JP7807031B2 - Film-forming composition and plastisol composition - Google Patents

Description

The present invention relates to a film-forming composition, a plastisol composition, etc.

In various molded products, such as decorative paper used in interior building materials or furniture, wallpaper used in building interiors, and leather used in bags or furniture, when dirt such as dust, cigarette tar, oil, food, cosmetics, writing implements, or mold adheres to the surface, it is required that the dirt can be easily wiped off with water, detergent, solvent, etc. This ease of wiping off dirt from the surface of various molded products is also known as "stain resistance."

As a technology for imparting stain resistance to various molded products, for example, Patent Document 1 discloses a stain-resistant agent comprising a synthetic resin emulsion (A), a wax (B) having a melting point in the range of 40 to 110°C, and a polyolefin (C) having an average particle size in the range of 1 to 100 μm and a dropping point in the range of 50 to 170°C, characterized in that the solid content of the wax (B) 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 per 100 parts by weight of the solid content of the synthetic resin emulsion (A). Furthermore, Patent Document 2 discloses a wallpaper coating agent containing an anionic polyester resin, wax, and silicone.

Japanese Patent Application Laid-Open No. 2004-059774 JP 2017-014430 A

Further improvements in stain resistance are required for various molded products such as decorative paper, wallpaper, and leather. Therefore, the present invention aims to improve the stain resistance of various molded products such as decorative paper, wallpaper, and leather.

The inventors have discovered that a specific polyvinyl chloride resin composition can improve the stain resistance of various molded products, such as decorative paper, wallpaper, and leather.

That is, the present invention provides a film-forming composition comprising a polyvinyl chloride polymer and one or more fibers 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 include a plasticizer.
The plasticizer may be a polycarboxylic acid ester-based plasticizer.
The plasticizer may be at least one 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 include a surfactant.
The surfactant may be a nonionic surfactant and/or a cationic surfactant.
The present invention also provides a film that is a cured product of the film-forming composition.
The present invention also provides a laminate comprising a film that 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 fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers.
According to one embodiment of the present invention, the plastisol composition may include a plasticizer.
The plasticizer may be a polycarboxylic acid ester-based plasticizer.
The plasticizer may be at least one selected from the group consisting of DINP, DOP, DOTP, DINA, TOTM, and DINCH.
In accordance with another embodiment of the present invention, the plastisol composition may include a surfactant.
The surfactant may 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 resin composition comprising a polyvinyl chloride polymer and one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers.

The film-forming composition and plastisol composition of the present invention can enhance the stain resistance of various molded articles such as decorative paper, wallpaper, and leather.
The effects of the present invention are not necessarily limited to the effects described herein, and may be any of the effects described in this specification.

The following describes in detail the embodiments of the present invention. The embodiments described below are representative examples of the present invention, and the present invention is not limited to these embodiments. In this specification, percentages are expressed by mass unless otherwise specified. The upper and lower limits of each numerical range can be combined as desired.

1. Film-forming composition The film-forming composition of the present invention contains at least a polyvinyl chloride polymer and one or more fibers selected from the group consisting of cellulose fiber, chitin fiber, and chitosan fiber. A cured product of the film-forming composition of the present invention is suitable for enhancing the stain resistance of various molded products such as decorative paper, wallpaper, and leather.

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

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

The polyvinyl chloride polymer is a polymer having a group represented by —CH ₂ —CHCl—. Examples of the polyvinyl chloride polymer include a homopolymer of vinyl chloride and a copolymer of a vinyl chloride monomer and another monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer, and one or more types selected from the group consisting of these may be used.

Examples of copolymers of vinyl chloride monomers with other monomers having unsaturated bonds copolymerizable with the vinyl chloride monomer include vinyl chloride-vinyl acetate copolymers, vinyl chloride-(meth)acrylic acid copolymers, vinyl chloride-methyl (meth)acrylate copolymers, vinyl chloride-ethyl (meth)acrylate copolymers, vinyl chloride-maleic ester copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-propylene copolymers, vinyl chloride-styrene copolymers, vinyl chloride-isobutylene copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-styrene-maleic anhydride terpolymers, vinyl chloride-styrene-acrylonitrile terpolymers, vinyl chloride-butadiene copolymers, vinyl chloride-isoprene copolymers, vinyl chloride-chlorinated propylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-acrylonitrile copolymers, and vinyl chloride-various vinyl ether copolymers.

The method for producing the polyvinyl chloride polymer is not particularly limited. The polyvinyl chloride polymer may be produced by various polymerization methods, such as emulsion polymerization, suspension polymerization, or bulk polymerization. Commercially available polyvinyl chloride polymers may also be used.

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

The polyvinyl chloride polymer may be a polymer blend. For example, a blend of a polyvinyl chloride polymer and a polyolefin may be used as the polymer blend. 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, propylene-α-olefin copolymer, polybutene, polypentene, chloropolyethylene, and chloropolypropylene. One or more selected from the group consisting of these may be used.

The polyvinyl chloride polymer may be further chlorinated. Methods for chlorinating the polyvinyl chloride polymer include, for example, thermal chlorination and photochlorination.

In the film-forming composition of the present invention, the average degree of polymerization of the polyvinyl chloride polymer is preferably 300 to 5000, more preferably 500 to 3000, even more preferably 500 to 2500, even more preferably 600 to 2500, even more preferably 600 to 2000, and even more preferably 600 to 1300, from the viewpoint of improving antifouling properties. 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 polymer is preferably 40 to 90, more preferably 50 to 90, and even more preferably 60 to 80, from the viewpoint of improving antifouling properties. Here, the K value is a value measured in accordance with ISO 1628-2 (JIS K7367-2 Plastics -- Determination of viscosity of diluted polymer solutions using a capillary viscometer -- Part 2: Vinyl chloride resins).

The polyvinyl chloride polymers can generally be classified into suspension vinyl chloride polymers, paste vinyl chloride polymers, and blend vinyl chloride polymers depending on the particle shape, particle size, characteristics, etc. (for example, Toshiro Igarashi, PVC Paste Processing: Characteristics and Applications, Section 1: Characteristics of PVC Paste (pp. 12-23), Section 5: Other Compounding Agents (pp. 93-107), Rubber Digest Co., Ltd., Paste Resin, November 1998).
In this specification, the "particle size" of a "polyvinyl chloride polymer" refers to the "particle size (D50)." The particle size (D50) is a volume-weighted median size (D50) measured in accordance with JIS Z8825. The particle size can be measured in accordance with a laser diffraction particle size analysis method, for example, using a particle size analyzer (SALD-2200, Shimadzu Corporation).

The film-forming composition of the present invention can use, as the polyvinyl chloride polymer, one or more selected from the group consisting of suspension vinyl chloride polymers, paste vinyl chloride polymers, and blend vinyl chloride polymers.
The film-forming composition of the present invention preferably contains at least a suspension vinyl chloride polymer as the polyvinyl chloride polymer, from the viewpoint of improving the antifouling property.
Furthermore, from the viewpoint of improving antifouling properties, it is more preferable that the film-forming composition of the present invention contains a combination of a suspension vinyl chloride polymer and a paste vinyl chloride polymer and/or a blend vinyl chloride polymer as the polyvinyl chloride polymer. It is preferable that the film-forming composition of the present invention further contains a paste vinyl chloride polymer from the viewpoint of improving dispersibility of fibers during raw material mixing.

The suspension vinyl chloride polymer is preferably in the form of particles with a porous structure, more specifically, irregularly shaped particles with many internal voids. The particle size (D50) of the suspension vinyl chloride polymer is preferably 50 to 200 μm, more preferably 100 to 150 μm. Because suspension vinyl chloride polymers are particles with a porous structure, they are able to absorb liquids such as plasticizers into their interiors, making them less likely to become paste-like. Suspension vinyl chloride polymers are also commonly referred to as "general-purpose PVC." Suspension vinyl chloride polymers can be obtained by known manufacturing methods, such as suspension polymerization. The vinyl chloride polymer may be in the form of a slurry in which particles are suspended in water, or a dry powder.

The vinyl chloride paste polymer is preferably spherical, more specifically, perfectly spherical with minimal internal and surface voids. The particle size (D50) of the vinyl chloride paste polymer is preferably 0.01 μm or more, more preferably 0.02 μm or more, with a preferred lower limit of 10 μm or less, more preferably 5 μm or less, and a preferred upper limit of 0.01 to 10 μm, more preferably 0.02 to 5 μm. A typical feature of vinyl chloride paste polymers is that they become paste-like upon the addition of a plasticizer. These vinyl chloride paste polymers are also commonly referred to as "specialty vinyl chlorides." These vinyl chloride paste polymers can be produced by emulsion polymerization or microsuspension polymerization, and may be in the form of a latex in which the polymer particles are emulsified in water.

The blended vinyl chloride polymer is preferably in the form of spherical particles. More specifically, rather than being perfectly spherical like paste vinyl chloride polymers, the particles preferably have an irregular shape but a relatively smooth surface and an appropriate degree of plasticity and affinity. 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. Blended vinyl chloride polymers are generally characterized by their ability to reduce the viscosity of paste vinyl chloride polymers and to create minute convexities on the surface of molded articles, thereby achieving a matte surface. Blended vinyl chloride polymers can be obtained by known manufacturing methods. For example, they can be obtained by suspension polymerization using a suspending agent, optionally with a small amount of emulsifier, in which vinyl chloride monomer droplets are finely dispersed.

In the film-forming composition of the present invention, the content of the suspension vinyl chloride polymer relative to the total mass of the polyvinyl chloride polymer is not particularly limited, but a suitable lower limit is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more. A suitable upper limit is not particularly limited and may be, for example, 100% by mass or less, 90% by mass or less, or 80% by mass or less. From the viewpoint of improving antifouling properties, the preferred range is more preferably 50 to 100% by mass, and even more preferably 50 to 90% by mass.

In the film-forming composition of the present invention, the content of the paste vinyl chloride polymer and/or the blend vinyl chloride polymer relative to the total mass of the polyvinyl chloride polymer is not particularly limited. A suitable lower limit is preferably 0% by mass or more. From the viewpoint of improving fiber dispersibility during raw material mixing and improving stain resistance, it is more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more. A suitable upper limit is not particularly limited and may be, for example, 100% by mass or less or 80% by mass or less. From the viewpoint of improving stain resistance, it is more preferably 70% by mass or less, even more preferably 60% by mass or less, more preferably 50% by mass or less, or even 40% by mass or less. From the viewpoint of improving stain resistance, the suitable numerical range is more preferably 0 to 50% by mass, and even more preferably 20 to 50% by mass.

In the film-forming composition of the present invention, the mass ratio of the suspension vinyl chloride polymer to the other vinyl chloride polymer relative to the total mass of the polyvinyl chloride polymer is not particularly limited, but is preferably 50-100:50-0, more preferably 60-95:40-5, and even more preferably 70-90:30-10, from the perspective of improving antifouling properties. The other vinyl chloride polymer is preferably the paste vinyl chloride polymer and/or the blend vinyl chloride polymer.

From the viewpoint of improving antifouling properties, the film-forming composition may contain, for example, the polyvinyl chloride polymer resin in a proportion of preferably 50% by mass or more, and more preferably 60% by mass or more, relative to the total mass of the film-forming composition. From the viewpoint of improving antifouling properties, the film-forming composition may contain, for example, the polyvinyl chloride polymer resin in a proportion of preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 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, relative to the total mass of the resin.

The resin may contain a resin other than the polyvinyl chloride polymer. Examples of the resin other than the polyvinyl chloride polymer include acrylic resins, polystyrene resins, polyethylene resins, polyimide resins, fluororesins, phenolic resins, epoxy resins, and urethane resins. One or more selected from the group consisting of these can be used. From the viewpoint of improving the antifouling properties, the resin may contain, for example, a resin other than the polyvinyl chloride polymer in an amount of preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the resin.
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 even more preferably 60 to 80, from the viewpoint of improving antifouling properties.

1-1(2) Cellulose Fibers, Chitin Fibers, and Chitosan Fibers From the viewpoint of improving the stain resistance, the film-forming composition of the present invention may contain one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers. The fibers may be (a) cellulose fibers and/or (b) chitin fibers and/or chitosan fibers, either singly or in combination.
The fibers may be commercially available products. The shape of the fibers may be any shape, such as fibrous or granular. An aqueous dispersion of fibers may be used as the fibers.

From the viewpoint of improving the antifouling property, the average fiber diameter of the fibers is preferably 1 nm or more, more preferably 2 nm or more, and is preferably 1,000 nm or less, more preferably 100 nm or less.
From the viewpoint of improving the stain resistance, the average fiber length of the fibers is preferably 0.1 μm or more, more preferably 1 μm or more, and is preferably 1000 μm or less, more preferably 100 μm or less.
The average fiber diameter and average fiber length in the present invention can be calculated, for example, by measuring the diameters of a plurality of fibers (for example, 10 or more fibers) using an electron microscope photograph and calculating the average value.

From the viewpoint of improving the stain resistance, the content of the fiber in the film-forming composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the resin, and is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the resin.

1-1(2)-1. Cellulose fiber

Examples of raw materials for the cellulose fibers 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 also be produced using plant fibers (also called "pulp") separated from these raw materials.
The cellulose fibers may have any shape, such as fibrous or granular, etc. An aqueous dispersion of cellulose fibers may be used as the cellulose fibers.

The method for producing the cellulose fibers is not particularly limited. For example, the cellulose fiber raw material may be chemically treated with an alkali such as sodium hydroxide, followed by mechanical grinding and/or beating using a refiner, a twin-screw kneader (twin-screw extruder), a twin-screw kneader/extruder, a high-pressure homogenizer, a media stirring mill, a millstone, a grinder, a vibration mill, a sand grinder, or the like. Alternatively, the cellulose fiber raw material may be subjected to ultra-high pressure treatment to remove lignin, and the resulting cellulose fiber may be used as the cellulose fiber.
The cellulose fibers may also be subjected to a chemical treatment such as an oxidation treatment using an N-oxyl compound such as 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical (TEMPO), a dilute acid hydrolysis treatment, or an enzyme treatment.
Among these, cellulose fibers that have been subjected to TEMPO oxidation treatment are preferred from the viewpoint of improving the stain resistance.

From the viewpoint of improving the stain resistance, the average fiber diameter of the cellulose fibers is preferably 1 nm or more, more preferably 2 nm or more, and is preferably 1,000 nm or less, more preferably 100 nm or less.
From the viewpoint of improving stain resistance, the average fiber length of the cellulose fibers is preferably 0.1 μm or more, more preferably 1 μm or more, and is preferably 1000 μm or less, more preferably 100 μm or less.

From the viewpoint of improving the stain resistance, the cellulose fiber may have cellulose type I crystals, and the crystallinity thereof is preferably 50% or more, more preferably 56% or more, and even more preferably 60% or more.
The degree of crystallinity in the present invention is the degree of cellulose type I crystallinity calculated by the Segal method from the diffraction intensity value obtained by X-ray diffraction, and can be determined by the following formula (1).
Cellulose I-type crystallinity (%)=[(I _22.6 −I _18.5 )/I _22.6 ]×100 (1)
In the above formula (1), _I22.6 is the diffraction intensity of the (002) lattice plane (diffraction angle 2θ = 22.6°) in X-ray diffraction, and _I18.5 is the diffraction intensity of the amorphous portion (diffraction angle 2θ = 18.5°). Cellulose type I refers to the crystalline form of native cellulose, and cellulose type I crystallinity refers to the proportion of crystalline regions in the entire cellulose.

The cellulose fibers may be commercially available products. Examples of commercially available products include nanoforest-S (manufactured by Chuetsu Pulp Co., Ltd.), BiNFi-s WFo-100 series (1002, 1005, 10010; manufactured by Sugino Machine Ltd.; WMa has been integrated into WFo), Cellenpia ^(R) series (TC-01A, TC-02X (TEMPO-oxidized CNF), CS-01, CS-01C (carboxymethyl CNF); manufactured by Nippon Paper Industries Co., Ltd.), Celish GY-100G (manufactured by Daicel FineChem Ltd.), and Rheocrysta I-2SX (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.). One or more types selected from the group consisting of these may be used.

From the viewpoint of improving stain resistance, the content of the cellulose fibers in the film-forming composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, even more preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the resin. Furthermore, the content of the cellulose fibers is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the resin.

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

The raw materials for the chitin fiber and/or chitosan fiber include, but are not limited to, the shells (exoskeletons) of crustaceans such as shrimp and crab, insects, shellfish, mushrooms, etc. One or more selected from the group consisting of these raw materials can be used.
The chitin and/or chitosan fibers may have any shape, such as fibrous or granular. A water dispersion of chitin and/or chitosan fibers may be used as the chitin and/or chitosan fibers.
Chitosan is generally called deacetylated chitin, and can be obtained by deacetylating chitin by hydrolysis or the like. Chitosan is generally defined as having a degree of deacetylation (%DA) of about 60% or more, and this %DA can be determined by colloid titration (see, for example, Yokoyama, Kota et al., Research on Chitin and Chitosan, Japanese Journal of Oral Implantology, pp. 16-24, Vol. 10, No. 1, March 1997).

The method for producing the chitosan fiber is not particularly limited, and examples thereof include a method in which the raw materials for the chitin fiber and/or chitosan fiber are mechanically ground and/or beaten using a refiner, a twin-screw kneader (twin-screw extruder), a twin-screw kneader extruder, a high-pressure homogenizer, a medium stirring mill, a millstone, a grinder, a vibration mill, a sand grinder, or the like to obtain chitin fiber, and a method in which the obtained chitin fiber is then boiled in a concentrated alkali to obtain chitosan fiber.
Before mechanically grinding and/or beating the raw material, the raw material may be treated with an alkali or acid to remove proteins, calcium, etc. from the raw material.

From the viewpoint of improving antifouling properties, the average fiber diameter of the chitin fibers and/or chitosan fibers is preferably 1 nm or more, more preferably 2 nm or more, and is preferably 1,000 nm or less, more preferably 100 nm or less.
From the viewpoint of improving the antifouling property, the average fiber length of the chitin fibers and/or chitosan fibers is preferably 0.1 μm or more, more preferably 1 μm or more, and is preferably 1000 μm or less, more preferably 100 μm or less.

The chitin fibers and/or chitosan fibers may be commercially available products. Examples of such commercially available products include Chitin-NF (manufactured by Marine Nanofiber Co., Ltd.), Partially Hydrolyzed Chitin-NF (manufactured by Marine Nanofiber Co., Ltd.), Daichitosan series (H, M, PVL, VLA: manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), BiNFi-s SFo-200 series (manufactured by Sugino Machine Co., Ltd.), and BiNFi-s Efoo-080 series (manufactured by Sugino Machine Co., Ltd.). One or more types selected from the group consisting of these can be used.

From the viewpoint of improving stain resistance, the content of the chitin fiber and/or chitosan fiber in the film-forming composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, even more preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the resin. Furthermore, 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, even more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the resin.

1-1(3) Plasticizers

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

From the viewpoint of improving stain resistance, examples of the plasticizer include, but are not limited to, polycarboxylic acid ester plasticizers and benzoic acid ester plasticizers. Examples of the polycarboxylic acid ester plasticizer include, but are not limited to, phthalic acid ester plasticizers, terephthalic acid ester plasticizers, adipic acid ester plasticizers, trimellitic acid ester plasticizers, and citrate ester plasticizers.

Examples of the polycarboxylic acid ester plasticizer include mono-, di-, or triesters obtained from polycarboxylic acids and monoalcohols or their (poly)oxyalkylene adducts.
The number of carbon atoms in the polycarboxylic acid is not particularly limited, but is preferably 3 to 10, and polycarboxylic acids having 3 to 10 carbon atoms are suitable. Examples of the polycarboxylic acid include, but are not limited to, trimellitic acid and dicarboxylic acids. Examples of the valence of the polycarboxylic acid include 2, 3, and 4.
The number of carbon atoms in 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 preferred.
The benzoate ester plasticizer can be obtained from benzoic acid and a monoalcohol or its (poly)oxyalkylene adduct. The monoalcohol or its (poly)oxyalkylene adduct is not particularly limited, but may be the same as the monoalcohol or its (poly)oxyalkylene adduct of the polycarboxylic acid described above.

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

From the viewpoint of improving the antifouling properties of the film-forming composition, it is preferable to use one or more plasticizers selected from the group consisting of DINP, DOP, DOTP, ATBC, DINA, TOTM, and DINCH. Of these, from the viewpoint of improving the antifouling properties and film formability of the film-forming composition, it is more preferable to use one or more plasticizers selected from the group consisting of DINP, DOP, DOTP, ATBC, TOTM, and DINA, and even more preferable to use one or more plasticizers selected from the group consisting of DINP, DOP, ATBC, and DINA.

In the film-forming composition, examples of plasticizers other than the polycarboxylic acid ester-based plasticizers and benzoic acid ester-based plasticizers include polyester-based plasticizers, glycerin-based plasticizers, polyalkylene glycol-based plasticizers, and epoxy-based plasticizers, and one or more types selected from these plasticizers may be used.
The plasticizer may be one produced by a known production method or may be a commercially available product.

From the viewpoint of improving antifouling properties, the content of the plasticizer in the film-forming composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more, relative to 100 parts by mass of the resin. Furthermore, the content of the plasticizer is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of the resin.

1-1(4) Surfactants

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

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants, and one or more surfactants selected from these groups can be used. From the viewpoint of dispersibility in plasticizers, the HLB of the surfactant is preferably 8 to 19.

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

In order to improve the antifouling properties of the film-forming composition, it is preferable to use a nonionic and/or cationic surfactant as the surfactant. Furthermore, when using a nonionic surfactant, it is preferable that the HLB be 8 to 19 in order to improve dispersibility in plasticizers.

The surfactant may be a commercially available product, such as Emulgen 1150S-60 (polyoxyethylene alkyl ether (HLB 18.5), manufactured by Kao Corporation), Emulgen 103 (polyoxyethylene lauryl ether (HLB 8.1), manufactured by Kao Corporation), or Acetamine 24 (coconutamine acetate, manufactured by Kao Corporation), and one or more surfactants selected from the group consisting of these may be used.

From the viewpoint of improving antifouling properties, the content of the surfactant in the film-forming composition is, for example, preferably 10 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less, relative to 100 parts by mass of the resin. Furthermore, there is no particular lower limit for the content of the surfactant. 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, relative to 100 parts by mass of the resin.

1-1(5) Other Components In addition to the components described above, the film-forming composition of the present invention may appropriately contain one or more components selected from the group consisting of matting agents, processing aids, release agents, stabilizers, softeners, antiaging agents (antioxidants), antibacterial agents, antifungal agents, coloring pigments, ultraviolet absorbers, flame retardants, and fillers.
Examples of matting agents include, but are not limited to, hydrophilic fumed silica, acrylic matting agents, etc. The content of the matting agent is not particularly limited, but the upper limit may be, for example, 10 parts by mass or less, 8 parts by mass or less, or 5 parts by mass or less, and the lower limit may be, for example, 0.01 parts by mass or more, 0.1 parts by mass or more, 0.5 parts by mass or more, or 1 part by mass or more, relative to 100 parts by mass of the resin.

1-2. Method for producing film-forming composition

The film-forming composition of the present invention can be produced by mixing raw materials, and examples thereof include the following Examples 1 and 2, but are not particularly limited thereto.
The form of the film-forming composition is not particularly limited and may be a paste, liquid, powder, or the like, but when forming the film-forming composition into a film, it is preferable to use the composition in powder form.

Example 1 of a method for producing the film-forming composition of the present invention may include the following steps:
A mixing process in which one or more types of fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers, a surfactant and/or plasticizer, a vinyl chloride polymer, and other raw materials (impact modifier, heat stabilizer) are mixed to obtain a mixture.
The mixing step may be carried out using a stirring device known in the art. The mixing step may be carried out, for example, at room temperature (20 to 30° C.). The ingredients may be added to the stirring device simultaneously or separately, but it is preferred to mix the ingredients 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 the film-forming composition of the present invention may include the following steps:
(1) a step of mixing one or more types of fiber selected from the group consisting of cellulose fiber, chitin fiber, and chitosan fiber with a surfactant and/or 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 with a vinyl chloride polymer and other raw materials (impact modifier, heat stabilizer) to obtain a mixture.
The steps of obtaining the fiber-containing material and obtaining the mixture may each be performed using a stirring device known in the art. The steps of obtaining the fiber-containing material and obtaining the mixture may each be performed at room temperature (20 to 30°C), for example.
In the step of obtaining the mixture, a surfactant and/or a plasticizer may be mixed in. In the step of obtaining the mixture, a resin other than the polyvinyl chloride polymer may also be mixed in.

1-3. Cured film-forming composition and laminate containing the cured film

The present invention provides a film that is a cured product of the film-forming composition. Use of this film can improve the stain resistance of various molded products.

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

The curing method may be carried out by a method known in the art, such as injection molding, calendar molding, blow molding, extrusion molding, inflation molding, etc. Heat curing is preferred.
The heating temperature in the curing method may be, for example, 150° C. or higher, and preferably 200° C. or higher. The upper limit of the temperature may be, for example, 300° C. or lower or 250° C. or lower, and the preferred range is preferably 200 to 250° C., and more preferably 200 to 220° C. The heating time is not particularly limited, but is desirably within a range in which the film is not thermally denatured while adjusting the film thickness.
Furthermore, when a thick film is obtained, the thickness of the film may be reduced from the viewpoint of subsequent use as a surface layer of a laminate. For example, after a thick film is obtained by a roll method, the film may be further reduced in thickness by a known method such as a heat press method. Examples of the heat press method include a heating temperature of 150 to 250°C and a pressure of 5 to 30 MPa.

From the viewpoint of enhancing stain resistance, a film that is a cured product of the film-forming composition of the present invention can be formed as a surface layer on the surface of a substrate of various molded products such as decorative paper, wallpaper, and leather. The substrate can be, for example, polyvinyl chloride, paper, nonwoven fabric, woven fabric, synthetic leather, etc. Furthermore, the film that is a cured product of the film-forming composition may be formed on the surface of the substrate via a binder such as an adhesive or a curing agent in order to bond well to the substrate.
The film-forming composition of the present invention may be used, for example, as a stain-resistant coating agent for decorative paper, wallpaper, or leather to prevent staining of a substrate. By applying the stain-resistant coating agent to the surface of a substrate and curing it, the stain-resistant properties of the substrate can be improved.

The thickness of the film that is the cured product of the film-forming composition is not particularly limited, but may be, for example, 1 μm or more, and preferably 10 μm or more. The thickness of the film may also be, for example, 500 μm or less, and preferably 100 μm or less, and more preferably 80 μm or less from the perspective of use as a surface layer. This film can improve the stain resistance of various molded products such as decorative paper, wallpaper, and leather.

Various molded articles can be provided that contain, as a surface layer, a film that is a cured product of the film-forming composition of the present invention.
More preferably, a laminate can be provided that includes a film that is a cured product of the film-forming composition of the present invention as at least one or both surface layers, thereby improving the stain resistance of various molded articles and the like.
Examples of the laminate of the present invention include, but are not limited to, laminate films, laminate sheets, and surface-coated molded articles.
The laminate of the present invention can be produced by a known method for producing a laminate, and examples of the production method include, but are not limited to, a top coating method, direct calendar lamination, and post-lamination.

Example 1 of the method for producing a laminate including a film that 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 film as a cured product;
(2) A film laminating step in which the film formed in the film forming step is disposed on a substrate as a surface layer and processed to form a film laminate.
In the film lamination step, a binder may be placed between the formed film and the substrate and then processed.

In the film formation process, the heating temperature during curing can be determined using known curing methods, such as the curing methods described above. The thickness of the film obtained in the film formation process is preferably 1 to 80 μm, more preferably 5 to 60 μm, even more preferably 10 to 25 μm, and even more preferably 10 to 20 μm.

A known film lamination method can be used in the film lamination process. In this case, the heating temperature, mold pressure, speed, etc. can be adjusted as appropriate to ensure good lamination of the film layer to the substrate.

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

In the present invention, further embossing or other processes may be performed to impart design features to the substrate. The embossing may be performed by methods known in the art. For example, the embossing may be performed by foaming the film layer using a heater embosser or a foam embosser during the lamination process, or it may be mechanical embossing.

2. Plastisol composition

The plastisol composition of the present invention contains at least a polyvinyl chloride polymer and one or more fibers selected from the group consisting of cellulose fiber, chitin fiber, and chitosan fiber. The plastisol composition of the present invention is suitable for enhancing the stain resistance of various molded products such as decorative paper, wallpaper, and leather.
An embodiment of the plastisol composition of the present invention will be described below. In the description of this embodiment, the explanation of the components, contents, production method, and usage method that overlap with those in "1. Film-forming composition" above will be omitted as appropriate, but the explanation in "1." also applies to this embodiment and can be adopted as appropriate.

2-1. Components of the Plastisol Composition Each component will now be described.

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 whose main component is a polyvinyl chloride polymer.

From the viewpoint of improving the stain resistance, the plastisol composition may contain, for example, the resin in a proportion of 50% by mass or more, preferably 60% by mass or more, relative to the mass of the plastisol composition. Furthermore, from the viewpoint of improving the stain resistance, the plastisol composition may contain, for example, the polyvinyl chloride polymer in a proportion of 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, relative to the mass of the resin.

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

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

The method for producing the polyvinyl chloride polymer, the crosslinking of the polyvinyl chloride polymer, the polymer blending of the polyvinyl chloride polymer, and the further chlorination of the polyvinyl chloride polymer are as described above in "1."

The average degree of polymerization and K value of the polyvinyl chloride polymer are as described above in "1."
In the plastisol composition of the present invention, the average degree of polymerization of the polyvinyl chloride polymer is preferably 300 to 5,000, more preferably 600 to 3,000, even more preferably 600 to 2,000, and still more preferably 700 to 2,000, from the viewpoint of improving the stain resistance.
In the plastisol composition of the present invention, the K value of the polyvinyl chloride polymer is preferably 40 to 90, more preferably 50 to 90, and even more preferably 60 to 80, from the viewpoint of improving the stain resistance.
The suspension vinyl chloride polymer, paste vinyl chloride polymer, and blend 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 polymer. Examples of the resin other than the polyvinyl chloride polymer include acrylic resins, polystyrene resins, polyethylene resins, polyimide resins, fluororesins, phenolic resins, epoxy resins, and urethane resins, and one or more resins selected from these may be used.
In the plastisol composition of the present invention, the resin may contain, for example, a resin other than a polyvinyl chloride polymer in an amount of 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the resin, from the viewpoint of improving the stain resistance.
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 even more preferably 60 to 80, from the viewpoint of improving the antifouling property.

2-1(2) Cellulose Fibers, Chitin Fibers, and Chitosan Fibers From the viewpoint of improving stain resistance, the plastisol composition of the present invention may contain at least one or two or more types of fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers. The fibers may be (a) cellulose fibers and/or (b) chitin fibers and/or chitosan fibers, either singly or in combination.
The shape of the fibers of the present invention, the average fiber diameter of the fibers, the average fiber length of the fibers, the content of the fibers in the plastisol composition, etc. are as described above in "1."

2-1(2)-1. Cellulose fiber

The raw materials for the cellulose fibers of the present invention, the method for producing the cellulose fibers, the average fiber diameter of the cellulose fibers, cellulose type I crystals, commercially available products, etc. are as described above in "1."

From the viewpoint of improving stain resistance, the content of the cellulose fibers in the plastisol composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.2 parts by mass or more, per 100 parts by mass of the resin. Furthermore, the content of the cellulose fibers is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the resin.

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

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

From the viewpoint of improving stain resistance, the content of the chitin fiber and/or chitosan fiber in the plastisol composition is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.2 parts by mass or more, per 100 parts by mass of the resin. Furthermore, 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, per 100 parts by mass of the resin.

2-1 (3) Plasticizers

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

Examples of the plasticizer in the plastisol composition, from the viewpoint of improving the stain resistance, include phthalate ester-based plasticizers such as diisononyl phthalate (DINP), bis(2-ethylhexyl) phthalate (DOP), diisodecyl phthalate (DIDP), dibutyl phthalate (DBP), and diundecyl phthalate (DUP); terephthalate ester-based plasticizers such as bis(2-ethylhexyl) terephthalate (DOTP); adipate ester-based plasticizers such as diisononyl adipate (DINA), bis(2-ethylhexyl) adipate (DOA), and diisodecyl adipate (DIDA); trimellitate ester-based plasticizers such as trioctyl trimellitate (TOTM); 1,2-cyclohexanedicarboxylic acid diisononyl ester (DINCH); and citrate ester-based plasticizers such as acetyl tributyl citrate (ATBC).
Of these, phthalate ester plasticizers are preferred from the viewpoint of improving antifouling properties and cost.
One or more kinds selected from the group consisting of these plasticizers can be used.

In the plastisol composition, from the viewpoint of improving the antifouling property, it is preferable to use one or more plasticizers selected from the group consisting of DINP, DOP, DOTP, ATBC, DINA, TOTM, and DINCH. Among these, from the viewpoint of improving the antifouling property in the plastisol composition and from the viewpoint of the plastisol, it is more preferable to use one or more plasticizers selected from the group consisting of DINP, DOP, DOTP, DINA, TOTM, and DINCH, and even more preferable to use one or more plasticizers selected from the group consisting of DINP, DOP, and DINCH.
The plastisol composition may contain a plasticizer other than the polycarboxylic acid ester plasticizer and the benzoic acid ester plasticizer, within a range that does not impair the effects of the present invention.

From the viewpoint of improving stain resistance, the content of the plasticizer in the plastisol composition is preferably 1 part by mass or more, more preferably 20 parts by mass or more, and even more preferably 40 parts by mass or more, per 100 parts by mass of the resin. Furthermore, the content of the plasticizer is preferably 120 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 95 parts by mass or less, per 100 parts by mass of the resin.

2-1 (4) Surfactants

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

Examples of the surfactant include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants, and one or more surfactants selected from these groups can be used. From the viewpoint of dispersibility in plasticizers, the HLB of the surfactant is preferably 8 to 19.

The nonionic surfactants, cationic surfactants, amphoteric surfactants, and commercially available products of the present invention are as described above in "1."

In order to improve the antifouling properties of the plastisol composition, it is preferable to use a nonionic and/or cationic surfactant as the surfactant. Furthermore, when using a nonionic surfactant, it is preferable that the HLB be 8 to 19 in order to improve dispersibility in plasticizers.

From the viewpoint of improving antifouling properties, the content of the surfactant in the plastisol composition is preferably, for example, 10 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.2 parts by mass or less, and even more preferably 0.1 parts by mass or less, relative to 100 parts by mass of the resin. Furthermore, there is no particular lower limit for the content of the surfactant. 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, relative to 100 parts by mass of the resin.

2-1(5) Other Components In addition to the components described above, the plastisol composition of the present invention may appropriately contain one or more components selected from the group consisting of matting agents, stabilizers, viscosity reducers, softeners, antiaging agents (antioxidants), diluents, thickeners, antibacterial agents, antifungal agents, coloring pigments, ultraviolet absorbers, flame retardants, and fillers.

2-2. Manufacturing method of plastisol composition

The method for producing the plastisol composition of the present invention can be exemplified by the following example, but is not particularly limited thereto.
The plastisol composition may be prepared in a paste, liquid, powder, or other form, and is not particularly limited thereto. However, when used, it is preferably in a liquid or paste form, and more preferably in a paste form, from the viewpoint of application.

An example of a method for making the plastisol composition of the present invention may include the following steps:
(1) a mixing step of mixing a polyvinyl chloride polymer with one or more types of fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers to obtain a mixture; and (2) a dehydration step of stirring and dehydrating the mixture obtained in the mixing step under reduced pressure.
Each step will be described in more detail below.

(1) Mixing process

In the mixing step, a polyvinyl chloride polymer is mixed with one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers. In the mixing step, resins other than the polyvinyl chloride polymer and the other components mentioned above (e.g., plasticizers, surfactants, etc.) may also be mixed.

The mixing step may be carried out using a stirring device known in the art. The mixing step may be carried out, 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 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. The dehydration step may also be carried out under absolute vacuum (0 kPa).
The mixture is stirred under reduced pressure to remove water contained in the fibers, etc. The dehydration step can be carried out at room temperature (20 to 30° C.), for example.

2-3. How to use plastisol compositions

The plastisol composition of the present invention is used by being applied to the surface of the substrate of various molded products such as decorative paper, wallpaper, and leather. The substrate can be, for example, polyvinyl chloride, paper, nonwoven fabric, woven fabric, synthetic leather, etc. By curing the plastisol composition applied to the substrate, the stain resistance of various molded products can be improved. The plastisol composition of the present invention can be suitably used to improve the stain resistance of, for example, decorative paper, wallpaper, leather, etc. The plastisol composition of the present invention can be used, for example, as a stain-resistant coating agent for decorative paper, a stain-resistant coating agent for wallpaper, or a stain-resistant coating agent for leather.

A method for using the plastisol composition of the present invention may, for example, include the following steps:
(1) a coating step in which a plastisol composition is applied to a substrate; and (2) a heating step in which the plastisol composition applied to the substrate in the coating step is heated to obtain a cured product.
Each step will be described in detail below.

(1) Coating process

In the coating step, the plastisol composition is coated onto a substrate.
The coating step may be performed using an apparatus known in the art. The coating step may 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, and preferably 10 μm or more. The coating thickness may be, for example, 500 μm or less, and preferably 100 μm or less.

(2) Heating process

In the heating step, the plastisol composition applied to the substrate in the application 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, and preferably 200°C or higher. The temperature may be, for example, 350°C or lower, and preferably 300°C or lower. The time in the heating step may be, for example, 10 seconds or longer, and preferably 30 seconds or longer. The time may be, for example, 120 seconds or shorter, and preferably 90 seconds or shorter.

In the present invention, embossing or other processes may be further performed to impart design features to the substrate. The embossing may be performed by methods known in the art.

2-4. Cured products of plastisol compositions and molded articles containing the cured products

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 one obtained by the method described above in "2-3. Method of using the plastisol composition." The cured product may be a foam.
The cured product can enhance the stain resistance of various molded articles such as decorative paper, wallpaper, and leather.
Furthermore, a molded article can be provided that includes a surface layer made of the cured product of the plastisol composition of the present invention. A laminate can be provided that includes a surface layer made of the cured product of the plastisol composition of the present invention and a substrate layer. This can improve the stain resistance of the molded article.

3. Polyvinyl chloride resin composition The present invention can provide a polyvinyl chloride resin composition containing a polyvinyl chloride polymer and one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers.
[0033] Hereinafter, an embodiment of the polyvinyl chloride resin composition of the present invention will be described. In the description of this embodiment, the explanations of the respective components, contents, production methods, and usage methods that overlap with those of the above-mentioned "1. Film-forming composition" and "2. Plastisol composition" will be omitted as appropriate, but the explanations of "1." and "2." also apply to this embodiment and can be adopted as appropriate.

The polyvinyl chloride resin composition of the present invention is suitable for enhancing the stain resistance of various molded products such as decorative paper, wallpaper, and leather. The polyvinyl chloride resin composition can be formed into a cured product such as a film or sheet, but the cured product is not particularly limited. The polyvinyl chloride resin composition can also be used in the form of a plastisol as described above.

The polyvinyl chloride resin composition may be an emulsion type, and the emulsion type may be either an oil-in-water type (O/W) or a water-in-oil type (W/O).
The polyvinyl chloride emulsion resin composition can be obtained by appropriately using raw materials such as an emulsifier, a surfactant, a dispersion medium (e.g., water), a crosslinking agent, and other additives, and mixing and emulsifying them by stirring or the like.
The polyvinyl chloride emulsion resin composition can be used as a film-forming composition, a sheet-forming composition, a coating agent, etc. More specifically, the emulsion resin composition can be used for producing, for example, a surface film, a laminated film, a laminated sheet, a foamed sheet, wallpaper, etc.
The polyvinyl chloride emulsion resin composition may be impregnated into an object, or may be applied or coated onto the surface of an object, such as a molded product, to enhance the antifouling properties of the object. Also, to enhance the antifouling properties of the object, a cured product formed from the polyvinyl chloride emulsion resin composition, such as a film or sheet, may be formed as a surface layer of the object.

The present invention will be described in further detail below based on examples, comparative examples, and test examples. Note that 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, its cured product, and laminate containing the cured product>

<Wallpaper base manufacturing>

As shown in Table 1 below, 100 parts by weight of paste polyvinyl chloride resin (PQLT, manufactured by Shin-Dai-Ichi Vinyl Corporation) as the resin, 60 parts by weight of DINP (manufactured by C.G. Ester Corporation) as the plasticizer, 100 parts by weight of BF-200S (manufactured by Bihoku Funka Kogyo Co., Ltd.) as the filler, 5 parts by weight of AZ-VI-25 (manufactured by Otsuka Chemical Co., Ltd.) as the foaming agent, 10 parts by weight of SR-1 (manufactured by Sakai Chemical Industry Co., Ltd.) as the white pigment, 3 parts by weight of FL-44 (manufactured by ADEKA Corporation) as the stabilizer, and 7 parts by weight of BYK-4041 (manufactured by BYK Corporation) as the viscosity reducer were mixed using a mixer, and the mixture was applied to flame-retardant paper using a film applicator with film thickness adjustment function (manufactured by Allgood Corporation).

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

Example 1
(1) Mixing step 50 parts by mass of nanoforest-S (fiber content 10%, manufactured by Chuetsu Pulp Industries Co., Ltd.) as cellulose fiber, 95 parts by mass of DINP (manufactured by C.G. Ester Co., Ltd.) as a plasticizer, and 2 parts by mass of Emulgen 1150S-60 (HLB 18.5, manufactured by Kao Corporation) as a surfactant were mixed in a stirrer to obtain a fiber-containing material 1. DINP was added to 6.5 parts by mass of the fiber-containing material 1 so that the total plasticizer content was 50 parts by mass, and then 35 parts by mass of PVC (product name: P21, average degree of polymerization: 1550, K value: 75.1, manufactured by Shin-Dai-Ichi Vinyl Corporation), 35 parts by mass of cross-linked PVC (product name: PN-900, manufactured by Shin-Dai-Ichi Vinyl Corporation), and 30 parts by mass of blended PVC (product name: PS-300K, K value: 69, manufactured by Kaneka Corporation) were added as resins, 3 parts by mass of a Ba/Zn-based stabilizer (manufactured by Katsuta Chemical Industry Co., Ltd.), and 1 part by mass of BYK-4041 (manufactured by BYK Corporation) as a viscosity reducer were added, and the mixture was mixed with a stirrer to obtain mixture 1.

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

(3) Coating Step and Heating Step The plastisol composition 1 obtained in (2) above was coated on 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 to foam, thereby obtaining wallpaper sample 1.

Example 2
Fiber-containing material 2 was obtained in the same manner as in Example 1, except that 50 parts by mass of BiNFi-s WMa-10010 (fiber content 10%, manufactured by Sugino Machine Co., Ltd.; as of March 2020, WMa has been integrated into WFo, and this "WMa-10010" has become "WFo-10010") was used as the cellulose fiber. Furthermore, plastisol composition 2 was obtained in the same manner as in Example 1, except that 6.5 parts by mass of fiber-containing material 2 was used. The fiber content of plastisol composition 2 was 0.22 parts by mass per 100 parts by mass of resin. Thereafter, wallpaper sample 2 was obtained in the same manner as in Example 1.

Example 3
Fiber-containing material 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 Co., Ltd.) was used as the cellulose fiber. Furthermore, plastisol composition 3 was obtained in the same manner as in Example 1, except that 6.5 parts by mass of fiber-containing material 3 was used. The fiber content of plastisol composition 3 was 0.22 parts by mass per 100 parts by mass of resin. Thereafter, wallpaper sample 3 was obtained in the same manner as in Example 1.

Example 4
Fiber-containing material 4 was obtained in the same manner as in Example 1, except that 250 parts by mass of Rheocrysta I-2SX (fiber content 2%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used as the cellulose fiber. Furthermore, plastisol composition 4 was obtained in the same manner as in Example 1, except that 15.4 parts by mass of fiber-containing material 4 was used. The fiber content of plastisol composition 4 was 0.22 parts by mass per 100 parts by mass of resin. Wallpaper sample 4 was then obtained in the same manner as in Example 1.

Example 5
Fiber-containing material 5 was obtained in the same manner as in Example 1, except that 500 parts by mass of marine nanofiber (partially hydrolyzed chitin) (fiber content 1%, manufactured by Marine Nanofiber Co., Ltd.) was used as the chitosan fiber. Furthermore, plastisol composition 5 was obtained in the same manner as in Example 1, except that 26.5 parts by mass of fiber-containing material 5 was used. The fiber content of plastisol composition 5 was 0.22 parts by mass per 100 parts by mass of resin. Wallpaper sample 5 was then obtained in the same manner as in Example 1.

Example 6
Plastisol composition 6 was obtained in the same manner as in Example 1, except that DOP (manufactured by C.G. Ester Co., Ltd.) was used as the plasticizer. Wallpaper sample 6 was then obtained in the same manner as in Example 1.

Example 7
Plastisol composition 7 was obtained in the same manner as in Example 1, except that DOTP (manufactured by LG Chemicals) was used as the plasticizer. Wallpaper sample 7 was then obtained in the same manner as in Example 1.

(Example 8)
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 the plasticizer. Wallpaper sample 8 was then obtained in the same manner as in Example 1.

Example 9
Plastisol composition 9 was obtained in the same manner as in Example 1, except that TOTM (manufactured by DIC Corporation) was used as the plasticizer. Wallpaper sample 9 was then obtained in the same manner as in Example 1.

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

Example 11
A 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. Wallpaper sample 11 was then obtained in the same manner as in Example 1.

Example 12
A plastisol composition 12 was obtained in the same manner as in Example 1, except that 2 parts by mass of Acetamine 24 (manufactured by Kao Corporation) was used as the surfactant. Thereafter, a wallpaper sample 12 was obtained in the same manner as in Example 1.

Example 13
Plastisol composition 13 was obtained in the same manner as in Example 1, except that the resins used were 35 parts by mass of PVC (product name: P21, average degree of polymerization: 1550, K value: 75.1, manufactured by Shin-Dai-Ichi Vinyl Corporation), 30 parts by mass of crosslinked PVC (product name: PN-900, manufactured by Shin-Dai-Ichi Vinyl Corporation), and 35 parts by mass of vinyl chloride-vinyl acetate copolymer (product name: PCH-12, K value: 74, manufactured by Kaneka Corporation). Wallpaper sample 13 was then obtained in the same manner as in Example 1.

Example 14
A plastisol composition 14 was obtained in the same manner as in Example 1, except that 35 parts by mass of PVC (product name: P21, average degree of polymerization: 1550, manufactured by Shin-Dai-Ichi Vinyl Corporation), 30 parts by mass of crosslinked PVC (product name: PN-900, manufactured by Shin-Dai-Ichi Vinyl Corporation), and 35 parts by mass of acrylic resin (manufactured by Mitsubishi Chemical Corporation) were used as the resins. Thereafter, a wallpaper sample 14 was obtained in the same manner as in Example 1.

Example 15
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-Dai-Ichi Vinyl Corporation) was used as the resin. Wallpaper sample 15 was then obtained in the same manner as in Example 1.

Example 16
Plastisol composition 16 was obtained in the same manner as in Example 1, except that 0.65 parts by mass of fiber-containing material 1 of Example 1 was used. The fiber content of plastisol composition 16 was 0.022 parts by mass per 100 parts by mass of resin. Wallpaper sample 16 was then obtained in the same manner as in Example 1.

(Example 17)
50 parts by mass of nanoforest-S as cellulose fibers, 44.5 parts by mass of DINP as a plasticizer, and 2 parts by mass of Emulgen 1150S-60 as a surfactant were mixed in a stirrer to obtain fiber-containing material 17. Plastisol composition 17 was obtained in the same manner as in Example 1, except that 6.5 parts by mass of fiber-containing material 17 was used. The fiber content of plastisol composition 17 was 0.41 parts by mass per 100 parts by mass of resin. Wallpaper sample 17 was then obtained in the same manner as in Example 1.

(Example 18)
50 parts by mass of nanoforest-S as cellulose fibers and 2 parts by mass of Emulgen 1150S-60 as a surfactant were mixed in a stirrer to obtain a fiber-containing material 18. A plastisol composition 18 was obtained in the same manner 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 per 100 parts by mass of the resin. Wallpaper sample 18 was then obtained in the same manner as in Example 1.

Example 19
50 parts by mass of nanoforest-S as cellulose fibers and 2 parts by mass of Emulgen 1150S-60 as a surfactant were mixed in a stirrer to obtain a fiber-containing material 19. 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 plastisol composition 19 was 1.25 parts by mass per 100 parts by mass of resin. Wallpaper sample 19 was then obtained in the same manner as in Example 1.

(Example 20)
50 parts by mass of nanoforest-S as cellulose fibers and 95 parts by mass of DINP as a plasticizer were mixed in a stirrer to obtain a fiber-containing material 20. A plastisol composition 20 was obtained in the same manner 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 per 100 parts by mass of resin. Thereafter, a wallpaper sample 20 was obtained in the same manner as in Example 1.

(Example 21)
50 parts by mass of nanoforest-S as cellulose fibers, 44.5 parts by mass of DINP as a plasticizer, and 1 part by mass of Emulgen 1150S-60 as a surfactant were mixed in a stirrer to obtain a fiber-containing material 21. A plastisol composition 21 was obtained in the same manner 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 per 100 parts by mass of resin. Wallpaper sample 21 was then obtained in the same manner as in Example 1.

(Comparative Example 1)
Wallpaper sample 101 of Comparative Example 1 was a wallpaper base to which nothing was applied.

(Comparative Example 2)
95 parts by mass of DINP was used as a plasticizer to obtain a fiber-containing material 102. A 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. Wallpaper sample 102 was then obtained in the same manner as in Example 1.

(Comparative Example 3)
95 parts by mass of DINP as a plasticizer and Emulgen 1150S-60 as a surfactant
The mixture was mixed with 4.22 parts by mass of the fiber-containing material 103 in a stirrer to obtain a fiber-containing material 103. A plastisol composition 103 was obtained in the same manner as in Example 1, except that 4.22 parts by mass of the fiber-containing material 103 was used. Wallpaper sample 103 was then obtained in the same manner as in Example 1.

<Evaluation of wallpaper samples>
(Evaluation of wallpaper samples 1-19, 101-103)
Each wallpaper sample obtained in each example and comparative example was evaluated for stain resistance in accordance with the stain-resistant wallpaper performance standards established by the Wallpaper Industry Association.
Specifically, crayon was applied to each wallpaper sample cut to 30 mm x 220 mm, and after 24 hours, the crayon was wiped off with a neutral detergent and visually evaluated. The wiped area was compared with the original piece, and a rating of grade 4 or higher was considered good. The staining gray scale was in accordance with JIS L 0805. In this experiment, the evaluation of the stain-resistant wallpaper performance standard was subdivided, and intermediate ratings for each grade were also added.
<Evaluation criteria>
Grade 5: Dirt is about the same as gray scale number 5 for contamination (no dirt remains)
Grades 4 to 5: Better than Grade 4, but not as good as Grade 5. Grade 4: The stain is about No. 4 on the staining gray scale (almost no stain remains).
Grades 3 to 4: Better than Grade 3, but not as good as Grade 4. Grade 3: The stain is about Gray Scale No. 3 for contamination (some stains remain).
Grades 2 to 3: Better than Grade 2, but not as good as Grade 3. Grade 2: The stain is about Gray Scale No. 2 for contamination (considerable staining remains).
Grades 1 to 2: Better than Grade 1, but not as good as Grade 2. Grade 1: The stain is about Gray Scale No. 1 for contamination (the stain remains dark).

The compositions and evaluation results for Examples 1 to 21 and Comparative Examples 1 to 3 are shown in Tables 2 to 4 below. Note that the numbers in the tables for items other than "Evaluation" indicate parts by mass.

The results of Examples 1 to 5 and Comparative Examples 1 to 3 demonstrate that the stain resistance of wallpaper can be improved by using a plastisol composition that combines a polyvinyl chloride polymer with one or more fibers selected from the group consisting of cellulose fiber, chitin fiber, and chitosan fiber.
The results of Examples 1 and 6 to 10 also show that a wide range of plasticizers can be used in the plastisol composition, and that the stain-resistant effect of wallpaper is excellent when at least one of DINP, DOP, DOTP, DINA, TOTM, and DINCH is used as the plasticizer.
Furthermore, the results of Examples 1, 11, and 12 show that a wide range of surfactants can be used in the plastisol composition. These results also show that the stain-resistant effect of wallpaper is excellent when a nonionic surfactant or a cationic surfactant is used as the surfactant. Furthermore, when a nonionic surfactant is used as the surfactant, the stain-resistant effect of wallpaper is excellent, especially when a nonionic surfactant with an HLB of 8 to 19 is used.
The results of Examples 1 and 13-15 show that a wide range of resins can be used in the plastisol composition.
The results of Examples 1 and 16 to 19 show that the stain-resistant effect of wallpaper is good, particularly when the content of cellulose fiber in the plastisol composition is 0.02 parts by mass or more per 100 parts by mass of resin.
The results of Examples 1, 20 and 21 show that the plastisol composition has a good stain-resistant effect on wallpaper even though it does not contain a surfactant.

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

A wallpaper base with a thickness of 170 μm was obtained according to the procedure described above in <Wallpaper base manufacturing>.

<Raw materials for polyvinyl chloride resin compositions>
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-Dai-Ichi Vinyl Co., Ltd.)
Suspension PVC (product name: ZEST 1300Z, K value 71.5, average polymerization degree: 1300, manufactured by Shin-Dai-Ichi Vinyl Co., Ltd.)
Paste PVC (product name: ZEST P21, K value 75.1, average degree of polymerization: 1550, manufactured by Shin-Dai-Ichi Vinyl Corporation)
Paste PVC (product name: ZEST PQLT, K value 61.6, average degree of polymerization: 800, manufactured by Shin-Dai-Ichi Vinyl Corporation)
Paste cross-linked PVC (product name: PN-900, manufactured by Shin-Daiichi Vinyl Corporation)
Blended PVC (product name: XPS-300L, manufactured by Kaneka Corporation)
The particle sizes (D50) of the suspension PVCs ZEST 700LS and ZEST 1300Z were in the range of 100 to 150 μm. The particle sizes (D50) of the paste PVCs ZEST P21 and ZEST PQLT, and the paste crosslinked PVC PN-900 were in the range of 0.02 to 5 μm.

Plasticizer: Diisononyl phthalate (DINP) (manufactured by C.G. Ester Co., Ltd.)
Bis(2-ethylhexyl) phthalate (DOP) (manufactured by C.G. Ester Co., Ltd.)
Bis(2-ethylhexyl) terephthalate (DOTP) (LG Chemicals)
Acetyl tributyl citrate (ATBC) (manufactured by Taoka Chemical Co., Ltd.)
Trioctyl trimellitate (TOTM) (DIC Corporation)
Diisodecyl adipate (DINA) (Taoka Chemical Co., Ltd.)

Impact resistance improver: Acrylic rubber (product name: Metablen W-300A, manufactured by Mitsubishi Chemical Corporation)
Heat stabilizer: Ba/Zn-based heat stabilizer (product name: AC-723, manufactured by ADEKA Corporation)
Epoxidized soybean oil (manufactured by Daikyo Chemical Industry Co., Ltd.)
Heat stabilizer (product name: SC-126, manufactured by ADEKA Corporation)
(Fiber: Cellulose fiber)
nanoforest-S (product name: nanoforest-S, fiber content 10%, fiber width several nm to several μm, manufactured by Chuetsu Pulp Industries Co., Ltd.)
CELLENPIA TC-02X (product name: CELLENPIA TC-02X, fiber content 5%, TEMPO-oxidized CNF, fiber length (short fiber) several hundred 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 Ltd.)
Celish GY-100G (product name: Celish GY-100G, fiber content 10%, average fiber diameter 0.01 to 50 μm, manufactured by Daicel FineChem Ltd.)
Rheocrysta I-2SX (product name: Rheocrysta I-2SX, fiber content 2%, fiber width approximately 3 nm, manufactured by Daiichi 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 nanometers, water 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 several tens of nm, water dispersion, manufactured by Marine Nanofiber Co., Ltd.)

(Surfactant)
Nonionic surfactant (product name: Emulgen 1150S-60, polyoxyethylene alkyl ether, HLB 18.5, manufactured by Kao Corporation)
Nonionic surfactant (product name: Emulgen 103, polyoxyethylene lauryl ether, HLB 8.1, manufactured by Kao Corporation)
Alkylamine acetate (product name: Acetamine 24, coconut amine acetate, manufactured by Kao Corporation)

Matting agent: Hydrophilic fumed silica (product name: Aerosil #300, manufactured by Evonik)
Acrylic matting agent (product name: Metablen F-310, manufactured by Mitsubishi Chemical Corporation)

<Production of film-forming composition>
(1) Mixing Step The raw materials and the amounts added shown in Tables 5 and 6 below were mixed to obtain the respective mixtures as film-forming compositions for the respective test examples.
As a specific addition procedure, fibers, surfactants, and plasticizers were mixed in a mixer at room temperature (approximately 20 to 30°C) to obtain a fiber-containing material, and the fiber-containing material was then mixed with resin and other raw materials (impact modifiers, heat stabilizers, matting agents, etc.) to obtain a mixture (Test Examples 2, 4 to 25).
In Test Examples 1 and 3, a plasticizer, a resin, and other raw materials (impact modifier, heat stabilizer) were mixed at room temperature (approximately 20 to 30°C) without adding fibers or surfactants, to obtain mixtures that did not contain fibers or surfactants.

The addition procedure for producing the mixture described above may be changed to "add each ingredient to a mixer and then stir all ingredients simultaneously." The mixture obtained by stirring all ingredients simultaneously will have the same quality (such as stain resistance) as the mixture obtained using the above addition procedure.

(Test Example 1)
As shown in Test Example 1 of Table 5, 15 parts by mass of a plasticizer (DINP), 100 parts by mass of suspension PVC as a resin, 3 parts by mass of an impact resistance improver (Metablen W-300A), 3 parts by mass of a Ba/Zn-based heat stabilizer (AC-723), 3 parts by mass of a heat stabilizer (epoxidized soybean oil), and 1 part by mass of a heat stabilizer (SC-126) were mixed in a stirrer to obtain a mixture of Test Example 1 that did not contain fibers or surfactants.

(Test Example 2)
As shown in Test Example 2 in Table 5, 15 parts by mass of plasticizer (DINP), 2.22 parts by mass of cellulose fiber (fiber content 10%), and 0.09 parts by mass of surfactant were mixed in a mixer to obtain a fiber-containing material. This fiber-containing material was mixed with 100 parts by mass of suspension PVC as a resin, 3 parts by mass of an impact modifier, and 3 parts by mass of AC-723, 3 parts by mass of epoxidized soybean oil, and 1 part by mass of SC-126 as heat stabilizers to obtain the mixture of Test Example 2. This mixture contained 0.222 parts by mass of fiber per 100 parts by mass of resin.

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

(Test Example 4)
As shown in Test Example 4 in Table 5, the mixture of Test Example 4 was obtained in the same manner as Test Example 2, except that the resin contained in Test Example 2 was changed from "100 parts by mass of suspension PVC" to "80 parts by mass of suspension PVC and 20 parts by mass of paste PVC (ZEST P21)." The mixture contained 0.222 parts by mass of fiber per 100 parts by mass of resin.

(Test Examples 5 to 9: Types of polycarboxylic acid ester plasticizers)
(Test Example 5)
As shown in Test Example 5 in Table 5, a mixture of Test Example 5 was obtained in the same manner as Test Example 4, except that diisononyl phthalate (DINP) in Test Example 4 was replaced with bis(2-ethylhexyl) phthalate (DOP).

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

(Test Example 7)
As shown in Test Example 7 in Table 5, the mixture of Test Example 7 was obtained in the same manner as Test Example 4, except that diisononyl phthalate (DINP) in Test Example 4 was replaced with acetyl tributyl citrate (ATBC).

(Test Example 8)
As shown in Test Example 8 in Table 5, the mixture of Test Example 8 was obtained in the same manner as Test Example 4, except that diisononyl phthalate (DINP) in Test Example 4 was replaced with trioctyl trimellitate (TOTM).

(Test Example 9)
As shown in Test Example 9 in Table 5, the mixture of Test Example 9 was obtained in the same manner as Test Example 4, except that diisononyl phthalate (DINP) in Test Example 4 was replaced with diisodecyl adipate (DINA).

(Test Examples 10 to 13 and 14 to 16: Fiber Type and Content)
(Test Example 10)
As shown in Test Example 10 in Table 5, the mixture of Test Example 10 was obtained in the same manner as Test Example 4, except that the cellulose fiber of Test Example 4 (nanoforest-S, fiber content 10%) was replaced with the cellulose fiber of Test Example 10 (Cellenpia TC-02X, fiber content 5%, TEMPO-oxidized CNF). The mixture contained 0.222 parts by mass of fiber per 100 parts by mass of resin.

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

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

(Test Example 13)
As shown in Test Example 13 in Table 5, the mixture of Test Example 13 was obtained in the same manner as Test Example 4, except that the cellulose fiber of Test Example 4 (nanoforest-S fiber content 10%) was replaced with the chitosan fiber of Test Example 13 (partially hydrolyzed chitin-NF, fiber content 1%, aqueous dispersion). The mixture contained 0.222 parts by mass of fiber per 100 parts by mass of resin.

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

(Test Example 16)
As shown in Test Example 16 in Table 6, a mixture of Test Example 16 was obtained in the same manner as Test Example 10, except that the content of the cellulose fiber (Cellenpia TC-02X, fiber content 5%, TEMPO-oxidized CNF) of Test Example 16 was 8.88 parts by mass, instead of 4.44 parts by mass of the cellulose fiber (Cellenpia TC-02X, fiber content 5%, TEMPO-oxidized CNF) of Test Example 10. The mixture contained 0.444 parts by mass of fiber per 100 parts by mass of resin.

(Test Examples 17 to 21: Resin Type and Mass Content Ratio)
(Test Example 17)
As shown in Test Example 17 in Table 6, a mixture of Test Example 17 was obtained in the same manner as Test Example 4, except that the amounts of "80 parts by mass of suspension PVC and 20 parts by mass of paste PVC (ZEST P21)" in Test Example 4 were changed to "50 parts by mass and 50 parts by mass," respectively.

(Test Example 18)
As shown in Test Example 18 in Table 6, the mixture of Test Example 18 was obtained in the same manner as Test Example 4, except that the "20 parts by mass of paste PVC (ZEST P21)" in Test Example 4 was replaced with "20 parts by mass of paste crosslinked PVC (PN-900)."

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

(Test Example 20)
As shown in Test Example 20 in Table 6, a mixture of Test Example 20 was obtained in the same manner as 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)."

(Test Example 21)
As shown in Test Example 21 in Table 6, a mixture of Test Example 21 was obtained in the same manner as Test Example 4, except that 80 parts by mass of suspension PVC (700LS) in Test Example 4 was replaced with 80 parts by mass of suspension PVC (1300Z).

(Test Examples 22 to 23: Amount of Polycarboxylic Acid Ester-Based Plasticizer)
(Test Example 22)
As shown in Test Example 22 in Table 6, a mixture of Test Example 22 was obtained in the same manner as Test Example 4, except that the content of "15 parts by mass of diisononyl phthalate (DINP)" in Test Example 4 was changed to 5 parts by mass.
(Test Example 23)
As shown in Test Example 23 in Table 6, a mixture of Test Example 23 was obtained in the same manner as Test Example 4, except that the content of "15 parts by mass of diisononyl phthalate (DINP)" in Test Example 4 was changed to 30 parts by mass.

(Test Examples 24-25: Addition of matting agent)
(Test Example 24)
As shown in Test Example 24 in Table 6, the mixture of Test Example 24 was obtained in the same manner as 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 materials of Test Example 4.
(Test Example 25)
As shown in Test Example 25 in Table 6, the mixture of Test Example 25 was obtained in the same manner as Test Example 4, except that 5 parts by mass of an acrylic matting agent (Metablen F-310) was further added as a matting agent to the raw materials of Test Example 4.

(2) Film forming process and lamination process (foamed raw sheet production)
<Topcoat film formation>
The mixture of Test Example 1 obtained in the mixing step (1) above was kneaded in a calendar roll (two-roll) device at 150°C for 5 minutes and rolled to a thickness of about 500 μm to produce a film. The 500 μm thick film was further rolled at 150°C for 2 minutes to a thickness of 100 μm to form a thin coated film.
The thin coated film (100 μm thick) of Test Example 1 was further thinned by heat pressing under the following conditions to form a top coat film having a thickness of 50 μm.
[Heat pressing conditions: preheating at 200°C for 1 minute, 1 MPa → pressure at 10 MPa at 200°C for 1 minute → pressure at 15 MPa at 200°C for 1 minute → pressure at 20 MPa at 200°C for 1 minute]
For each of the mixtures of Test Examples 2 to 25, a top coat film was formed in the same manner as in the above-mentioned method for forming the top coat film.
The film-forming compositions of Test Examples 1 to 25 can be used to prepare top coat films having a thickness of 10 to 20 μm using an actual machine capable of extrusion molding or calendar molding.

<Gluing foam raw material>
The top coat film of Test Example 1 thus prepared was placed on one surface of the wallpaper base via a binder, and the wallpaper base with the top coat film placed thereon was heat-pressed at 100°C for 1 minute at 5 MPa, and then heated in a gear oven (manufactured by Toyo Seiki Seisakusho) at 220°C for 60 seconds to foam, thereby obtaining a wallpaper sample of Test Example 1.
Wallpaper samples of each of Test Examples 2 to 25 were obtained using the films of Test Examples 2 to 25 in the same manner as in the above-mentioned foam raw fabric lamination.
For each of the wallpaper samples of Test Examples 1 to 25, the stain resistance of the surface of each wallpaper sample was evaluated based on the above <Evaluation of Wallpaper Samples>.

The compositions and evaluation results of Test Examples 1 to 25 are shown in Tables 5 and 6. In the tables, the numbers for each item other than "Evaluation" indicate parts by mass.

As described above, the film-forming composition was thermally cured, and then rolled or otherwise processed to form a topcoat film. This topcoat film was then attached to the surface of the wallpaper base via a binder, producing wallpaper that is a laminate containing the topcoat film as a surface layer.

The results of Test Examples 1 to 25 show that the stain resistance of wallpaper can be improved by using a film-forming composition that combines a polyvinyl chloride polymer with cellulose fibers and/or chitin fibers and/or chitosan fibers.
The results of Test Examples 1 to 4 and Test Examples 10 to 13 show 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, the results of Test Examples 14 to 16 show that when the content of fibers in the film-forming composition is at least 0.2 parts by mass or more per 100 parts by mass of resin, the stain-resistant effect of wallpaper is good, and up to about 0.7 parts by mass the stain-resistant effect of wallpaper is good.
The results of Test Examples 4 to 9 also show that a wide range of plasticizers can be used in the film-forming composition. These results also show that the stain-resistant effect of wallpaper is good when at least one of DINP, DOP, DOTP, ATBC, TOTM, and DINA is used as the plasticizer. Additionally, the results of Test Examples 22 and 23 show that the stain-resistant effect of wallpaper is good when the content of plasticizer in the film-forming composition is 5 to 30 parts by mass per 100 parts by mass of resin.
Furthermore, the results of Test Examples 1 to 4 show that a good antifouling effect on wallpaper can be achieved when a surfactant, particularly a nonionic surfactant or a cationic surfactant, is used in the film-forming composition. Furthermore, when a nonionic surfactant is used as the surfactant, particularly a nonionic surfactant with an HLB of 8 to 19, the antifouling effect on wallpaper can be achieved.
The results of Test Examples 4, 14, and 16 to 21 show that a wide range of resins can be used in the film-forming composition. In particular, it is preferable to use at least a suspension vinyl chloride polymer, and it is more preferable to combine a suspension vinyl chloride polymer with a paste vinyl chloride polymer and/or a blend vinyl chloride polymer.
The results of Test Examples 4 and 24 to 25 show that the film-forming composition has a good stain-resistant effect on wallpaper even when it contains a matting agent.

Claims (11)

a resin containing a polyvinyl chloride polymer;
one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers;
A plasticizer,
a surfactant using a nonionic surfactant and/or a cationic surfactant;
Including,
The polyvinyl chloride polymer includes a suspension vinyl chloride polymer, a paste vinyl chloride polymer, and/or a blend vinyl chloride polymer,
the content of the polyvinyl chloride polymer is 95% by mass or more based on the total amount of the resin,
the content of the polyvinyl chloride polymer is 60% by mass or more based on the total mass of the composition,
the content of the suspension vinyl chloride polymer is 40% by mass or more and 80% by mass or less, and the content of the paste vinyl chloride polymer and/or blend vinyl chloride polymer is 20% by mass or more and 60% by mass or less, based on the total mass of the polyvinyl chloride polymer;
The content of the fiber is 0.02 parts by mass or more and 0.7 parts by mass or less with respect to 100 parts by mass of the resin,
the content of the plasticizer is 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin,
the content of the surfactant is 0.01 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the resin,
The suspension vinyl chloride polymer is a particle having a porous structure and an average particle size (D50) of 50 to 200 μm,
The vinyl chloride polymer paste is a spherical particle having an average particle size (D50) of 0.02 to 5 μm,
The blended vinyl chloride polymer is obtained by dispersing vinyl chloride monomer droplets and subjecting them to suspension polymerization (optionally in combination with an emulsifier) and is composed of irregularly shaped particles having an average particle size (D50) of 20 to 100 μm.
A film-forming composition for use in antifouling. The film-forming composition according to claim 1, wherein the plasticizer is a polycarboxylic acid ester-based plasticizer. The film-forming composition according to claim 1 or 2, wherein the plasticizer is one or more selected from the group consisting of DINP, DOP, DOTP, ATBC, TOTM, and DINA. An antifouling film that is a cured product of the film-forming composition described in any one of claims 1 to 3. A laminate comprising, as at least one surface layer, an antifouling film that is a cured product of the film-forming composition described in any one of claims 1 to 4. a resin containing a polyvinyl chloride polymer;
one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers;
A plasticizer,
a surfactant using a nonionic surfactant and/or a cationic surfactant;
Including,
the polyvinyl chloride polymer contains at least a paste vinyl chloride polymer,
the content of the polyvinyl chloride polymer is ([ 100/205.46] x 100) mass% or more based on the total mass of the composition ,
The content of the fiber is 0.02 parts by mass or more and 1.25 parts by mass or less with respect to 100 parts by mass of the resin,
the content of the plasticizer is 40 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin,
the content of the surfactant is 0.001 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the resin,
The vinyl chloride polymer paste is a spherical particle having an average particle size (D50) of 0.02 to 5 μm.
A plastisol composition for forming a cured product for use in antifouling. The plastisol composition according to claim 6, wherein the plasticizer is a polycarboxylic acid ester-based plasticizer. The plastisol composition according to claim 6 or 7, wherein the plasticizer is one or more selected from the group consisting of DINP, DOP, DOTP, DINA, TOTM, and DINCH. The plastisol composition according to any one of claims 6 to 8, wherein the HLB of the nonionic surfactant is 8 to 19. A cured product for use in antifouling, which is a cured product of the plastisol composition described in any one of claims 6 to 9. A polyvinyl chloride resin composition for forming a cured product for use in antifouling, as set forth in (i) or (ii) below:
(i) a resin containing a polyvinyl chloride polymer;
one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers;
A plasticizer,
a surfactant using a nonionic surfactant and/or a cationic surfactant;
Including,
The polyvinyl chloride polymer includes a suspension vinyl chloride polymer, a paste vinyl chloride polymer, and/or a blend vinyl chloride polymer,
the content of the polyvinyl chloride polymer is 95% by mass or more based on the total amount of the resin,
the content of the polyvinyl chloride polymer is 60% by mass or more based on the total mass of the composition,
the content of the suspension vinyl chloride polymer is 40% by mass or more and 80% by mass or less, and the content of the paste vinyl chloride polymer and/or blend vinyl chloride polymer is 20% by mass or more and 60% by mass or less, based on the total mass of the polyvinyl chloride polymer;
The content of the fiber is 0.02 parts by mass or more and 0.7 parts by mass or less with respect to 100 parts by mass of the resin,
the content of the plasticizer is 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin,
the content of the surfactant is 0.01 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the resin,
The suspension vinyl chloride polymer is a particle having a porous structure and an average particle size (D50) of 50 to 200 μm,
The vinyl chloride polymer paste is a spherical particle having an average particle size (D50) of 0.02 to 5 μm,
a polyvinyl chloride resin composition for forming a cured product for use in an antifouling application, wherein the blended vinyl chloride polymer is irregularly shaped particles having an average particle size (D50) of 20 to 100 μm, obtained by dispersing vinyl chloride monomer droplets and performing suspension polymerization (optionally in combination with an emulsifier); or (ii) a resin containing a polyvinyl chloride polymer;
one or more fibers selected from the group consisting of cellulose fibers, chitin fibers, and chitosan fibers;
A plasticizer,
a surfactant using a nonionic surfactant and/or a cationic surfactant;
Including,
the polyvinyl chloride polymer contains at least a paste vinyl chloride polymer,
the content of the polyvinyl chloride polymer is ([ 100/205.46] x 100) mass% or more based on the total mass of the composition ,
The content of the fiber is 0.02 parts by mass or more and 1.25 parts by mass or less with respect to 100 parts by mass of the resin,
the content of the plasticizer is 40 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin,
the content of the surfactant is 0.001 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the resin,
The vinyl chloride polymer paste is a spherical particle having an average particle size (D50) of 0.02 to 5 μm.
A polyvinyl chloride resin composition for forming a cured product for use in antifouling.