, and chitin fiber and chitosan fiber The film-forming composition of the present invention is selected from the group consisting of cellulose fiber, chitin fiber, and chitosan fiber from the viewpoint of improving antifouling property. It may contain one or more or two or more fibers. The fibers may be (a) cellulose fibers and / or (b) chitin fibers and / or chitosan fibers alone or in combination of two or more.
Further, as the fiber, a commercially available product may be used. The shape of the fiber may be any shape such as fibrous or granular. As the fiber, an aqueous dispersion of the fiber may be used.

The average fiber diameter of the fibers is preferably 1 nm or more, more preferably 2 nm or more, from the viewpoint of improving the antifouling property. The average fiber diameter is preferably 1000 nm or less, more preferably 100 nm or less.
Further, the average fiber length of the fibers is preferably 0.1 μm or more, and more preferably 1 μm or more, from the viewpoint of improving the antifouling property. The average fiber length is preferably 1000 μm or less, more preferably 100 μm or less.
The average fiber diameter and the average fiber length in the present invention can be calculated by, for example, measuring the diameters of a plurality of fibers (for example, 10 or more fibers) by electron micrographs and calculating the average values.

The content of the fiber in the film-forming composition is preferably 0.01 part by mass or more, preferably 0.02 part by mass with respect to 100 parts by mass of the resin, from the viewpoint of improving antifouling property. It is more preferably 0.2 parts by mass or more, and further preferably 0.2 parts by mass or more. The content of the chitosan fiber is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the resin. It is 3 parts by mass or less, more preferably 1 part by mass or less.

1-1 (2) -1. Cellulose fiber

Examples of the raw material of the cellulose fiber include, but are not limited to, wood, straw, bamboo, hemp, bagasse, kenaf, bamboo grass, reeds, cotton, and rice husks. One or more selected from the group consisting of these raw materials can be used. Cellulose fibers may be produced from plant fibers (also referred to as “pulp”) separated from these raw materials.
Further, the shape of the cellulose fiber may be any shape such as fibrous or granular. As the cellulose fiber, an aqueous dispersion of cellulose fiber may be used.

The method for producing the cellulose fiber is not particularly limited. For example, after chemically treating the above-mentioned raw material of cellulose fiber with an alkali such as sodium hydroxide, a refiner, a twin-screw kneader (biaxial extruder), a twin-screw kneader extruder, a high-pressure homogenizer, a medium stirring mill, a stone mill, and a grinder. , A method of mechanically grinding and / or beating with a vibration mill, a sand grinder, or the like. Further, the cellulose fiber obtained by subjecting the above-mentioned raw material of the cellulose fiber to an ultrahigh pressure treatment and removing lignin may be used as the cellulose fiber.
In addition, the cellulose fibers are subjected to oxidation treatment, dilute acid hydrolysis treatment, enzyme treatment, etc. using an N-oxyl compound such as 2,2,6,6-tetramethyl-1-piperidin-N-oxy radical (TEMPO). May be chemically treated.
Of these, TEMPO-oxidized cellulose fibers are preferable from the viewpoint of improving antifouling properties.

The average fiber diameter of the cellulose fibers is preferably 1 nm or more, more preferably 2 nm or more, from the viewpoint of improving the antifouling property. The average fiber diameter is preferably 1000 nm or less, more preferably 100 nm or less.
The average fiber length of the cellulose fibers is preferably 0.1 μm or more, and more preferably 1 μm or more, from the viewpoint of improving the antifouling property. The average fiber length is preferably 1000 μm or less, more preferably 100 μm or less.

From the viewpoint of improving the antifouling property, the cellulose fiber may have cellulose type I crystals, and the crystallinity thereof is preferably 50% or more, more preferably 56% or more. It is more preferably 60% or more.
The crystallinity in the present invention is the cellulose type I crystallinity calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and can be obtained by the following formula (1).
Cellulose type I crystallinity (%) = [(I _22.6- I _18.5 ) / I _22.6 ] x 100 ... (1)
In the above formula (1), I _22.6 is the diffraction intensity of the lattice plane (002) plane (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I _18.5 is the amorphous portion (diffraction angle). It shows a diffraction intensity of 2θ = 18.5 °). Cellulose type I refers to the crystalline form of natural cellulose, and cellulose type I crystallinity means the proportion of the total amount of crystalline regions in the total cellulose.

The cellulose fiber may be a commercially available product, and as the commercially available product, for example, nanoforest-S (manufactured by Chuetsu Pulp & Paper Co., Ltd.), BiNFi-s WFo-100 series (1002, 1005, 10010; manufactured by Sugino Machine Limited; WMa is ⁽ Integrated into WFo), Serenpia ^(R) series (TC-01A, TC-02X (TEMPO oxide CNF), CS-01, CS-01C (CMized CNF); manufactured by Nippon Paper Industries, Ltd.), Serish GY-100G ( (Manufactured by Daicel Fine Chem Ltd.), Leocrysta I-2SX (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like, and one or more selected from the group consisting of these can be used.

The content of the cellulose fibers in the film-forming composition is preferably 0.01 parts by mass or more, preferably 0.02 parts by mass, based on 100 parts by mass of the resin, from the viewpoint of improving antifouling properties. It is more preferably parts or more, still more preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more. The content of the cellulose fibers is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the resin. Is 3 parts by mass or less, more preferably 1 part by mass or less.

1-1 (2) -2. Chitin fiber, chitosan fiber

Examples of the raw materials for the chitin fiber and / or chitosan fiber include, but are not limited to, shells (exoskeleton) of crustaceans such as shrimp and crab, insects, shellfish, and mushrooms. One or more selected from the group consisting of these raw materials can be used.
The shape of the chitin fiber and / or the chitosan fiber may be any shape such as fibrous or granular. As the chitin fiber and / or chitosan fiber, an aqueous dispersion of chitin fiber and / or chitosan fiber may be used.
Generally, chitosan is also called deacetylated chitin, and can be obtained by de-acetylating chitin by hydrolysis or the like. Generally, a degree of deacetylation (% DA) of about 60% or more is called chitosan, and this% DA can be determined by colloid titration (for example, studies on chitin and chitosan by Kota Yokoyama et al., Journal of Japanese Oral Implantology, p16-24, Vol. 10, No. 1, March 1997).

The method for producing the chitosan fiber is not particularly limited. For example, the raw materials of the above-mentioned chitin fiber and / or chitosan fiber can be used as a refiner, a twin-screw kneader (biaxial extruder), a twin-screw kneader extruder, a high-pressure homogenizer, a medium stirring mill, a stone mill, a grinder, a vibration mill or a sand grinder. Examples thereof include a method of obtaining chitin fibers by mechanically grinding and / or beating with the like, a method of obtaining chitin fibers and then boiling treatment in a concentrated alkali to obtain chitosan fibers.
Before mechanically grinding and / or beating the raw material, the raw material may be treated with an alkali or an acid to remove proteins, calcium and the like from the raw material.

The average fiber diameter of the chitin fiber and / or chitosan fiber is preferably 1 nm or more, and more preferably 2 nm or more, from the viewpoint of improving the antifouling property. The average fiber diameter is preferably 1000 nm or less, more preferably 100 nm or less.
The average fiber length of the chitin fiber and / or chitosan fiber is preferably 0.1 μm or more, and more preferably 1 μm or more, from the viewpoint of improving the antifouling property. The average fiber length is preferably 1000 μm or less, more preferably 100 μm or less.

The chitin fiber and / or chitosan fiber may be a commercially available product, and examples of the commercially available product include chitin-NF (manufactured by Marine Nanofiber), partially hydrolyzed chitin-NF (manufactured by Marine Nanofiber), and Daichitosan series (manufactured by Marine Nanofiber). H, M, PVL, VLA: manufactured by Dainichiseika Kogyo Co., Ltd.), BiNFi-s SFo-200 series (manufactured by Sugino Machine Limited), BiNFi-s Efo-080 series (manufactured by Sugino Machine Limited), etc. One or more selected from the group consisting of can be used.

The content of the chitin fiber and / or chitosan fiber in the film-forming composition is preferably 0.01 part by mass or more with respect to 100 parts by mass of the resin from the viewpoint of improving antifouling property. , 0.02 parts by mass or more, more preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more. The content of the chitin fiber and / or chitosan fiber is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass with respect to 100 parts by mass of the resin. Hereinafter, it is more preferably 3 parts by mass or less, and more preferably 1 part by mass or less.

1-1 (3) Plasticizer

The film-forming composition of the present invention may contain a plasticizer.

Examples of the plasticizer include, but are not limited to, polyvalent carboxylic acid ester-based plasticizers and benzoic acid ester-based plasticizers from the viewpoint of improving antifouling properties. Examples of the polyvalent carboxylic acid ester-based plasticizer include phthalate ester-based plasticizers, terephthalate ester-based plasticizers, adipic acid ester-based plasticizers, trimellitic acid ester-based plasticizers, and citric acid ester-based plasticizers. However, it is not limited to these.

Examples of the polyvalent carboxylic acid ester-based plasticizer include mono, di, and triesters obtained from a polyvalent carboxylic acid and a monoalcohol or a (poly) oxyalkylene adduct thereof.
The carbon number of the polyvalent carboxylic acid is not particularly limited, but is preferably 3 to 10 carbon atoms, and a polyvalent carboxylic acid having 3 to 10 carbon atoms is preferable. Examples of the polyvalent carboxylic acid include, but are not limited to, trimellitic acid and dicarboxylic acid. Examples of the valence of the polyvalent carboxylic acid include 2, 3, and 4.
The carbon number of the monoalcohol is preferably 1 to 20, more preferably 1 to 12, and even more preferably 4 to 11. Examples of the monoalcohol include, but are not limited to, n-butanol, 2-ethylhexanol, octyl alcohol, isononyl alcohol, and isodecyl alcohol. As the monoalcohol or its (poly) oxyalkylene adduct, a monoalcohol having 1 to 4 carbon atoms or its (poly) oxyalkylene adduct is suitable.
The benzoic acid ester-based plasticizer can be obtained from benzoic acid and a monoalcohol or a (poly) oxyalkylene adduct thereof. The monoalcohol or its (poly) oxyalkylene adduct is not particularly limited, but may be the same as the monoalcohol of the polyhydric carboxylic acid or its (poly) oxyalkylene adduct.

Examples of the plasticizer in the film-forming composition include diisononyl phthalate (DINP), bis (2-ethylhexyl) phthalate (DOP), diisodecyl phthalate (DIDP), dibutyl phthalate (DBP) and diundecyl phthalate. Phthalate-based plasticizers such as (DUP); terephthalate-based plasticizers such as bis (2-ethylhexyl) terephthalate (DOTP); diisononyl adipate (DINA), bis (2-ethylhexyl) adipate (DOA) , Adiponic acid ester-based plasticizers such as diisodecyl adipate (DIDA); trimellitic acid ester-based plasticizers such as trioctyl trimellitic acid (TOTM); 1,2-cyclohexanedicarboxylic acid diisononyl ester (DINCH), etc .; acetylcitrate Examples thereof include citrate ester-based plasticizers such as tributyl (ATBC).
Of these, a phthalate ester-based plasticizer is preferable from the viewpoint of improving antifouling property and cost.
One or more selected from the group consisting of these plasticizers can be used.

In the film-forming composition, from the viewpoint of improving antifouling property, one or more selected from the group consisting of DINP, DOP, DOTP, ATBC, DINA, TOTM, and DINCH is used as the plasticizer. Is preferable. Of these, one or more selected from the group consisting of DINP, DOP, DOTP, ATBC, TOTM, and DINA from the viewpoint of improving antifouling property and film forming property in the film-forming composition. Is more preferably used, and more preferably one or more selected from the group consisting of DINP, DOP, ATBC, and DINA.

In the film-forming composition, examples of the plasticizer other than the polyvalent carboxylic acid ester plasticizer and the benzoic acid ester plasticizer include polyester plasticizers, glycerin plasticizers, polyalkylene glycol plasticizers and epoxys. Examples thereof include system plasticizers, and one or more selected from these plasticizers may be used.
The plasticizer may be manufactured by a known manufacturing method or may be a commercially available product.

The content of the plasticizer in the film-forming composition is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the resin from the viewpoint of improving antifouling property, and is preferably 1 part by mass or more. It is more preferably 3 parts by mass or more, more preferably 4 parts by mass or more, still more preferably 5 parts by mass or more. The content of the plasticizer is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 50 parts by mass or less with respect to 100 parts by mass of the resin. , More preferably 40 parts by mass or less, further preferably 30 parts by mass or less, and more preferably 20 parts by mass or less.

1-1 (4) Surfactant

The film-forming composition of the present invention may contain a surfactant.

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and the like, and one or more selected from the group consisting of these. Can be used. The HLB of the surfactant is preferably 8 to 19 from the viewpoint of dispersibility in the plasticizer.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyalkylene cured castor oil and the like. Examples of the cationic surfactant include amine salts and quaternary ammonium salts. Examples of the anionic surfactant include carboxylates, sulfates, sulfonates, phosphate salts and the like. Examples of amphoteric surfactants include carboxybetaine and sulfobetaine.
One or more selected from the group consisting of these surfactants can be used.

From the viewpoint of improving the antifouling property, it is preferable to use a nonionic and / or cationic surfactant as the surfactant in the film-forming composition. When a nonionic surfactant is used, the HLB is preferably 8 to 19 from the viewpoint of dispersibility in the plasticizer.

The surfactant may be a commercially available product, and examples of the commercially available product include Emargen 1150S-60 (polyoxyethylene alkyl ether (HLB 18.5), manufactured by Kao Corporation) and Emargen 103 (polyoxyethylene lauryl ether (HLB 8)). .1), Kao Corporation), Acetamine 24 (coconut amine acetate, Kao Corporation) and the like can be used, and one or more selected from the group consisting of these can be used.

From the viewpoint of improving the antifouling property, the content of the surfactant in the film-forming composition is preferably, for example, 10 parts by mass or less with respect to 100 parts by mass of the resin, and is preferably 1 part by mass or less. It is more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less. Further, the lower limit of the content of the surfactant is not particularly limited. The content of the surfactant may be, for example, 0.0001 parts by mass or more, 0.001 parts by mass or more, or 0.01 parts by mass or more with respect to 100 parts by mass of the resin. There may be.

1-1 (5) Other Ingredients In addition to the above-mentioned ingredients, the film-forming composition of the present invention contains a matting agent, a processing aid, a mold release agent, a stabilizer, a softener, and an antioxidant (antioxidant). ), Antibacterial agent, antifungal agent, coloring pigment, ultraviolet absorber, flame retardant, filler and the like may be appropriately contained.
Examples of the matting agent include, but are not limited to, hydrophilic fumed silica and acrylic matting agents. The content of the matting agent is not particularly limited, but the upper limit thereof may be, for example, 10 parts by mass or less, 8 parts by mass or less, or 5 parts by mass or less with respect to 100 parts by mass of the resin. The lower limit may be, for example, 0.01 part by mass or more, 0.1 part by mass or more, 0.5 part by mass or more, or 1 part by mass or more.

1-2. Method for producing a film-forming composition

The method for producing a film-forming composition of the present invention can be obtained by mixing raw materials, and examples thereof include Examples 1 and 2 below, but the present invention is not particularly limited thereto.
The form of the film-forming composition is not particularly limited, such as paste, liquid, and powder, but it is preferable to use the film-forming composition in powder form when forming the film.

Example 1 of the method for producing a film-forming composition of the present invention may include the following steps:
One or more fibers selected from the group consisting of cellulosic fibers, chitin fibers, and chitosan fibers, surfactants and / or plasticizers, vinyl chloride polymers, and other raw materials (impact improver, thermal stability). A mixing step of mixing with an agent) to obtain a mixture.
The mixing step may be performed by a stirrer known in the art. The mixing step can be performed, for example, at room temperature (20 to 30 ° C.). The raw materials may be added to the stirrer at the same time or separately, but it is preferable to mix the raw materials together to obtain a mixture.
In the step of obtaining the mixture, a resin other than the polyvinyl chloride polymer may also be mixed.

Example 2 of the method for producing a film-forming composition of the present invention may include the following steps:
(1) A step of mixing one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers with a surfactant and / or a plasticizer to obtain a fiber-containing material; and (2). ) A step of mixing the fiber-containing material obtained in the step of obtaining the fiber-containing material, a vinyl chloride-based polymer, and other raw materials (impact resistance improver, heat stabilizer) to obtain a mixture.
The step of obtaining the fiber-containing material and the step of obtaining the mixture may be carried out by a stirring device known in the art, respectively. The step of obtaining the fiber-containing material and the step of obtaining the mixture can be carried out, for example, at room temperature (20 to 30 ° C.), respectively.
In the step of obtaining the mixture, the surfactant and / or the plasticizer may be mixed. In the step of obtaining the mixture, a resin other than the polyvinyl chloride polymer may be mixed.

1-3. A cured product of a film-forming composition and a laminate containing the cured product

The present invention can provide a film which is a cured product of the film-forming composition. By using the film, the antifouling property of various molded products can be enhanced.

The film, which is a cured product of the film-forming composition of the present invention, can be obtained by curing the film-forming composition by a known curing method. The cured product may be a foam.

The curing method may be performed by a method known in the art, and examples thereof include an injection molding method, a calender molding method, a blow molding method, an extrusion molding method, and an inflation molding method. Heat curing is preferable for the curing.
The heating temperature in the curing method may be, for example, 150 ° C. or higher, preferably 200 ° C. or higher. Further, the upper limit of the temperature may be, for example, 300 ° C. or lower or 250 ° C. or lower, and the suitable numerical range is preferably 200 to 250 ° C., and more preferably 200 to 220 ° C. The heating time is not particularly limited, but it is desirable to adjust the thickness of the film within a range in which the film is not heat-denatured.
Further, when a thick film is obtained, the thickness of the film may be reduced from the viewpoint of being used for the surface layer of the laminated body. For example, after obtaining a thick film by a roll method, the thickness of the film may be further reduced by a known method such as a heat pressing method. Examples of the hot pressing method include a heating temperature of 150 to 250 ° C. and a pressurization of 5 to 30 MPa.

The film, which is a cured product of the film-forming composition of the present invention, is used as a surface layer formed on the surface of a base material of various molded products such as decorative paper, wallpaper, and leather from the viewpoint of enhancing antifouling property. Can be done. The substrate may be, for example, polyvinyl chloride, paper, non-woven fabric, woven fabric, synthetic leather or the like. Further, the film, which is a cured product of the film-forming composition, may be formed on the surface of the base material via a binder such as an adhesive or a curing agent in order to bond well with the base material.
The film-forming composition of the present invention may be used as, for example, an antifouling coating agent for decorative paper, an antifouling coating agent for wallpaper, or an antifouling coating agent for leather in order to stain the base material. By applying the antifouling coating agent to the surface of the base material and curing it, the antifouling property of the base material can be enhanced.

The thickness of the film, which is a cured product of the film-forming composition, is not particularly limited, but may be, for example, 1 μm or more, preferably 10 μm or more. The thickness of the film may be, for example, 500 μm or less, preferably 100 μm or less, and more preferably 80 μm or less from the viewpoint of being used for the surface layer. The film can enhance antifouling properties in various molded products such as decorative paper, wallpaper and leather.

It is possible to provide various molded products containing a film, which is a cured product of the film-forming composition of the present invention, as a surface layer.
More preferably, it is possible to provide a laminate containing a film, which is a cured product of the film-forming composition of the present invention, as at least one or both surface layers. As a result, the antifouling property of various molded products can be improved.
Examples of the laminated body of the present invention include, but are not limited to, laminated films, laminated sheets, and surface-coated molded products.
The laminate of the present invention can be produced by a known method for producing a laminate, and examples of the production method include a top coating method, a direct calendar bonding method, and a post-bonding method. Not limited.

Example 1 of a method for producing a laminate containing a film which is a cured product of the film-forming composition of the present invention may include, for example, the following steps:
(1) A film forming step of curing the film-forming composition of the present invention to form a cured film.
(2) A film laminating step in which the film formed in the film forming step is placed on a base material as a surface layer and processed to form a film laminate.
In the film laminating step, a binder may be placed between the formed film and the base material and processed.

In the film forming step, a known curing method can be used as the heating temperature for curing, and for example, the above-mentioned curing method may be adopted. It is desirable that the thickness of the film obtained in the film forming step is preferably 1 to 80 μm, more preferably 5 to 60 μm, still more preferably 10 to 25 μm, and even more preferably 10 to 20 μm.

In the film laminating step, a known film laminating method can be used. At this time, the heating temperature, mold pressure, speed, and the like can be appropriately adjusted in order to satisfactorily laminate the film layer on the substrate.

Example 2 of the method for producing a laminate containing a film which is a cured product of the film-forming composition of the present invention may include, for example, the following steps:
A laminating step in which the film-forming composition of the present invention is applied to one or both surfaces of a base material and cured to form a surface layer and then laminated.
Examples of the laminating method include, but are not limited to, a paste coating method and a calendar method. In the film laminating step, a binder may be placed between the formed film and the base material and processed.

Further, in the present invention, further embossing or the like may be performed in order to impart designability to the base material. The embossing may be performed by a method known in the art. The embossing may be performed by, for example, foaming the film layer with a heater embossing machine or a foam embossing machine during the laminating step, or mechanical embossing.

2. 2. Plastisol composition

The plastisol composition of the present invention contains at least a polyvinyl chloride-based polymer and at least one selected from the group consisting of cellulosic fibers, chitin fibers, and chitosan fibers. The plastisol composition of the present invention is suitable for enhancing antifouling properties in various molded products such as decorative paper, wallpaper and leather.
Hereinafter, embodiments of the plastisol composition of the present invention will be described. In the description of the present embodiment, the description of each composition, content, production method, usage method, etc. that overlaps with the above-mentioned "1. film forming composition" will be omitted as appropriate, but the description of "1." It also applies to embodiments and can be adopted as appropriate.

2-1. Each component of the plastisol composition Each component will be described below.

2-1 (1) Resin

The plastisol composition of the present invention contains at least a polyvinyl chloride polymer. For example, the plastisol composition may contain a resin containing a polyvinyl chloride polymer as a main component.

From the viewpoint of improving the antifouling property, the plastisol composition may contain, for example, the resin in a proportion of 50% by mass or more, preferably 60% by mass or more, based on the amount of the plastisol composition substance. Further, from the viewpoint of improving the antifouling property, the plastisol composition contains, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more of the polyvinyl chloride polymer with respect to the resin mass. , More preferably, it may be contained in a proportion of 90% by mass or more.

The polyvinyl chloride-based polymer is as described in "1." above.

The copolymer of the vinyl chloride monomer and another monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer is as described in "1." above.

The method for producing the polyvinyl chloride polymer, cross-linking of the polyvinyl chloride polymer, the polymer blend of the polyvinyl chloride polymer, further chlorination of the polyvinyl chloride polymer, and the like are described in the above-mentioned "1". . ”.

The average degree of polymerization and K value of the polyvinyl chloride polymer are as described in "1." above.
In the plastisol composition of the present invention, the average degree of polymerization of the polyvinyl chloride polymer is preferably 300 to 5000, more preferably 600 to 3000, and 600 to 600, from the viewpoint of improving the antifouling property. It is more preferably ~ 2000, and more preferably 700 to 2000.
In the plastisol composition of the present invention, the K value of the polyvinyl chloride-based polymer is preferably 40 to 90, more preferably 50 to 90, and more preferably 60 to 90, from the viewpoint of improving the antifouling property. More preferably, it is 80.
Further, the suspension vinyl chloride polymer, the paste vinyl chloride polymer, and the blended vinyl chloride polymer are as described in "1." above.

In the plastisol composition of the present invention, the resin may contain a resin other than the polyvinyl chloride-based polymer. Examples of the resin other than the polyvinyl chloride polymer include acrylic resin, polystyrene resin, polyethylene resin, polyimide resin, fluororesin, phenol resin, epoxy resin, urethane resin and the like, and are selected from the group consisting of these. One or more types can be used.
In the plastisol composition of the present invention, from the viewpoint of improving the antifouling property, for example, the resin other than the polyvinyl chloride polymer is 40% by mass or less, preferably 30% by mass, based on the total mass of the resin. Hereinafter, it can be contained in a proportion of 20% by mass or less, more preferably 10% by mass or less.
In the plastisol composition of the present invention, the K value of the resin is preferably 40 to 90, more preferably 50 to 90, and 60 to 80 from the viewpoint of improving the antifouling property. Is more preferable.

2-1 (2) Cellulose fiber, and chitin fiber and chitosan fiber The plastisol composition of the present invention is selected from the group consisting of cellulose fiber, chitin fiber, and chitosan fiber from the viewpoint of improving antifouling property. It may contain at least one or more fibers or two or more fibers. The fibers may be (a) cellulose fibers and / or (b) chitin fibers and / or chitosan fibers alone or in combination.
The shape of the fiber, the average fiber diameter of the fiber, the average fiber length of the fiber, the content of the fiber in the plastisol composition, and the like of the present invention are as described in "1."

2-1 (2) -1. Cellulose fiber

The raw material of the cellulose fiber of the present invention, the method for producing the cellulose fiber, the average fiber diameter of the cellulose fiber, the cellulose type I crystal, the commercially available product, and the like are as described in "1."

The content of the cellulose fibers in the plastisol composition is preferably 0.01 parts by mass or more, and 0.02 parts by mass or more with respect to 100 parts by mass of the resin, from the viewpoint of improving antifouling property. It is more preferable that the amount is 0.2 parts by mass or more. The content of the cellulose fibers is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the resin.

2-1 (2) -2. Chitin fiber, chitosan fiber

The raw material of the chitin fiber and / or chitosan fiber of the present invention, the degree of deacetylation (% DA), the method for producing the chitin fiber and / or the chitosan fiber, the average fiber diameter of the chitin fiber and / or the chitosan fiber, the chitin fiber. And / or the average fiber length of chitosan fibers, commercial products, etc. are as described in "1." above.

The content of the chitin fiber and / or chitosan fiber in the plastisol composition is preferably 0.01 part by mass or more with respect to 100 parts by mass of the resin from the viewpoint of improving antifouling property, and is 0. It is more preferably .02 parts by mass or more, and further preferably 0.2 parts by mass or more. The content of the chitin fiber and / or chitosan fiber is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the resin.

2-1 (3) Plasticizer

The plastisol composition of the present invention may contain a plasticizer.
The plasticizers of the present invention, polyvalent carboxylic acid ester-based plasticizers, benzoic acid ester-based plasticizers, and plasticizers other than polyvalent carboxylic acid ester-based plasticizers and benzoic acid ester-based plasticizers are described in the above-mentioned "1. . ”.

As the plasticizer in the plastizol composition, for example, diisononyl phthalate (DINP), bis (2-ethylhexyl) phthalate (DOP), diisodecyl phthalate (DIDP), dibutyl phthalate from the viewpoint of improving antifouling property. Phthalate-based plasticizers such as (DBP) and diundecyl phthalate (DUP); terephthalate-based plasticizers such as bis (2-ethylhexyl) terephthalate (DOTP); diisononyl adipate (DINA), bis adipate (bis (DINA)) Adipic acid ester-based plasticizers such as 2-ethylhexyl) (DOA) and diisodecyl adipate (DIDA); Trimellitic acid ester-based plasticizers such as trioctyl trimellitic acid (TOTM); 1,2-cyclohexanedicarboxylic acid diisononyl ester ( DINCH) and the like; citrate ester-based plasticizers such as tributyl acetyl citrate (ATBC) and the like can be mentioned.
Of these, a phthalate ester-based plasticizer is preferable from the viewpoint of improving antifouling property and cost.
One or more selected from the group consisting of these plasticizers can be used.

In the plastisol composition, from the viewpoint of improving antifouling property, it is preferable to use one or more selected from the group consisting of DINP, DOP, DOTP, ATBC, DINA, TOTM and DINCH as the plasticizer. .. Of these, in the plastisol composition, one or more selected from the group consisting of DINP, DOP, DOTP, DINA, TOTM and DINCH may be used from the viewpoint of improving antifouling property and from the viewpoint of plastisol. More preferably, it is one or more selected from the group consisting of DINP, DOP, and DINCH.
The plastisol composition may contain a plasticizer other than the polyvalent carboxylic acid ester plasticizer and the benzoic acid ester plasticizer as long as the effects of the present invention are not impaired.

The content of the plasticizer in the plastisol composition is preferably 1 part by mass or more and 20 parts by mass or more with respect to 100 parts by mass of the resin from the viewpoint of improving antifouling property. More preferably, it is 40 parts by mass or more. The content of the plasticizer is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and further preferably 95 parts by mass or less with respect to 100 parts by mass of the resin.

2-1 (4) Surfactant

The plastisol composition of the present invention may contain a surfactant.

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, and the like, and one or more selected from the group consisting of these. Can be used. The HLB of the surfactant is preferably 8 to 19 from the viewpoint of dispersibility in the plasticizer.

The nonionic surfactant, cationic surfactant, amphoteric surfactant, commercially available product, etc. of the present invention are as described in "1." above.

In the plastisol composition, from the viewpoint of improving the antifouling property, it is preferable to use a nonionic and / or cationic surfactant as the surfactant. When a nonionic surfactant is used, the HLB is preferably 8 to 19 from the viewpoint of dispersibility in the plasticizer.

From the viewpoint of improving the antifouling property, the content of the surfactant in the plastisol composition is preferably, for example, 10 parts by mass or less, and 1 part by mass or less, based on 100 parts by mass of the resin. More preferably, it is more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less. Further, the lower limit of the content of the surfactant is not particularly limited. The content of the surfactant may be, for example, 0.0001 parts by mass or more, 0.001 parts by mass or more, or 0.01 parts by mass or more with respect to 100 parts by mass of the resin. There may be.

2-1 (5) Other Ingredients In addition to the above ingredients, the plastisol composition of the present invention contains matting agents, stabilizers, thickeners, softeners, antioxidants (antioxidants), diluents, and additives. One or more selected from thickeners, antibacterial agents, fungicides, coloring pigments, ultraviolet absorbers, flame retardants, fillers and the like may be appropriately contained.

2-2. Method for producing plastisol composition

The method for producing a plastisol composition of the present invention can be taken as an example of the following example, but is not particularly limited thereto.
The plastisol composition may be prepared in the form of a paste, liquid, powder, or the like, and is not particularly limited thereto, but when used, it is preferably in the form of a liquid or a paste, and more preferably in the form of a paste. Is desirable from the viewpoint of application use.

An example of a method for producing a plastisol composition of the present invention may include the following steps:
(1) A mixing step of mixing a polyvinyl chloride-based polymer with one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers to obtain a mixture; and (2) the mixing. A dehydration step in which the mixture obtained in the step is stirred under reduced pressure and dehydrated.
Hereinafter, each step will be described in more detail.

(1) Mixing process

In the mixing step, the polyvinyl chloride polymer and one or more fibers selected from the group consisting of cellulosic fibers, chitin fibers, and chitosan fibers are mixed. In the mixing step, a resin other than the polyvinyl chloride polymer and other components (for example, a plasticizer, a surfactant, etc.) described above may also be mixed.

The mixing step may be performed by a stirrer known in the art. The mixing step can be performed, for example, at room temperature (20 to 30 ° C.).

(2) Dehydration process

In the dehydration step, the mixture obtained in the mixing step is stirred under reduced pressure. In addition, in this specification, "under reduced pressure" may mean, for example, an absolute pressure of 10 kPa or less, 5 kPa or less, 3 kPa or less, or 2.5 kPa or less. Further, the dehydration step may be performed under absolute vacuum (0 kPa).
By stirring the mixture under reduced pressure, the water contained in the fibers and the like is removed. The dehydration step can be performed, for example, at room temperature (20 to 30 ° C.).

2-3. How to use the plastisol composition

The plastisol composition of the present invention is used by being applied to the surface of a base material of various molded products such as decorative paper, wallpaper, and leather. The substrate may be, for example, polyvinyl chloride, paper, non-woven fabric, woven fabric, synthetic leather or the like. By curing the plastisol composition applied on the base material, the antifouling property of various molded products can be enhanced. The plastisol composition of the present invention can be suitably used for enhancing antifouling properties in, for example, decorative paper, wallpaper and leather. The plastisol composition of the present invention can be used, for example, as an antifouling coating agent for decorative paper, an antifouling coating agent for wallpaper, or an antifouling coating agent for leather.

The method of using the plastisol composition of the present invention may include, for example, the following steps:
(1) A coating step of applying the plastisol composition to the base material; and (2) a heating step of heating the plastisol composition applied to the base material in the coating step to obtain a cured product.
Hereinafter, each step will be described in detail.

(1) Coating process

In the coating step, the plastisol composition is coated on the substrate.
The coating step may be performed by an apparatus known in the art. The coating step can be performed, for example, at room temperature (20 to 30 ° C.). The coating thickness is not particularly limited, but may be, for example, 1 μm or more, preferably 10 μm or more. Further, the coating thickness may be, for example, 500 μm or less, preferably 100 μm or less.

(2) Heating process

In the heating step, the plastisol composition coated on the substrate in the coating step is heated to obtain a cured product.
The heating step may be performed by a method known in the art. The temperature in the heating step may be, for example, 150 ° C. or higher, preferably 200 ° C. or higher. Further, the temperature may be, for example, 350 ° C. or lower, preferably 300 ° C. or lower. Further, the time in the heating step may be, for example, 10 seconds or more, preferably 30 seconds or more. Further, the time may be, for example, 120 seconds or less, preferably 90 seconds or less.

In the present invention, further embossing or the like may be performed in order to impart designability to the base material. The embossing may be performed by a method known in the art.

2-4. A cured product of the plastisol composition and a molded product containing the cured product.

The present invention provides a cured product of the plastisol composition. The thickness of the cured product is not particularly limited, but may be, for example, 1 μm or more, preferably 10 μm or more. The thickness of the cured product may be, for example, 500 μm or less, preferably 100 μm or less.
The cured product may be obtained by the method described in "2-3. How to use the plastisol composition" above. The cured product may be a foam.
The cured product can enhance antifouling properties in various molded products such as decorative paper, wallpaper and leather.
Further, it is possible to provide a molded product containing a cured product of the plastisol composition of the present invention as a surface layer. A laminate including a surface layer of a cured product of the plastisol composition of the present invention and a base material layer can be provided. This makes it possible to improve the antifouling property of the molded product.

3. 3. Polyvinyl Chloride Resin Composition The present invention contains a polyvinyl chloride polymer and one or more selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers. A resin composition can be provided.
Hereinafter, embodiments of the polyvinyl chloride-based resin composition of the present invention will be described. In the description of the present embodiment, the description of each composition, content, production method, usage method, etc. that overlaps with the above-mentioned "1. film forming composition" and "2. plastisol composition" will be omitted as appropriate. The explanations of "1." and "2." also apply to the present embodiment and can be appropriately adopted.

The polyvinyl chloride-based resin composition of the present invention is suitable for enhancing antifouling properties in various molded products such as decorative paper, wallpaper and leather. The polyvinyl chloride-based resin composition can be formed on a cured product such as a film or a sheet, but the cured product is not particularly limited. Further, the polyvinyl chloride-based resin composition can be used in the state of plastisol as described above.

The polyvinyl chloride-based resin composition may be an emulsion type, and the emulsion type may be either an oil droplet type in water (O / W) or a water droplet type in oil (W / O).
In the polyvinyl chloride emulsion resin composition, raw materials such as an emulsifier, a surfactant, a dispersion medium (for example, water), a cross-linking agent and other additives are appropriately used, and these are mixed by stirring or the like. It can be obtained by emulsifying.
The polyvinyl chloride emulsion resin composition can be used as a film-forming composition, a sheet-forming composition, a coating agent, or the like. More specifically, the emulsion resin composition can be used, for example, in the production of surface films, laminated films, laminated sheets, foam sheets, wallpaper and the like.
In order to enhance the antifouling property of an object such as a molded product, the polyvinyl chloride emulsion resin composition may be impregnated into the object, or may be applied or coated on the surface of the object. Further, in order to enhance the antifouling property of the object, a cured product, for example, a film or a sheet formed from the polyvinyl chloride emulsion resin composition may be formed as a surface layer of the object.

Hereinafter, the present invention will be described in more detail based on Examples, Comparative Examples, and Test Examples. The examples, comparative examples, and test examples described below are representative examples of the present invention, and the scope of the present invention is not limited to these examples and test examples.

<1-Plastisol composition, this cured product, and a laminate containing the cured product>

<Wallpaper-based manufacturing>

As shown in Table 1 below, 100 parts by mass of paste vinyl chloride resin (PQLT, manufactured by Shin-Daiichi PVC) as a resin, 60 parts by mass of DINP (manufactured by CG Esther) as a plasticizer, and BF-200S (BF-200S) as a filler. (Manufactured by Bikita Powder Industry Co., Ltd.) 100 parts by mass, AZ-VI-25 (manufactured by Otsuka Chemical Co., Ltd.) 5 parts by mass as a foaming agent, SR-1 (manufactured by Sakai Chemical Industry Co., Ltd.) 10 parts by mass as a white pigment, FL as a stabilizer Mix 3 parts by mass of -44 (manufactured by ADEKA) and 7 parts by mass of BYK-4041 (manufactured by BYK) as a thickener with a stirrer, and mix the mixed solution on flame-retardant paper with a film applicator with a film thickness adjustment function (all). It was applied using (manufactured by Good).

Next, the flame-retardant paper coated with the mixed solution was heated in a gear oven (manufactured by Toyo Seiki Seisakusho) at 150 ° C. for 60 seconds to gel the base agent to obtain a wallpaper base having a thickness of 170 μm.

(Example 1)
(1) Mixing step 50 parts by mass of nanoforcest-S (fiber content 10%, manufactured by Chuetsu Pulp & Paper Co., Ltd.) as a cellulose fiber, 95 parts by mass of DINP (manufactured by CG Esther) as a plasticizer, and Emargen 1150S as a surfactant. 2 parts by mass of -60 (HLB 18.5, manufactured by Kao Co., Ltd.) was mixed with a stirrer to obtain a fiber content 1. DINP was added to 16.5 parts by mass of the fiber-containing material so that the total content of the plasticizer was 50 parts by mass, and PVC (product name: P21, average degree of polymerization: 1550, K value 75) was added as a resin. .1, 35 parts by mass of Shin Daiichi PVC (manufactured by Shin Daiichi PVC), 35 parts by mass of crosslinked PVC (product name: PN-900, manufactured by Shin Daiichi PVC) and blended PVC (product name: PS-300K, K value 69, Kaneka) 30 parts by mass of Ba / Zn-based stabilizer (manufactured by Katsuta Kako) and 1 part by mass of BYK-4041 (manufactured by BYK) as a thickener are added and mixed with a stirrer. 1 was obtained.

(2) Dehydration Step The mixture 1 obtained in (1) above was stirred under reduced pressure using a vacuum stirring defoamer (manufactured by Otsuka Seisakusho Co., Ltd.) and dehydrated to obtain a plastisol composition 1. The fiber content of the plastisol composition 1 was 0.22 parts by mass with respect to 100 parts by mass of the resin.

(3) Coating step and heating step The plastisol composition 1 obtained in (2) above is applied to a wallpaper base to a thickness of 20 μm, and heated in a gear oven (manufactured by Toyo Seiki Seisakusho) at 220 ° C. for 60 seconds. And foamed to obtain wallpaper sample 1.

(Example 2)
As a cellulose fiber, BiNFi-s WMa-10010 (fiber content 10%, manufactured by Sugino Machine Limited; as of March 2020, WMa was integrated into WFo, and this "WMa-10010" became "WFo-10010". The fiber-containing material 2 was obtained in the same manner as in Example 1 except that 50 parts by mass was used. Further, the plastisol composition 2 was obtained by the same method as in Example 1 except that 6.5 parts by mass of the fiber-containing material was used. The fiber content of the plastisol composition 2 was 0.22 parts by mass with respect to 100 parts by mass of the resin. Then, wallpaper sample 2 was obtained by the same method as in Example 1.

(Example 3)
Fiber content 3 was obtained in the same manner as in Example 1 except that 50 parts by mass of Celish GY-100G (fiber content 10%, manufactured by Daicel Finechem Ltd.) was used as the cellulose fiber. Further, the plastisol composition 3 was obtained by the same method as in Example 1 except that 6.5 parts by mass of the fiber-containing material was used. The fiber content of the plastisol composition 3 was 0.22 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 3 was obtained by the same method as in Example 1.

(Example 4)
The fiber content 4 was obtained by the same method as in Example 1 except that 250 parts by mass of Leocrysta I-2SX (fiber content 2%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used as the cellulose fiber. Further, the plastisol composition 4 was obtained by the same method as in Example 1 except that 15.4 parts by mass of the fiber-containing material 4 was used. The fiber content of the plastisol composition 4 was 0.22 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 4 was obtained by the same method as in Example 1.

(Example 5)
The fiber content 5 was obtained by the same method as in Example 1 except that 500 parts by mass of marine nanofibers (partially hydrolyzed chitin) (fiber content 1%, manufactured by Marine Nanofibers Co., Ltd.) were used as chitosan fibers. Further, the plastisol composition 5 was obtained by the same method as in Example 1 except that 26.5 parts by mass of the fiber-containing material 5 was used. The fiber content of the plastisol composition 5 was 0.22 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 5 was obtained by the same method as in Example 1.

(Example 6)
A plastisol composition 6 was obtained in the same manner as in Example 1 except that DOP (manufactured by CGG Ester) was used as a plasticizer. Then, wallpaper sample 6 was obtained by the same method as in Example 1.

(Example 7)
A plastisol composition 7 was obtained in the same manner as in Example 1 except that DOTP (manufactured by LG Chem) was used as a plasticizer. Then, the wallpaper sample 7 was obtained by the same method as in Example 1.

(Example 8)
A plastisol composition 8 was obtained in the same manner as in Example 1 except that DINA (manufactured by Taoka Chemical Co., Ltd.) was used as a plasticizer. Then, the wallpaper sample 8 was obtained by the same method as in Example 1.

(Example 9)
A plastisol composition 9 was obtained in the same manner as in Example 1 except that TOTM (manufactured by DIC Corporation) was used as a plasticizer. Then, the wallpaper sample 9 was obtained by the same method as in Example 1.

(Example 10)
The plastisol composition 10 was obtained in the same manner as in Example 1 except that DINCH (manufactured by BASF) was used as the plasticizer. Then, the wallpaper sample 10 was obtained by the same method as in Example 1.

(Example 11)
The plastisol composition 11 was obtained in the same manner as in Example 1 except that 2 parts by mass of Emulgen 103 (HLB 8.1, manufactured by Kao Corporation) was used as the surfactant. Then, the wallpaper sample 11 was obtained by the same method as in Example 1.

(Example 12)
The plastisol composition 12 was obtained by the same method as in Example 1 except that 2 parts by mass of acetamine 24 (manufactured by Kao Corporation) was used as the surfactant. Then, the wallpaper sample 12 was obtained by the same method as in Example 1.

(Example 13)
As a resin, 35 parts by mass of PVC (product name: P21, average degree of polymerization: 1550, K value 75.1, manufactured by Shin Daiichi PVC Co., Ltd.), crosslinked PVC (product name: PN-900, manufactured by Shin Daiichi PVC Co., Ltd.) 30 The plastisol composition 13 was obtained by the same method as in Example 1 except that 35 parts by mass and 35 parts by weight of a vinyl chloride / vinyl acetate copolymer (product name: PCH-12, K value 74, manufactured by Kaneka Co., Ltd.) were used. It was. Then, the wallpaper sample 13 was obtained by the same method as in Example 1.

(Example 14)
As resin, 35 parts by mass of PVC (product name: P21, average degree of polymerization: 1550, manufactured by Shin-Daiichi PVC), 30 parts by mass of cross-linked PVC (product name: PN-900, manufactured by Shin-Daiichi PVC) and acrylic resin ( A plastisol composition 14 was obtained in the same manner as in Example 1 except that 35 parts by mass (manufactured by Mitsubishi Chemical Co., Ltd.) was used. Then, the wallpaper sample 14 was obtained by the same method as in Example 1.

(Example 15)
A plastisol composition 15 was obtained in the same manner as in Example 1 except that 100 parts by mass of PVC (product name: P29E, average degree of polymerization: 1450, manufactured by Shin-Daiichi PVC Co., Ltd.) was used as the resin. Then, the wallpaper sample 15 was obtained by the same method as in Example 1.

(Example 16)
A plastisol composition 16 was obtained in the same manner as in Example 1 except that 0.65 parts by mass of the fiber-containing material of Example 1 was used. The fiber content of the plastisol composition 16 was 0.022 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 16 was obtained by the same method as in Example 1.

(Example 17)
50 parts by mass of nanoforcest-S as a cellulose fiber, 44.5 parts by mass of DINP as a plasticizer, and 2 parts by mass of Emargen 1150S-60 as a surfactant were mixed with a stirrer to obtain a fiber content 17. The plastisol composition 17 was obtained by the same method as in Example 1 except that 6.5 parts by mass of the fiber-containing material 17 was used. The fiber content of the plastisol composition 17 was 0.41 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 17 was obtained by the same method as in Example 1.

(Example 18)
50 parts by mass of nanoforcest-S as a cellulose fiber and 2 parts by mass of Emargen 1150S-60 as a surfactant were mixed with a stirrer to obtain a fiber content 18. The plastisol composition 18 was obtained by the same method as in Example 1 except that 6.5 parts by mass of the fiber-containing material 18 was used. The fiber content of the plastisol composition 18 was 0.625 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 18 was obtained by the same method as in Example 1.

(Example 19)
50 parts by mass of nanoforcest-S as a cellulose fiber and 2 parts by mass of Emargen 1150S-60 as a surfactant were mixed with a stirrer to obtain a fiber content 19. A plastisol composition 19 was obtained in the same manner as in Example 1 except that 13 parts by mass of the fiber-containing material 19 was used. The fiber content of the plastisol composition 19 was 1.25 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 19 was obtained by the same method as in Example 1.

(Example 20)
50 parts by mass of nanoforcest-S as a cellulose fiber and 95 parts by mass of DINP as a plasticizer were mixed with a stirrer to obtain a fiber content 20. The plastisol composition 20 was obtained by the same method as in Example 1 except that 6.42 parts by mass of the fiber-containing material 20 was used. The fiber content of the plastisol composition 20 was 0.22 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 20 was obtained by the same method as in Example 1.

(Example 21)
50 parts by mass of nanoforcest-S as a cellulose fiber, 44.5 parts by mass of DINP as a plasticizer, and 1 part by mass of Emargen 1150S-60 as a surfactant were mixed with a stirrer to obtain a fiber content 21. The plastisol composition 21 was obtained by the same method as in Example 1 except that 6.46 parts by mass of the fiber-containing material 21 was used. The fiber content of the plastisol composition 21 was 0.22 parts by mass with respect to 100 parts by mass of the resin. Then, the wallpaper sample 21 was obtained by the same method as in Example 1.

(Comparative Example 1)
The wallpaper sample 101 of Comparative Example 1 was obtained by applying nothing to the wallpaper base.

(Comparative Example 2)
Using 95 parts by mass of DINP as a plasticizer, a fiber-containing material 102 was obtained. The plastisol composition 102 was obtained in the same manner as in Example 1 except that 4.22 parts by mass of the fiber-containing material 102 was used. Then, the wallpaper sample 102 was obtained by the same method as in Example 1.

(Comparative Example 3)
95 parts by mass of DINP as a plasticizer and Emargen 1150S-60 as a surfactant
2 parts by mass were mixed with a stirrer to obtain a fiber content 103. The plastisol composition 103 was obtained by the same method as in Example 1 except that 4.22 parts by mass of the fiber-containing material 103 was used. Then, the wallpaper sample 103 was obtained by the same method as in Example 1.

<Evaluation of wallpaper sample>
(Evaluation of wallpaper samples 1-19, 101-103)
Each wallpaper sample obtained in each Example and Comparative Example was evaluated for stain prevention in accordance with the stain prevention wallpaper performance regulation established by the Wallpaper Industry Association.
Specifically, a crayon was attached to each wallpaper sample cut into a size of 30 mm × 220 mm, and after 24 hours, the wallpaper sample wiped off with a neutral detergent was visually determined. The wiped part was compared with the original piece, and if the evaluation was grade 4 or higher, the evaluation was good. The gray scale for contamination was in accordance with JIS L 0805. In this experiment, the evaluation of the antifouling wallpaper performance regulation was subdivided, and the intermediate evaluation of each grade was added.
<Evaluation criteria>
Grade 5: Dirt is about grayscale No. 5 for pollution (no dirt remains)
Grades 4-5: Better than Grade 4, but not as good as Grade 5 Grade 4: Dirt is about grayscale No. 4 for pollution (almost no stains remain)
Grades 3-4: Better than Grade 3, but not as good as Grade 3 Grade 3: Dirt is about grayscale No. 3 for pollution (some stains remain)
2nd to 3rd grade: Better than 2nd grade, but not as good as 3rd grade 2nd grade: Dirt is about grayscale No. 2 for pollution (quite dirt remains)
Grades 1 and 2 are better than grade 1, but not as good as grade 2. Grade 1: Dirt is about grayscale No. 1 for pollution (dirt remains thick)

The compositions of Examples 1 to 21 and Comparative Examples 1 to 3 and the evaluation results are shown in Tables 2 to 4 below. In addition, each number of the item other than "evaluation" in a table indicates a mass part.

From the results of Examples 1 to 5 and Comparative Examples 1 to 3, a polyvinyl chloride-based polymer and one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers were used. It can be seen that the combined plastisol composition can enhance the antifouling property of the wallpaper.
Further, from the results of Examples 1 and 6 to 10, it can be seen that a wide range of plasticizers can be used for the plastisol composition. Further, from these results, it can be seen that the antifouling effect of the wallpaper is good, especially when at least one or more of DINP, DOP, DOTP, DINA, TOTM, and DINCH is used as the plasticizer.
Furthermore, from the results of Examples 1, 11 and 12, it can be seen that a wide range of surfactants can be used in the plastisol composition. In addition, from these results, it can be seen that the antifouling effect of the wallpaper is good, especially when a nonionic surfactant or a cationic surfactant is used as the surfactant. Further, it can be seen that when a nonionic surfactant is used as the surfactant, particularly when a nonionic surfactant having an HLB of 8 to 19 is used, the antifouling effect of the wallpaper is good.
From the results of Examples 1 and 13 to 15, it can be seen that a wide range of resins can be used for the plastisol composition.
From the results of Examples 1 and 16 to 19, the antifouling effect of the wallpaper is good when the content of the cellulose fibers in the plastisol composition is 0.02 parts by mass or more with respect to 100 parts by mass of the resin. It turns out that there is.
From the results of Examples 1, 20 and 21, it can be seen that the antifouling effect of the wallpaper is good even if the plastisol composition does not contain a surfactant.

<2-Film-forming composition, this cured product, and a laminate containing the cured product>

According to the above <Manufacturing of wallpaper base>, a wallpaper base having a thickness of 170 μm was obtained.

<Raw material for polyvinyl chloride resin composition>
Examples of raw materials for the polyvinyl chloride resin composition are shown below.
(resin)
Suspension PVC (Product name: ZEST 700LS, K value 59.4, Average degree of polymerization: 720, manufactured by Shin Daiichi PVC Co., Ltd.)
Suspension PVC (Product name: ZEST 1300Z, K value 71.5, average degree of polymerization: 1300, manufactured by Shin Daiichi PVC Co., Ltd.)
Paste PVC (Product name: ZEST P21, K value 75.1, Average degree of polymerization: 1550, manufactured by Shin-Daiichi PVC Co., Ltd.)
Paste PVC (Product name: ZEST PQLT, K value 61.6, Average degree of polymerization: 800, manufactured by Shin Daiichi PVC Co., Ltd.)
Paste cross-linked PVC (Product name: PN-900, manufactured by Shin Daiichi PVC Co., Ltd.)
Blended PVC (Product name: XPS-300L, manufactured by Kaneka Corporation)
The particle diameters (D50) of ZEST 700LS and ZEST 1300Z of suspension PVC were in the range of 100 to 150 μm. The particle diameters (D50) of ZEST P21 and ZEST PQLT of paste PVC and PN-900 of paste cross-linked PVC were in the range of 0.02 to 5 μm.

Plasticizer Diisononyl phthalate (DINP) (manufactured by CG Esther)
Bis phthalate (2-ethylhexyl) (DOP) (manufactured by CG Esther)
Bis terephthalate (2-ethylhexyl) (DOTP) (manufactured by LG Chem)
Tributyl Acetyl Citrate (ATBC) (manufactured by Taoka Chemical Co., Ltd.)
Trioctyl trimellitic acid (TOTM) (manufactured by DIC Corporation)
Diisodecyl adipic acid (DINA) (manufactured by Taoka Chemical Co., Ltd.)

Impact resistance improver Acrylic rubber (Product name: Metabren W-300A, manufactured by Mitsubishi Chemical Corporation)
Heat stabilizer Ba / Zn-based heat stabilizer (Product name: AC-723, manufactured by ADEKA Corporation)
Epoxyd soybean oil (manufactured by Daikyo Kasei Kogyo Co., Ltd.)
Heat stabilizer (Product name: SC-126, manufactured by ADEKA Corporation)
(Fiber: Cellulose fiber)
nanoforcest-S (Product name: nanoforcest-S, fiber content 10%, fiber width several nm to several μm, manufactured by Chuetsu Pulp & Paper Co., Ltd.)
Serenpia TC-02X (Product name: Serenpia TC-02X, fiber content 5%, TEMPO oxide CNF, fiber length (short fiber) number 100 nm to 1 μm, average fiber diameter 3 to 4 nm)
BiNFi-s WFo-10010 (Product name: BiNFi-s WFo-10010, fiber content 10%, fiber length (standard fiber), average fiber diameter 10 to 50 nm, average degree of polymerization 650, manufactured by Sugino Machine Limited)
Serish GY-100G (Product name: Serish GY-100G, fiber content 10%, average fiber diameter 0.01-50 μm, manufactured by Daicel Fine Chem Ltd.)
Leocrysta I-2SX (Product name: Leocrysta I-2SX, fiber content 2%, fiber width approx. 3 nm, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
(Fiber: chitin fiber, chitosan fiber)
Chitin-NF (Product name: Chitin-NF, fiber content 1%, chitin fiber, average fiber diameter several tens of nm, aqueous dispersion, manufactured by Marine Nanofiber Co., Ltd.)
Partially hydrolyzed chitin-NF (Product name: Partially hydrolyzed chitin-NF, fiber content 1%, chitosan fiber, average fiber diameter tens of nm, aqueous dispersion, manufactured by Marine Nanofiber Co., Ltd.)

(Surfactant)
Nonionic surfactant (Product name: Emargen 1150S-60, Polyoxyethylene alkyl ether, HLB 18.5, manufactured by Kao Corporation)
Nonionic surfactant (Product name: Emargen 103, Polyoxyethylene lauryl ether, HLB 8.1, manufactured by Kao Corporation)
Alkylamine acetate (Product name: Acetamine 24, Coconatamine acetate, manufactured by Kao Corporation)

Matte hydrophilic fumed silica (Product name: Aerosil # 300, manufactured by Evonik)
Acrylic matte (Product name: Metabren F-310, manufactured by Mitsubishi Chemical Corporation)

<Manufacturing of film-forming composition>
(1) Mixing Step The raw materials and the addition amounts shown in Tables 5 and 6 below were mixed to obtain each mixture as a film-forming composition of each Test Example.
As a specific addition procedure, fibers, a surfactant, and a plasticizer are mixed with a stirrer under normal temperature (about 20 to 30 ° C.) conditions to obtain a fiber-containing material, and the fiber-containing material, resin, and others are obtained. Raw materials (impact improver, heat stabilizer, matting agent, etc.) were mixed to obtain a mixture (Test Examples 2, 4 to 25).
For Test Examples 1 and 3, a plasticizer, a resin, and other raw materials (impact resistance improver, heat stabilizer) were used under normal temperature (about 20 to 30 ° C.) conditions without adding fibers and surfactants. ) Was mixed to obtain a mixture containing no fibers and a surfactant.

The addition procedure for producing the above-mentioned mixture may be changed to "adding each raw material to the mixer and then stirring all the raw materials at the same time", and the mixture obtained by stirring all the raw materials at the same time is described above. It is possible to obtain the same quality (antifouling property, etc.) as the mixture obtained by the addition procedure of.

(Test Example 1)
As shown in Test Example 1 of Table 5, 15 parts by mass of plasticizer (DINP), 100 parts by mass of suspension PVC as resin, 3 parts by mass of impact resistance improver (Metabrene W-300A), and Ba / Zn-based heat. Stabilizer (AC-723) 3 parts by mass, heat stabilizer (epoxidized soybean oil) 3 parts by mass, heat stabilizer (SC-126) 1 part by mass are mixed with a stirrer and contain fibers and surfactant. No mixture of Test Example 1 was obtained.

(Test Example 2)
As shown in Test Example 2 of Table 5, 15 parts by mass of plasticizer (DINP), 2.22 parts by mass of cellulose fibers (fiber content 10%), and 0.09 parts by mass of surfactant were mixed with a stirrer. Mixing gave fiber content. The fiber-containing material, 100 parts by mass of suspension PVC, 3 parts by mass of impact-resistant improver, 3 parts by mass of AC-723 as a heat stabilizer, 3 parts by mass of epoxidized soybean oil, and 1 part by mass of SC-126 as a resin. The parts were mixed to obtain a mixture of Test Example 2. The mixture contained 0.222 parts by mass of fibers with respect to 100 parts by mass of the resin.

(Test Example 3)
As shown in Test Example 3 of Table 5, "100 parts by mass of suspension PVC" contained as the resin of Test Example 1 was changed to "80 parts by mass of suspension PVC and 20 parts by mass of paste PVC (ZEST P21)". Obtained a mixture of Test Example 3 containing no fibers and a surfactant by the same method as in Test Example 1.

(Test Example 4)
As shown in Test Example 4 of Table 5, "100 parts by mass of suspension PVC" contained as the resin of Test Example 2 was changed to "80 parts by mass of suspension PVC and 20 parts by mass of paste PVC (ZEST P21)". Obtained a mixture of Test Example 4 in the same manner as in Test Example 2. The mixture contained 0.222 parts by mass of fibers with respect to 100 parts by mass of the resin.

(Test Examples 5 to 9: Types of polyvalent carboxylic acid ester plasticizers)
(Test Example 5)
As shown in Test Example 5 in Table 5, Test Example 5 was carried out in the same manner as in Test Example 4 except that diisononyl phthalate (DINP) in Test Example 4 was changed to bis (2-ethylhexyl) phthalate (DOP). A mixture of

(Test Example 6)
As shown in Test Example 6 in Table 5, the mixture of Test Example 6 was prepared in the same manner as in Test Example 4 except that diisononyl phthalate (DINP) in Test Example 4 was converted to bis (2-ethylhexyl) terephthalate DOTP. Got

(Test Example 7)
As shown in Test Example 7 in Table 5, a mixture of Test Example 7 was obtained in the same manner as in Test Example 4 except that diisononyl phthalate (DINP) in Test Example 4 was converted to tributyl acetylcitrate (ATBC). It was.

(Test Example 8)
As shown in Test Example 8 in Table 5, a mixture of Test Example 8 was obtained in the same manner as in Test Example 4 except that diisononyl phthalate (DINP) in Test Example 4 was converted to trioctyl trimellitic acid (TOTM). It was.

(Test Example 9)
As shown in Test Example 9 in Table 5, a mixture of Test Example 9 was obtained in the same manner as in Test Example 4 except that diisononyl phthalate (DINP) in Test Example 4 was changed to diisononyl phthalate (DINA). ..

(Test Examples 10 to 13 and 14 to 16: type and content of fiber)
(Test Example 10)
As shown in Test Example 10 of Table 5, the cellulose fiber of Test Example 4 (nanoforest-S, fiber content 10%) was converted into the cellulose fiber of Test Example 10 (Serenpia TC-02X, fiber content 5%, TEMPO oxidation). A mixture of Test Example 10 was obtained in the same manner as in Test Example 4 except that CNF) was used. The mixture contained 0.222 parts by mass of fibers with respect to 100 parts by mass of the resin.

(Test Example 11)
As shown in Test Example 11 of Table 5, the cellulose fiber of Test Example 4 (nanofost-S, fiber content 10%) was used as the cellulose fiber of Test Example 11 (BiNFi-s WFo-10010, fiber content 10%). A mixture of Test Example 11 was obtained in the same manner as in Test Example 4 except that The mixture contained 0.222 parts by mass of fibers with respect to 100 parts by mass of the resin.

(Test Example 12)
As shown in Test Example 12 in Table 5, the cellulose fiber (nanoforest-S fiber content 10%) of Test Example 4 was used as the chitin fiber (chitin-NF, fiber content 1%, aqueous dispersion) of Test Example 12. A mixture of Test Example 12 was obtained in the same manner as in Test Example 4 except that The mixture contained 0.222 parts by mass of fibers with respect to 100 parts by mass of the resin.

(Test Example 13)
As shown in Test Example 13 of Table 5, the cellulose fiber (nanoforest-S fiber content 10%) of Test Example 4 was used as the chitosan fiber (partially hydrolyzed chitin-NF, fiber content 1%, water) of Test Example 13. A mixture of Test Example 13 was obtained in the same manner as in Test Example 4 except that it was made into a dispersion). The mixture contained 0.222 parts by mass of fibers with respect to 100 parts by mass of the resin.

(Test Example 14)
As shown in Test Example 14 of Table 6, the content of 2.22 parts by mass of the cellulose fiber (nanoforest-S fiber content 10%) of Test Example 4 is the cellulose fiber (nanoforest-S fiber content) of Test Example 14. A mixture of Test Example 14 was obtained in the same manner as in Test Example 4 except that the content was 4.44 parts by mass (10%). The mixture contained 0.444 parts by mass of fibers with respect to 100 parts by mass of the resin.
(Test Example 15)
As shown in Test Example 15 of Table 6, the content of 2.22 parts by mass of the cellulose fiber (nanoforest-S fiber content 10%) of Test Example 4 is the cellulose fiber (nanoforest-S fiber content) of Test Example 15. A mixture of Test Example 15 was obtained in the same manner as in Test Example 4 except that the content was 6.66 parts by mass (10%). The mixture contained 0.666 parts by mass of fibers with respect to 100 parts by mass of the resin.

(Test Example 16)
As shown in Test Example 16 of Table 6, the content of 4.44 parts by mass of the cellulose fiber (Serenpia TC-02X, fiber content 5%, TEMPO oxide CNF) of Test Example 10 was added to the cellulose fiber of Test Example 16 ( A mixture of Test Example 16 was obtained in the same manner as in Test Example 10 except that the content of Serempia TC-02X, fiber content 5%, and TEMPO oxide CNF) was set to 8.88 parts by mass. The mixture contained 0.444 parts by mass of fibers with respect to 100 parts by mass of the resin.

(Test Examples 17-21: Resin type and mass content ratio)
(Test Example 17)
As shown in Test Example 17 of Table 6, "80 parts by mass of suspension PVC and 20 parts by mass of paste PVC (ZEST P21)" of Test Example 4 are changed to "50 parts by mass and 50 parts by mass", respectively. Obtained a mixture of Test Example 17 in the same manner as in Test Example 4.

(Test Example 18)
As shown in Test Example 18 of Table 6, except that "20 parts by mass of paste PVC (ZEST P21)" of Test Example 4 was changed to "20 parts by mass of paste cross-linked PVC (PN-900)", it was the same as Test Example 4. A mixture of Test Example 18 was obtained in the same manner.

(Test Example 19)
As shown in Test Example 19 of Table 6, Test Example except that "20 parts by mass of paste PVC (ZEST P21)" in Test Example 4 was changed to "20 parts by mass of blended PVC (product name: XPS-300L)". A mixture of Test Example 19 was obtained in the same manner as in 4.

(Test Example 20)
As shown in Test Example 20 of Table 6, the same method as in Test Example 4 except that "20 parts by mass of paste PVC (ZEST P21)" in Test Example 4 was changed to "20 parts by mass of paste PVC (ZEST PQLT)". To obtain a mixture of Test Example 20.

(Test Example 21)
As shown in Test Example 21 of Table 6, the test was carried out in the same manner as in Test Example 4 except that "80 parts by mass of suspension PVC (700LS)" in Test Example 4 was changed to 80 parts by mass of "suspension PVC (1300Z)". A mixture of Example 21 was obtained.

(Test Examples 22 to 23: Amount of polyvalent carboxylic acid ester plasticizer)
(Test Example 22)
As shown in Test Example 22 of Table 6, Test Example 22 was carried out in the same manner as in Test Example 4 except that the content of "15 parts by mass of diisononyl phthalate (DINP)" in Test Example 4 was set to 5 parts by mass. A mixture of
(Test Example 23)
As shown in Test Example 23 of Table 6, Test Example 23 was carried out in the same manner as in Test Example 4 except that the content of "15 parts by mass of diisononyl phthalate (DINP)" in Test Example 4 was 30 parts by mass. A mixture of

(Test Examples 24 to 25: Addition of matting agent)
(Test Example 24)
As shown in Test Example 24 of Table 6, the same method as in Test Example 4 except that "3 parts by mass of hydrophilic fumed silica (Aerosil # 300)" was further added as a matting agent to the raw material of Test Example 4. To obtain a mixture of Test Example 24.
(Test Example 25)
As shown in Test Example 25 of Table 6, it is the same as Test Example 4 except that "5 parts by mass of an acrylic matting agent (Metabrene F-310)" is further added as a matting agent to the raw material of Test Example 4. By the method, a mixture of Test Example 25 was obtained.

(2) Film forming process and laminating process (foaming raw fabric production)
<Film formation for top coat>
The mixture of Test Example 1 obtained in the above (1) mixing step is kneaded at 150 ° C. for 5 minutes with a calendar roll (two roll) device, and rolled to a film thickness of about 500 μm to form a film. Was produced. A film having a film thickness of 500 μm was further rolled at 150 ° C. for 2 minutes so as to have a film thickness of 100 μm to form a thin coating film.
The thin coating film (thickness 100 μm) of Test Example 1 was further thinned by a hot press under the following conditions to form a topcoat film having a film thickness of 50 μm.
[Hot press conditions: Preheating 200 ° C x 1 minute, 1 MPa → Pressurized 10 MPa 200 ° C x 1 minute → Pressurized 15 MPa 200 ° C x 1 minute → Pressurized 20 MPa 200 ° C x 1 minute]
For each mixture of Test Examples 2 to 25, the top coat film of each Test Example 2 to 25 was formed in the same manner as in the above-mentioned method for forming the top coat film.
From the film-forming compositions of Test Examples 1 to 25, a top-coat film having a film thickness of 10 to 20 μm can be produced by an actual machine capable of extrusion molding or calender molding.

<Lasting of foamed fabric>
The prepared topcoat film of Test Example 1 was placed on one surface of the wallpaper base via a binder, and the wallpaper base on which the topcoat film was placed was heated at 100 ° C. for 1 minute at 5 MPa. The film was pressed and further heated in a gear oven (manufactured by Toyo Seiki Seisakusho) at 220 ° C. for 60 seconds to foam to obtain a wallpaper sample of Test Example 1.
The wallpaper samples of Test Examples 2 to 25 were obtained by using the films of Test Examples 2 to 25 in the same manner as the above-mentioned foaming raw fabric bonding.
For each wallpaper sample of Test Examples 1 to 25, the antifouling property of the surface of each wallpaper sample was evaluated based on the above <evaluation of wallpaper sample>.

The compositions of Test Examples 1 to 25 and the evaluation results are shown in Tables 5 to 6 below. In addition, each number of the item other than "evaluation" in a table indicates a mass part.

As described above, the film-forming composition was thermoset and further rolled to form a topcoat film. By laminating this topcoat film on the surface of the wallpaper base via a binder, a wallpaper which is a laminated body containing the topcoat film in the surface layer was manufactured.

From the results of Test Examples 1 to 25, it is possible to enhance the antifouling property of the wallpaper by a film-forming composition in which a polyvinyl chloride-based polymer and a cellulose fiber and / or a chitin fiber and / or a chitosan fiber are combined. I know I can do it.
From the results of Test Examples 1 to 4 and Test Examples 10 to 13, it can be seen that a wide range of fibers, particularly cellulose fibers and / or chitin fibers and / or chitosan fibers, can be used in the film-forming composition. In addition, from the results of Test Examples 14 to 16, the antifouling effect of the wallpaper is good when the fiber content in the film-forming composition is at least 0.2 parts by mass or more with respect to 100 parts by mass of the resin. It can be seen that the antifouling effect of the wallpaper is good up to about 0.7 parts by mass.
Further, from the results of Test Examples 4 to 9, it can be seen that a wide range of plasticizers can be used in the film-forming composition. Further, from these results, it can be seen that the antifouling effect of the wallpaper is good especially when at least one or more of DINP, DOP, DOTP, ATBC, TOTM, and DINA is used as the plasticizer. In addition, from the results of Test Examples 22 and 23, it can be seen that the content of the plasticizer in the film-forming composition is 5 to 30 parts by mass with respect to 100 parts by mass of the resin, and the antifouling effect of the wallpaper is good. ..
Furthermore, from the results of Test Examples 1 to 4, when a surfactant, particularly a nonionic surfactant or a cationic surfactant, is used in the film-forming composition, the antifouling effect of the wallpaper is good. I understand. Further, it can be seen that when a nonionic surfactant is used as the surfactant, particularly when a nonionic surfactant having an HLB of 8 to 19 is used, the antifouling effect of the wallpaper is good.
From the results of Test Example 4, Test Example 14, and Test Examples 16 to 21, it can be seen that a wide range of resins can be used in the film-forming composition. In particular, it can be seen that it is preferable to use at least a suspension vinyl chloride polymer, and it is more preferable to combine the suspension vinyl chloride polymer with a paste vinyl chloride polymer and / or a blended vinyl chloride polymer.
From the results of Test Examples 4 and 24 to 25, it can be seen that the antifouling effect of the wallpaper is good even if the film-forming composition contains a matting agent.

Claims (17)

Polychlorinated polymer and
One or more selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers, and
A composition for forming a film. The film-forming composition according to claim 1, which comprises a plasticizer. The film-forming composition according to claim 2, wherein the plasticizer is a polyvalent carboxylic acid ester-based plasticizer. The film-forming composition according to claim 2 or 3, wherein the plasticizer is at least one selected from the group consisting of DINP, DOP, DOTP, ATBC, TOTM, and DINA. The film-forming composition according to any one of claims 1 to 4, which comprises a surfactant. The film-forming composition according to claim 5, wherein the surfactant is a nonionic surfactant and / or a cationic surfactant. A film that is a cured product of the film-forming composition according to any one of claims 1 to 6. A laminate containing a film, which is a cured product of the film-forming composition according to any one of claims 1 to 6, as at least one surface layer. Polychlorinated polymer and
One or more selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers, and
A plastisol composition comprising. The plastisol composition according to claim 9, which comprises a plasticizer. The plastisol composition according to claim 10, wherein the plasticizer is a polyvalent carboxylic acid ester-based plasticizer. The plastisol composition according to claim 10 or 11, wherein the plasticizer is at least one selected from the group consisting of DINP, DOP, DOTP, DINA, TOTM, and DINCH. The plastisol composition according to any one of claims 9 to 12, which comprises a surfactant. The plastisol composition according to claim 13, wherein the surfactant is a nonionic surfactant and / or a cationic surfactant. The plastisol composition according to claim 13 or 14, wherein the surfactant is a nonionic surfactant, and the HLB of the nonionic surfactant is 8 to 19. A cured product of the plastisol composition according to any one of claims 9 to 15. Polychlorinated polymer and
One or more selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers, and
A polyvinyl chloride-based resin composition containing.