Pulp composition

Abstract

Provided is a novel pulp composition containing a modified polyol, a pulp base material, and a paper strengthening agent, wherein: the paper strengthening agent is at least one selected from the group consisting of a polyacrylamide-based paper strengthening agent, a polysaccharide-based paper strengthening agent, and a polyamide-based paper strengthening agent; and the amount of the modified polyol is 0.2-30 parts by weight with respect to 100 parts by weight of the pulp base material. With this pulp composition, it is possible to produce a pulp molded article having improved strength.

Description

Pulp composition

[0001] The present disclosure relates to pulp compositions.

[0002] Patent Document 1 discloses a water repellent agent containing a glycerin fatty acid ester with a monoester content of 1 to 50%.

[0003] Japanese Patent Application Laid-Open No. 2020-54393

[0004] Patent Document 1 neither describes nor suggests paper strength agents, nor does it describe or suggest the strength of pulp products.

[0005] An object of the present disclosure is to provide a novel pulp composition that can be used to produce molded pulp products with improved strength.

[0006] The present disclosure includes the following aspects: [Item 1] A pulp composition comprising a polyol modifier, a pulp base material, and a paper strength agent, wherein the paper strength agent is at least one selected from the group consisting of polyacrylamide-based paper strength agents, polysaccharide-based paper strength agents, and polyamide-based paper strength agents, and the amount of the polyol modifier is 0.2 parts by weight to 30 parts by weight per 100 parts by weight of the pulp base material. [Item 2] The pulp composition according to Item 1, wherein the polyol modifier is a compound obtained by modifying a polyol with a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group. [Item 3] The pulp composition according to Item 1 or 2, wherein the polyol modifier has an aliphatic hydrocarbon group having from 6 to 40 carbon atoms, which may have a substituent. [Item 4] The polyol modifier is a compound obtained by modifying one or more hydroxy groups of the polyol with a compound represented by the following formula: -Y Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｏ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２(wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and Y Ｏ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｏ [Item 5] The pulp composition according to any one of Items 1 to 3, wherein Y is a monovalent hydrocarbon group or a monovalent polysiloxane group having 1 to 40 carbon atoms, which may have a substituent, and n is an integer of 1 to 3. Ｏ ga -O-Y Ｏ１１ - or -O-Y Ｏ１１ -Y Ｏ２１ -Y Ｏ１２ wherein each symbol represents independently at each occurrence: Y Ｏ１１ is a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—; Y Ｏ２１ is a hydrocarbon group having 1 to 40 carbon atoms, and Y Ｏ１２ is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(= O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２Item 6. The pulp composition according to any one of Items 1 to 5, wherein the polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and polymers of hydroxy group-containing compounds. [Item 7] The polyol is selected from the group consisting of glucose, fructose, galactose, xylose; sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, and lactitol; starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, and tamarind seed gum; ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid; glucosamine; ascorbic acid and inositol; catechin, quercetin, and anthocyanin; Item 6. The pulp composition according to any one of Items 1 to 6, wherein the polyol-modified product is at least one selected from the group consisting of glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, and trimethylolethane; polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers. [Item 8] The pulp composition according to any one of Items 1 to 7, wherein the polyol-modified product has a hexadecane contact angle of 30° or more. [Item 9] The pulp composition according to any one of Items 1 to 8, wherein the polyol-modified product is a polyglycerin-modified product. [Item 10] The pulp composition according to Item 9, wherein the hydroxy group substitution rate of the polyglycerin-modified product is 40% or more. [Item 11] The pulp composition according to any one of Items 1 to 10, wherein the amount of the paper strength agent is 2 parts by weight or more and 200 parts by weight or less per 100 parts by weight of the polyol modified product.[Item 12] The polyol modification product is a compound in which a hydroxy group of a monosaccharide or polyglycerin is replaced with a group represented by the following formula: -OC(=O)-Z. Ｏ [In the formula, Z Ｏ is an aliphatic hydrocarbon group having 14 to 24 carbon atoms. ], and the hydroxy group substitution rate in the polyol modified product is 40% or more. [Item 13] A molded pulp product formed from the pulp composition of any one of Items 1 to 12. [Item 14] The molded pulp product of Item 13, having a further polyol modified product and a further strength agent attached to its surface. [Item 15] The molded pulp product of Item 13 or 14, which is for food contact. [Item 16] A method for producing the pulp composition of any one of Items 1 to 12, comprising a polyol modified product addition step of adding the polyol modified product to the pulp base material, and a strength agent addition step of adding the strength agent to the pulp base material.

[0007] According to the present disclosure, a molded pulp product with improved strength can be produced.

[0008] The pulp composition of the present disclosure contains a repellent component, and a pulp molded product formed from the pulp composition not only has excellent strength but can also have excellent liquid repellency.

[0009] <Definition of Terms> As used herein, an "n-valent group" refers to a group having n bonds, i.e., a group that forms n bonds. Furthermore, an "n-valent organic group" refers to an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. A hydrocarbon group derivative refers to a group having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the end or molecular chain of the hydrocarbon group.

[0010] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a group obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C １－２０Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents, if explicitly stated.

[0011] In this specification, when a term (symbol) that may appear multiple times in a chemical structure is defined, that definition applies independently at each occurrence, unless otherwise stated, regardless of whether "independently at each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated.

[0012] The chemical structures described herein should be understood not to encompass chemical structures that would be recognized by those skilled in the art as chemically impossible or extremely unstable.

[0013] <Repellent Agent> The repellent agent in the present disclosure adheres to a substrate (particularly a pulp substrate) and can impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can also function as a water resistance agent, oil resistance agent, water repellent agent, oil repellent agent, and / or stain resistance agent.

[0014] The repellent of the present disclosure may contain a modified polyol as an active ingredient (the modified polyol will be described in detail separately in [Modified Polyol]). The modified polyol may be used as a repellent by itself, or may be used as a repellent in combination with other ingredients as described below.

[0015] The repellent agent in the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.

[0016] The volumetric abundance ratio of particles of 100 μm or larger in the repellent agent of the present disclosure, as measured by laser diffraction scattering, may be 0.1% or larger, 0.3% or larger, 0.5% or larger, 1% or larger, 1.5% or larger, 3% or larger, 4% or larger, 5% or larger, or 10% or larger, or may be 50% or smaller, 30% or smaller, 20% or smaller, 15% or smaller, 10% or smaller, 5% or smaller, 3% or smaller, or 1.5% or smaller, preferably 20% or smaller, particularly less than 10%. The method for achieving the volumetric abundance ratio of particles of 1 μm or larger, as measured by laser diffraction scattering, within the above range is not limited, and may involve, for example, micronizing the particles in the raw material and / or dispersion using a grinder, homogenizer, or the like.

[0017] The volume median diameter of the repellent agent of the present disclosure, as measured by a laser diffraction scattering method, may be 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, or 0.6 μm or more, or may be 75 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, 10 μm or less, 5 μm or less, 3 μm or less, 1 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, or 0.2 μm or less, and is preferably 40 μm or less, particularly 30 μm or less, for example 1 μm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution measured by a laser diffraction scattering method.

[0018] The ionic charge density in the repellent of the present disclosure may be −1000 μeq / g or more, −800 μeq / g or more, −600 μeq / g or more, −500 μeq / g or more, −400 μeq / g or more, −250 μeq / g or more, −100 μeq / g or more, −50 μeq / g or more, −25 μeq / g or more, 0 μeq / g or more, 1 μeq / g or more, 25 μeq / g or more, 50 μeq / g or more, 100 μeq / g or more, 200 μeq / g or more, preferably −600 μeq / g or more, for example −400 μeq / g or more. The ionic charge density may be 5000 μeq / g or less, 2500 μeq / g or less, 1000 μeq / g or less, 750 μeq / g or less, 500 μeq / g or less, 400 μeq / g or less, 350 μeq / g or less, 300 μeq / g or less, 200 μeq / g or less, 100 μeq / g or less, or 50 μeq / g or less, preferably 1000 μeq / g or less, more preferably 500 μeq / g or less, for example 300 μeq / g or less. In particular, the ionic charge density of the repellent of the present disclosure is preferably -600 μeq / g or more and 100 μeq / g or less. The ionic charge density of the repellent of the present disclosure can be measured, for example, by the following method.

[0019] The anion demand of a sample liquid with a solid content of 0.1 g / L is measured using a 1 / 1000 N potassium polyvinyl sulfonate solution with a particle charge meter (MUTEK PCD-04 manufactured by BTG), and the ionic charge density (cationic charge density) is calculated using the following formula (1). Alternatively, the cation demand is measured in the same manner using a polydiallyldimethylammonium chloride solution instead of potassium polyvinyl sulfonate, and the ionic charge density (anionic charge density) is calculated using the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: cation demand or anionic demand (μeq / L) B: sample liquid concentration (g / L)

[0020] [Modified Polyol] The modified polyol in the present disclosure can adhere to a substrate (particularly a pulp substrate) and impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or stain resistance, to the substrate, and can function as a liquid repellent compound.

[0021] [Characteristics, etc.] The properties, etc. that the modified polyol may have are listed below. These properties, etc. may vary depending on the type of compound.

[0022] The HD (n-hexadecane) contact angle of the polyol-modified product may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may be 100° or less, 90° or less, or 75° or less. When the polyol-modified product has an HD contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly oil repellency) to the substrate. The HD contact angle is the static contact angle of the polyol-modified product with respect to a spin-coated film, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0023] The water contact angle of the polyol-modified material may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the polyol-modified material has a water contact angle equal to or greater than the above lower limit, it can impart good liquid repellency (particularly water repellency) to the substrate. The water contact angle is the static contact angle of the polyol-modified material with respect to a spin-coated film, and is obtained by dropping 2 μL of water on the spin-coated film and measuring the contact angle 1 second after the drop has landed.

[0024] The modified polyol is preferably a biobased compound containing carbon of biobased origin. The biobased content is measured in accordance with ASTM D6866. The biobased content may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, even more preferably 70% or more, and most preferably 80% or more or 90% or more, for example, 100%. A high biobased content means that the amount of fossil resource-based materials, such as petroleum, used is reduced. From this perspective, the higher the biobased content of the modified polyol, the more preferable it is.

[0025] The biodegradability of the polyol-modified product after 180 days is preferably 5% or more. Higher biodegradability is preferable because it reduces the environmental impact. The biodegradability of the polyol-modified product after 180 days may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, and most preferably 80% or more. The biodegradability of the polyol-modified product after 60 days is preferably 5% or more. Higher biodegradability is preferable because it reduces the environmental impact. The biodegradability of the polyol-modified product after 60 days may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. Such biodegradability may be biodegradability as defined in JIS K 6953-1 or ASTM D6400.

[0026] The melting point of the modified polyol may be 30°C or higher, 40°C or higher, 60°C or higher, 80°C or higher, 100°C or higher, or 120°C or higher, preferably 40°C or higher, and may be 250°C or lower, 225°C or lower, 200°C or lower, 150°C or lower, 130°C or lower, 120°C or lower, 110°C or lower, 100°C or lower, 80°C or lower, or 50°C or lower.

[0027] [Structure etc.] The modified polyol in the present disclosure does not necessarily have any group selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. Even if the modified polyol does not contain these fluorine-containing groups, it can impart liquid repellency to a substrate.

[0028] The polyol-modified compound may be a compound having a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group. From the viewpoint of liquid repellency, the polyol-modified compound may have a hydrocarbon group having from 6 to 40 carbon atoms (for example, an alkyl group).

[0029] (Optionally Substituted Monovalent Hydrocarbon Group) The modified polyol may have a substituted or unsubstituted monovalent hydrocarbon group.

[0030] The hydrocarbon group may be a monovalent hydrocarbon group having from 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, such as an alkenyl group or alkyl group having 1 to 3 double bonds. The hydrocarbon group may be branched, cyclic, or linear, more preferably linear.

[0031] The number of carbon atoms in the hydrocarbon group may be 1 or more, 3 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less.

[0032] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR' and -N(R'). ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (e.g., 1) —OR′ (particularly —OH) as a substituent (e.g., other than at the terminal).

[0033] (Monovalent Polysiloxane Group) The polyol-modified product may have a monovalent polysiloxane group. Like the (monovalent) hydrocarbon group, the (monovalent) polysiloxane group can impart liquid repellency to the substrate.

[0034] The polysiloxane group has the following formula: —[—Si(R ｓ ) ２ -O-] ａ - [wherein, R ｓ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and a is an integer of 5 or more and 10,000 or less.

[0035] R ｓ is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.

[0036] Examples of hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms and hydrocarbon groups having 6 to 40 carbon atoms.

[0037] Examples of the hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and other hydrocarbon groups having 1 to 5 carbon atoms (particularly an aliphatic hydrocarbon group, particularly an alkyl group such as a methyl group or an ethyl group, particularly a methyl group).

[0038] The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and particularly preferably a saturated aliphatic hydrocarbon group (alkyl group). The hydrocarbon group may be cyclic, linear, or branched, preferably linear. The number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.

[0039] Examples of reactive groups include groups having functional groups (e.g., hydroxy groups, amino groups, mercapto groups, epoxy groups, carboxyl groups, halogen-substituted alkyl groups, vinyl groups, (meth)acrylic groups, (meth)acryloyloxy groups, (meth)acrylamide groups, hydrogen atoms directly bonded to silicon atoms, etc.). These functional groups may be directly bonded to the silicon atom, or may be bonded to an organic group directly bonded to the silicon atom. The organic group may be a hydrocarbon group, such as an alkylene group or a divalent aromatic group. The hydrocarbon group may have from 2 to 12 carbon atoms, and the alkylene group preferably has from 2 to 10 carbon atoms. The divalent aromatic group preferably has from 6 to 12 carbon atoms. The reactive group may be a group selected from the group consisting of a hydroxy group, an epoxy ring, a carboxyl group, a (meth)acrylic group, and an amino group, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0040] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, and is preferably 10 or more, and may be 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, and is preferably 500 or less.

[0041] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms. ｓ The amount of R ｓ It may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, and may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, based on the total of R ｓ With respect to the total number of groups, 50 mol % or more may be methyl groups or ethyl groups (particularly methyl groups).

[0042] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms. ｓ The amount of R ｓand may be 100 mol % or less, 90 mol % or less, 80 mol % or less, or 70 mol % or less, based on the total of

[0043] In the polysiloxane group, reactive groups R ｓ The amount of R ｓ and may be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may be 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less, based on the total of

[0044] R ｓ The groups may be introduced randomly or in blocks, but are preferably introduced randomly.

[0045] The terminal structure of the polysiloxane group is not limited, but may be -OR ｓ , -Si(R ｓ ) ３ etc. The R of the terminal structure ｓ Examples of the reactive group are as described above, and may be, for example, at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group, and a carboxyl group.

[0046] The polysiloxane group may have a linker, and the raw material compound and the polysiloxane group may be bonded via a linker. Such a linker may be, but is not limited to, a hydrocarbon group having 1 to 40 (e.g., 1 to 20) carbon atoms which may be interrupted by an oxygen atom, for example, a (poly)oxyalkylene group having 1 to 40 (e.g., 1 to 20) carbon atoms.

[0047] Examples of polysiloxane groups include -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -O-Lｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３ -L ｓ１ -O-L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -Si(R ｓ ) ３、 -L ｓ１ -[-Si(R ｓ ) ２ -O-] ａ -R ｓ [In the formula, R ｓ is independently in each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R ｓ has one or more reactive groups, and R ｓ 50 mol % or more of the total groups are methyl groups, and L ｓ１ is a hydrocarbon group having 1 to 20 carbon atoms, and a is 5 or more and 10,000 or less. [In the formula, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a+b) is 5 to 200, and n is an integer of 0 to 36.]

[0048] [Structural Aspects of Modified Polyols] An example of a modified polyol is a compound having a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group (for example, a hydrocarbon group having from 6 to 40 carbon atoms, such as an alkenyl group or alkyl group having 1 to 3 double bonds). Examples and preferred ranges of the hydrocarbon group are as described above.

[0049] The polyol modification may include an ester group, an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonurea group, a sulfonurethane group, or a sulfonimide group (e.g., an ester group, an amide group, a urethane group, a urea group, an imide group). For example, the polyol modification may include —C(═O)—O—, —O—C(═O)—, —C(═O)—NR′—, —O—C(═O)—NR′—, —NR′—C(═O)—NR′—, or —SO ２ The modified polyol may contain NR'- (R', in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms)). The modified polyol may be a compound obtained by bonding a raw material compound and a modifying group (particularly the monovalent hydrocarbon group which may have the above-mentioned substituent) via at least one of these groups. The modified polyol may contain an amide structure. When the modified polyol contains at least an amide structure, the liquid repellency can be improved. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures such as amide (acid amide) groups, urethane groups, urea groups, imide groups, thioamide groups, thiourethane groups, thiourea groups, thioimide groups, sulfonamide groups, sulfoneurethane groups, sulfoneurea groups, and sulfonimide groups. The amide structure is -(C=O)N(-) ２ , -(C=S)N(-) ２ , and -S(=O) ２ N (-) ２ (Note that each group may be inverted). Here, at least one of the bonds possessed by N in the amide structure may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-) ２ and may be an amide structure in a group selected from the group consisting of an amide group, a urethane group, a urea group, and an imide group.

[0050] The polyol-modified product may be a compound that has been chemically modified so as to exhibit liquid repellency against polyols. The polyol-modified product may be a polymer having a degree of polymerization of 1 or more. From the viewpoint of improving liquid repellency, the degree of polymerization of the polyol-modified product may be 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. Furthermore, from the viewpoint of improving the handleability of the repellent, it may be 100 or less, preferably 50 or less, more preferably 30 or less, and even more preferably 15 or less. Here, the degree of polymerization refers to the number of repeating monomer units that constitute the polymer.

[0051] The degree of polymerization in the present disclosure refers to the average degree of polymerization. The average degree of polymerization in the present disclosure refers to the polymerization obtained by measurement under the following conditions. When the polyol-modified product in the present disclosure is a polyglycerol-modified product obtained by modifying polyglycerol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyglycerol. The average degree of polymerization of polyglycerol is the average degree of polymerization (n) calculated from the hydroxyl value by end group analysis. Specifically, the average degree of polymerization and the average molecular weight are calculated from the following formulas (Formula 1) and (Formula 2). (Formula 1) Average molecular weight = 74n + 18 (Formula 2) Hydroxyl value = 56110(n + 2) / average molecular weight The hydroxyl value in the above (Formula 2) is a numerical value that serves as an index of the number of hydroxyl groups contained in the polyglycerol. The hydroxyl value is calculated from the amount of potassium hydroxide required to neutralize the acetic acid required to acetylate the free hydroxyl groups contained in 1 g of polyglycerol, and is calculated in accordance with "Standard Test Methods for the Analysis of Fats, Oils and Related Compounds (I), 2003 Edition," compiled by the Japan Oil Chemists' Society. The hydroxyl value of the raw material polyglycerol is measured according to the above-mentioned Standard Test Methods for the Analysis of Fats, Oils and Related Compounds, and the average degree of polymerization and average molecular weight of the polyglycerol can be calculated from the above-mentioned relational equation.

[0052] When the polyol-modified product in the present disclosure is a polyvinyl alcohol-modified product obtained by modifying polyvinyl alcohol, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polyvinyl alcohol, which can be measured in accordance with JIS K 6726, Testing Method for Polyvinyl Alcohol.

[0053] When the polyol-modified product in the present disclosure is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product refers to the average degree of polymerization of the polysaccharide. Analysis of the average degree of polymerization of a polysaccharide can be performed as follows. The degree of polymerization refers to the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is determined, for example, by taking the top of the peak in each analysis result obtained by a conventional analytical method such as HPLC, GC, or HPAEC as the average degree of polymerization. Measurements can be performed using, for example, an ULTRON PS-80N (8 x 300 mm) column manufactured by Shinwa Chemical Industry Co., Ltd. (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or a TSK-GEL G30000 PWXL (7.8 x 300 mm) column manufactured by TOSOH Corporation (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) and a differential refractometer as a detector.

[0054] The modified polyol may be low molecular weight (eg, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or may be 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0055] The hydroxy group substitution rate in the modified polyol may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, preferably 40% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, for example, 95% or less. Here, the "substitution rate" refers to the proportion (mol %) of hydroxy groups derived from a polyol that are modified, and may refer to the proportion (mol %) that are modified with a monovalent hydrocarbon group having from 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0056] The residual rate of hydroxyl groups in the modified polyol may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 5% or more, or may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, preferably 60% or less, for example, 50% or less, 30% or less, or 10% or less. Here, the "residual rate" refers to the proportion (mol %) of hydroxyl groups derived from the polyol that are not modified.

[0057] The number of modifying groups in the polyol modified product may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more, and may be 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0058] The modifying group equivalent of the polyol modified product may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1000 or more, and may be 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 400 or less. This is the value obtained by dividing the weight average molecular weight of the polyol modified product by the number of modifying groups. Here, the modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent.

[0059] The polyol-modified product is a polyol in which one or more hydroxy groups are substituted with a modifying group. The modifying group is preferably a monovalent hydrocarbon group or a monovalent polysiloxane group which may have a substituent. From the viewpoint of improving liquid repellency, the polyol-modified product may have a structure in which a polyol is modified with an aliphatic hydrocarbon group having from 6 to 40 carbon atoms, for example, an alkenyl group or alkyl group having 1 to 3 double bonds.

[0060] For details of the monovalent hydrocarbon group which may have a substituent and the monovalent polysiloxane group, the above descriptions of the (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0061] (-Y Ｏ -Z Ｏ ｎ In the present disclosure, the modified polyol is a polyol in which one or more hydroxy groups of the polyol are represented by the following formula: Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｏ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２(wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and Y Ｏ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles, Ｏ is a monovalent hydrocarbon group having from 1 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and n is an integer of from 1 to 3.

[0062] (Y Ｏ ) Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more groups selected from the group consisting of Ｏ１ represents a direct bond, —O—, —C(═O)—, —C(═NR′)—, —S—, —S(═O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein R′ is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and Y Ｏ２ is a group composed of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent hydrocarbon aromatic rings, and optionally substituted di- to tetravalent heterocycles.

[0063] n is Y Ｏ Z combines with Ｏ and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

[0064] Y ＯThe molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0065] Y Ｏ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｏ is -C(=O)-NR'-, -C(=S)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may contain NR'-. Ｏ By including these groups, the liquid repellency can be improved.

[0066] ○ Y Ｏ１ Y Ｏ１ is a non-hydrocarbon linker.

[0067] Y Ｏ１ is a direct bond or a divalent or higher valent group. Ｏ１ The valence of Y may be 2 to 4, 2 to 3, or 2. Ｏ１ is preferably not only a direct bond.

[0068] Y Ｏ１ The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0069] Y Ｏ１ represents a direct bond, —O—, —C(═O)—, —S(═O) ２ -, -NR'-, -C(OR')R'-, and -C(OR')(-) ２ (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms).) Ｏ１Examples of include a direct bond, —O—, —O—C(═O)—, —O—C(═O)—O—, —O—C(═O)—NR′—, —NR′—, —NR′-C(═O)—O—, —NR′-C(═O)—NR′—, —C(═O)—, —C(═O)—O—, —C(═O)—NR′—, —SO ２ -, -SO ２ NR'-, -C(OR')R'-, -C(OR')(-) ２ and the like (wherein R' in each occurrence is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (eg, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0070] Y Ｏ１ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｏ２ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may contain NR'-. Ｏ１ By including these groups, the liquid repellency can be improved.

[0071] ○ Y Ｏ２ Y Ｏ２ is a linker of a hydrocarbon ring which may have a substituent, a hydrocarbon aromatic ring which may have a substituent, or a heterocyclic ring which may have a substituent.

[0072] Y Ｏ２ Y may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms). Ｏ２ Y may be aliphatic or aromatic. Ｏ２ may be linear, branched or cyclic.

[0073] Y Ｏ２ is a divalent or higher valent group. Ｏ２ The valency of may be, for example, 2-4, 2-3, or 2.

[0074] Y Ｏ２may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0075] Y Ｏ２ is composed of one or more selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles.

[0076] The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group. The di- to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 40 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. The valence of the aliphatic hydrocarbon group may be 2 or more, 3 or more, or 4 or less, 3 or less, or 2.

[0077] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include —OR′ and —N(R′). ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted aliphatic hydrocarbon group, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0078] Examples of divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring-constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0079] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R', -OR', and -N(R'). ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted hydrocarbon aromatic ring, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0080] The divalent to tetravalent heterocycle may be an aliphatic group or an aromatic group. Examples of divalent to tetravalent heterocycles include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. The number of ring-constituting atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12. The valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.

[0081] The heterocycle may have a substituent. Examples of the substituent include -R', -OR', and -N(R'). ２ , —COOR′, and halogen atoms (wherein R′, in each occurrence, is independently a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the substituted heterocycle, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example, 65 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0082] Y Ｏ２ Examples of -Ali- -Cy- -Ali(-) ２ -Cy(-) ２ (-) ２ Ali- (-) ２ Cy- (-) ２ Ali (-) ２ (-) ２ Cy(-)２ -Ali-Cy- -Cy-Ali- -Cy-Ali-Cy- -Ali-Cy-Ali- (wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and Cy is a hydrocarbon aromatic ring or heterocycle.)

[0083] Y Ｏ２ Specific examples of -(CH ２ ) ｐ -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0084] (Y Ｏ Example: Y Ｏ In the following, R' is independently in each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).

[0085] Y Ｏ An example of this is Y Ｏ When is divalent, -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ --etc.

[0086] Y ＯAs an example, when Y Ｏ is trivalent, -Y Ｏ１ (-) ２ , -Y Ｏ１ -Y Ｏ２ (-) ２ , -Y Ｏ１ -(Y Ｏ２ -) ２ , -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ２ , -Y Ｏ１ -Y Ｏ２ (-Y Ｏ１ -) ２ , -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -)<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Ｏ２ -Y Ｏ１ (-) ２ ,-Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -) ２、 -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ２、 -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -) ２ etc. can be mentioned.

[0087] Y Ｏ As an example of Y Ｏ when Y is tetravalent, -Y Ｏ１ (-) ３ ,-Y Ｏ１ -Y Ｏ２ (-) ３ [[ID=五十二]],-Y Ｏ１ -(Y Ｏ２ -) ３ ,-Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ３ ,-Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -) ３ ,-Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ３ ,-Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ３ ,-Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -) ３、 -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ３、 -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -) ３ ; -Y Ｏ２ (-) ３, -Y Ｏ２ -Y Ｏ１ (-) ３ , -Y Ｏ２ -(Y Ｏ１ -) ３ , -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ (-) ３ , -Y Ｏ２ -Y Ｏ１ (-Y Ｏ２ -) ３ , -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -) ３ , -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ (-) ３ , -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -(Y Ｏ１ -) ３、 -Y Ｏ２ -Y Ｏ１ -(Y Ｏ２ -Y Ｏ１ -) ３、 -Y Ｏ２ -(Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -) ３ ; etc.

[0088] Y Ｏ Preferred examples of -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ１ -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ１ -Y Ｏ２ (-) ２ , -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ -, -Y Ｏ２ -Y Ｏ１ -Y Ｏ２ -, -Y Ｏ２ -Y Ｏ１ (-) ２ , etc.

[0089] (Preferred Y ＯPreferably, Y Ｏ ga -O-Y Ｏ１１ - or -O-Y Ｏ１１ -Y Ｏ２１ -Y Ｏ１２ wherein each symbol represents independently at each occurrence: Y Ｏ１１ is a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—; Y Ｏ２１ is a hydrocarbon group having 1 to 40 carbon atoms, and Y Ｏ１２ is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(= O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ ], or

[0090] Y Ｏ１１ is a non-hydrocarbon linker, which is a direct bond or a divalent or higher valent group.

[0091] Y Ｏ１１ The molecular weight of may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.

[0092] Y Ｏ１１ may be a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—.

[0093] Y Ｏ２１ is a divalent hydrocarbon linker, which may be a hydrocarbon group having 1 to 40 carbon atoms.

[0094] Y Ｏ２１ may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0095] Here, the hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched, or straight chain hydrocarbon group, and may be a saturated or unsaturated (eg, saturated) aliphatic hydrocarbon group.

[0096] Y Ｏ２１ Specific examples of -(CH ２ ) ｐ -(p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure and having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH ２ ) ｑ -Cy-(CH ２ ) ｒ -(q and r each independently represent a number from 0 to 20, for example, from 1 to 10, and Cy represents a hydrocarbon aromatic ring or a heterocycle), and the like.

[0097] Y Ｏ１２ -O-, -OC(=O)-, -OC(=O)-O-, -OC(=O)-NR'-, -NR'-, -NR'-C(=O)-, - NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ It may be.

[0098] Y Ｏ１２ may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfoneurea group, a sulfoneurethane group, or a sulfonimide group. Ｏ１２ is -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO ２ It may be NR'-. Ｃ１２ By including these groups, the liquid repellency can be improved.

[0099] (Z Ｏ ) Z Ｏrepresents a monovalent hydrocarbon group or monovalent polysiloxane group having from 1 to 40 carbon atoms which may have a substituent, and the above descriptions of (monovalent hydrocarbon group which may have a substituent) and (monovalent polysiloxane group) are incorporated herein by reference.

[0100] (Other modifying groups) The hydroxy group of the polyol is -Y Ｏ -Z Ｏ ｎ Examples of modifying groups are anionic and / or cationic groups.

[0101] Examples of the anionic group include a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0102] Examples of salts of anionic groups include alkali metal salts, alkaline earth metal salts, and ammonium salts, such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0103] The cationic group is an amino group, preferably a tertiary amino group or a quaternary amino group. In the tertiary amino group, two groups bonded to the nitrogen atom may be the same or different and may be an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (particularly an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (particularly an aralkyl group, for example a benzyl group (C ６ H ５ -CH ２ In the tertiary amino group and the quaternary amino group, the remaining group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0104] The cationic group in the form of a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred.

[0105] [Method for Producing Modified Polyol] The modified polyol may be produced by reacting a modifying agent having a modifying group (or a precursor structure of the modifying group) with a hydroxy group of a polyol.

[0106] (Polyol) A polyol is a compound having two or more hydroxy groups and is a compound that serves as a raw material for a modified polyol. A polyol is a compound having two or more hydroxy groups in the molecule. The polyol may be aliphatic or aromatic, but is preferably aliphatic.

[0107] The polyol may have an ether bond. Preferably, the polyol may have two or more ether bonds. Specifically, the polyol is preferably a compound having two or more hydroxy groups and two or more ether bonds. In other words, the polyol is preferably a polyether having two or more hydroxy groups.

[0108] When the polyol is a polymer, the repeating structure of the monomer unit may contain a hydroxy group and an ether bond.

[0109] The polyol may be low molecular weight (e.g., weight average molecular weight less than 1,000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol may be 50 or more, 100 or more, 300 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more; or 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0110] The number of hydroxy groups in the polyol may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more, and may be 3000 or less, 1000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less.

[0111] The hydroxy group equivalent weight of the polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The hydroxy group equivalent weight of the polyol is the value obtained by dividing the weight average molecular weight of the polyol by the number of hydroxyl groups.

[0112] The polyol may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The above natural products also include compounds converted from microorganisms. Examples of polyols include monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, hydroxy group-containing compound polymers, polyether polyols, polymer polyols, polyester polyols, and other polyols.

[0113] Examples of monosaccharides include glucose, fructose, galactose, and xylose.

[0114] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, and sucralose.

[0115] Examples of sugar alcohols (reducing sugars) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, and lactitol.

[0116] Examples of polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, and tamarind seed gum.

[0117] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid, and gluconic acid.

[0118] Examples of amino acids include glucosamine.

[0119] Examples of vitamins include ascorbic acid and inositol.

[0120] Examples of flavonols include catechin, quercetin, and anthocyanin.

[0121] Examples of hydroxy hydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, etc. Hydroxy hydrocarbons are hydrocarbons having a hydroxy group and may be aromatic or aliphatic, but are preferably aliphatic. The term "hydroxy hydrocarbon" may also refer to hydroxy hydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxy hydrocarbons).

[0122] Examples of the hydroxy group-containing compound polymer include polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer, and hydroxybutyl (meth)acrylate polymer.

[0123] An example of a polyether polyol may be a compound obtained by addition polymerization of an alkylene oxide with an initiator. Examples of initiators include compounds having two or more functional hydroxyl groups. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerin, polyglycerin, trimethylolpropane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamines, diethylenetriamine, sorbitol, and sucrose. Examples of alkylene oxides include ethylene oxide and propylene oxide. Polyether polyols obtained by addition polymerization of alkylene oxide with the above initiators are also referred to as polyoxyalkylene polyols or oxyalkylene derivatives of polyols. Representative examples of polyether polyols include polyoxypropylene triols obtained by addition polymerization of propylene oxide with glycerin, and polyoxypropylene polyglyceryl ethers obtained by addition polymerization of propylene oxide with polyglycerin.

[0124] An example of a polymer polyol is a compound obtained by polymerizing at least a portion of a polyether polyol with an ethylenically unsaturated monomer, such as acrylonitrile or styrene.

[0125] Examples of polyester polyols include compounds obtained by dehydration condensation of a compound having a bifunctional or higher carboxyl group and a compound having a bifunctional or higher hydroxyl group. Examples of compounds having a bifunctional or higher carboxyl group include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof. Examples of compounds having a bifunctional or higher hydroxyl group include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0126] (Modifying Agent) The modifying agent is a compound reactive with a polyol, and is preferably a compound having the above-mentioned monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

[0127] Examples of modifying agents are: Acid halides G(O=)C-Z Ｏ Acid anhydride O(C(=O)-Z Ｏ ) ２ Carboxylic acid HO(O=)C-Z Ｏ Isocyanate O=C=N-Z Ｏ Thioisocyanate S=C=N-Z Ｏ Epoxy (CH ２ OCH)CH ２ O-Z Ｏ Halide G-Z Ｏ Amine H ２ N-Z Ｏ Hydroxy HO-Z Ｏ [In the formula, Z Ｏ is as defined above, and G is a halogen atom (e.g., F, Cl, Br, or I).

[0128] Z in the structure of the above-mentioned modifier Ｏmay be replaced with any group constituting the modifying group, for example, Z Ｏ may be a group having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group, or, for example, Z Ｏ Wo-Y Ｏ -Z Ｏ ｎ It may also be possible to use the following.

[0129] The modified polyol may be synthesized by reacting a polyol with a modifying agent. For example, a modified polyol can be synthesized by reacting a modifying agent such as an acid halide compound, an acid anhydride, or a carboxylic acid with a hydroxy group of a polyol to form an ester bond. Alternatively, a modified polyol can be produced by reacting a modifying agent such as a halide or an epoxy compound with a hydroxy group of a polyol to form an ether bond. Those skilled in the art can appropriately design the reaction conditions between the polyol and the modifying agent, such as by using a catalyst (e.g., an acid catalyst or a base catalyst) or a condensing agent, depending on the desired product.

[0130] [Amount of Polyol Modifier] The amount of polyol modifier in the repellent may be 0.01 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 70 wt% or more, or 80 wt% or more, or may be 95 wt% or less, 90 wt% or less, 80 wt% or less, 70 wt% or less, 60 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, or 3 wt% or less. The polyol modifier may be used alone as the repellent.

[0131] [Dispersant] The repellent of the present disclosure may contain a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant, and an inorganic dispersant.

[0132] As the dispersant, an organic dispersant and an inorganic dispersant may be used individually, or a combination of an organic dispersant and an inorganic dispersant may be used.

[0133] An organic dispersant may be used as the dispersant. The organic dispersant can be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant, and an amphoteric dispersant, and the organic dispersant may refer to a surfactant.

[0134] The dispersant may be fluorine-free.

[0135] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant, which may be a nonionic surfactant.

[0136] The nonionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0137] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

[0138] An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0139] An example of the ester is an ester of an alcohol and a fatty acid. An example of the alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms). An example of the fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0140] An example of an ester ether is a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. An example of an alcohol is a mono- to trio-hydric (particularly di- to deca-hydric) alcohol (e.g., aliphatic alcohol) having 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms). An example of a fatty acid is a saturated or unsaturated fatty acid having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0141] Examples of alkanolamides are those formed from fatty acids and alkanolamines. The alkanolamides may be monoalkanolamides or dialkanolamines. Examples of fatty acids include saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0142] The polyol may be a di- to penta-hydric alcohol having 10 to 30 carbon atoms. The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0143] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group in the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0144] The nonionic dispersant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides, and is preferably a nonionic dispersant having an oxyalkylene group.

[0145] The nonionic dispersant may be an alkylene oxide adduct of a linear and / or branched aliphatic (saturated and / or unsaturated) group, a polyalkylene glycol ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sorbitan ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a glycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyglycerin ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a sucrose ester of a linear and / or branched fatty acid (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, those in which the alkylene oxide adduct moiety and the polyalkylene glycol moiety have a structure of polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not have to contain an aromatic group.

[0146] The nonionic dispersant has the formula: １ O-(CH ２ CH ２ O) ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms, ２ are independently the same or different and are alkylene groups having 3 or more carbon atoms (e.g., 3 to 10), ３ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more.

[0147] R １ R preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. １Preferred specific examples of R include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group, and a stearyl group. ２ Examples of the nonionic dispersant are a propylene group and a butylene group. In the nonionic dispersant, p may be a number of 3 or more (for example, 5 to 200). q may be a number of 2 or more (for example, 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) at the center. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, and a styrene chain, with the oxypropylene chain being preferred.

[0148] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkanes (C １２ -C １６ ) thiol, sorbitan mono fatty acid (C ７ -C １９ ) or alkyl(C １２ -C １８ ) condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycol, polyethyleneimine ethoxylate, etc.

[0149] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, based on the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, and polyoxypropylenes having an HLB value of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

[0150] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound having no amide group.

[0151] The cationic dispersant may be a low molecular weight type (e.g., a molecular weight of 2000 or less, particularly 1000 or less) or a high molecular weight type (e.g., a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 100000 or less, 7500 or less, 5000 or less, 2500 or less, 1 ... or less, or 250 or less.

[0152] The cationic dispersant may be aliphatic or aromatic, and examples thereof include ammonium salts (e.g., quaternary ammonium salts). The cationic dispersant may be an oxyethylene adduct ammonium salt. Specific examples include amine salt-type dispersants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines; quaternary ammonium salt-type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride; and polymer-type cationic dispersants such as Polyquaternium-1 to 47. Examples of cationic dispersants include alkylamine salts and quaternary ammonium salts.

[0153] The low molecular weight cationic dispersant is R ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. ２１ , R ２２ , R ２３ and -R ２４ Specific examples of X include alkyl groups (e.g., methyl, butyl, stearyl, and palmityl groups) and aromatic groups (e.g., benzyl and phenyl groups). Specific examples of X include halogens (e.g., chlorine) and acids (e.g., hydrochloric acid and acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms) and benzalkonium chloride.

[0154] Specifically, the low molecular weight cationic dispersant is represented by the formula: １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or more (e.g. C１２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group of the formula R ２ is H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group (the number of oxyethylene groups is, for example, 1 (particularly 2, particularly 3) to 50) (CH ３ , C ２ H ５ is particularly preferred), and X is a halogen atom (e.g., chlorine), or C １ ~C ４ or a fatty acid salt of C １ ~C ４ where p is 1 or 2, q is 2 or 3, and p+q=4. １ may have 12 to 50 carbon atoms, for example, 12 to 30 carbon atoms.

[0155] Examples of low molecular weight cationic dispersants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyldi(hydropolyoxyethylene)ammonium chloride, benzyldodecyldi(hydropolyoxyethylene)ammonium chloride, N-[2-(diethylamino)ethyl]oleamide hydrochloride, and the like.

[0156] The polymeric cationic dispersant may be any of various polymers (e.g., polyquaternium-1 to -47) having a cationic group (e.g., ammonium group, quaternary ammonium group). Examples of the polymeric cationic dispersant include cationic natural products (particularly cationic sugars) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationic guar gum, cationic xanthan gum, and chitosan; and polymers of cationic group-containing monomers such as aziridine, vinylimidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternized dimethylammonium ethyl methacrylate, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0157] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not contain an anionic dispersant.

[0158] The anionic dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0159] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonic acid salts, N-acylamino acid type dispersants, phosphate mono- or diester type dispersants, and sulfosuccinate esters. An example of an anionic dispersant is a carboxylate (e.g., a fatty acid salt).

[0160] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant, which may be an amphoteric surfactant.

[0161] The amphoteric dispersant may be a low molecular weight or a high molecular weight dispersant, and may have a molecular weight of 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may have a molecular weight of 100,000 or less, 10,000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0162] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amido betaines, and acetic acid betaine, and specific examples include lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyl dimethylamino acetic acid betaine.

[0163] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0164] The average primary particle size of the inorganic dispersant may be 5 nm or more, 30 nm or more, 100 nm or more, 1 μm or more, 10 μm or more, or 25 μm or more, and may be 100 μm or less, 50 μm or less, 10 μm or less, 1 μm or less, 500 nm or less, or 300 nm or less. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may be hydrophilic particles.

[0165] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0166] [Amount of Dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the modified polyol. Alternatively, the amount of dispersant may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

[0167] [Liquid Medium] The repellent agent of the present disclosure may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent agent may be a dispersion or a solution. The repellent agent of the present disclosure may contain at least water.

[0168] Examples of organic solvents include esters (e.g., esters having 2 to 40 carbon atoms, specifically, ethyl acetate and butyl acetate), ketones (e.g., ketones having 2 to 40 carbon atoms, specifically, methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols having 1 to 40 carbon atoms, specifically, isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyols such as glycol-based solvents, ethers of polyols (e.g., monoethers), etc.). These may be used alone or in combination.

[0169] [Amount of Liquid Medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, relative to 1 part by weight of the polyol modified product, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0170] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per part by weight of the polyol modified product.

[0171] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, and may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per part by weight of the polyol modified product.

[0172] [Silicone] The repellent agent according to the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, it is possible to obtain good texture and durability in addition to good liquid repellency.

[0173] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified silicone, carboxy-modified silicone, methylhydrogen silicone, etc.). The silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.

[0174] The weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0175] [Amount of Silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the polyol modified product, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0176] [Organic Acid] The repellent of the present disclosure may contain an organic acid. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of the carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0177] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the polyol-modified product, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0178] [Inorganic Acid] The repellent of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one type of inorganic acid may be used, or two or more types may be used in combination. Adding an inorganic acid can improve the stability of the aqueous dispersion.

[0179] [Amount of Inorganic Acid] The amount of inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the modified polyol. It may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of inorganic acid may be adjusted so that the pH of the repellent is 3 to 10, for example, 5 to 9, particularly 6 to 8. The repellent may be acidic (pH 7 or less, for example, 6 or less).

[0180] [Hardening Agent] The repellent of the present disclosure may contain a hardening agent (active hydrogen-reactive compound or active hydrogen-containing compound).

[0181] The curing agent (crosslinking agent) in the repellent agent can cure the agent well. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with active hydrogen or an active hydrogen-reactive group. Examples of active hydrogen-reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of active hydrogen-containing compounds are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0182] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound functions as a crosslinking agent. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0183] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate, Aliphatic diisocyanates such as cyanatomethyl caproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0184] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.

[0185] Examples of araliphatic polyisocyanates include araliphatic diisocyanates and araliphatic triisocyanates. Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.

[0186] Examples of aromatic polyisocyanates include aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used alone or in combination of two or more.

[0187] Examples of the polyisocyanate derivatives include various derivatives of the above-mentioned polyisocyanate compounds, such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretimines, isocyanurates, and iminooxadiazinediones. These may be used alone or in combination of two or more.

[0188] These polyisocyanates can be used alone or in combination of two or more. As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which is a compound in which the isocyanate group of a polyisocyanate compound is blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable in solution and can be used in the same solution as the repellent.

[0189] The blocking agent blocks free isocyanate groups. When the blocked polyisocyanate compound is heated to, for example, 100°C or higher, e.g., 130°C or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups. Examples of blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, and oxime compounds. The polyisocyanate compounds can be used alone or in combination of two or more.

[0190] An epoxy compound is a compound having an epoxy group. Examples of epoxy compounds include epoxy compounds having a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. A chloromethyl group-containing compound is a compound having a chloromethyl group. An example of a chloromethyl group-containing compound is chloromethyl polystyrene. A carboxyl group-containing compound is a compound having a carboxyl group. Examples of a carboxyl group-containing compound are (poly)acrylic acid, (poly)methacrylic acid, etc.

[0191] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resins and methyl etherified melamine resins.

[0192] [Amount of Curing Agent] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the modified polyol. Alternatively, the amount may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0193] [Other Components] The repellent may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength agents, flocculants, retention aids, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more. In addition to the above components, other components include other water and / or oil repellents, dispersants, texture adjusters, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, UV absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, shrinkage inhibitors, anti-wrinkle agents after washing, shape retention agents, drape retention agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, dye transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain release agents, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, and anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine. The following may be blended: stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers; foam inhibitors; silk protein powder, surface-modified products thereof, or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos)); stain inhibitors (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by GOO Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.) that can impart silk texture and functionality such as moisture absorption and release. These may be used alone or in combination of two or more.

[0194] [Amount of Other Components] The amount of each or the total amount of the other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the polyol modified product, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0195] <Pulp Composition> The pulp composition of the present disclosure includes a modified polyol and a pulp base material. The pulp composition of the present disclosure may have excellent oil resistance and / or water resistance, preferably both.

[0196] The pulp composition of the present disclosure is obtained by adding a polyol modifier to a pulp base material. The pulp composition may be obtained by treating the pulp base material with a repellent containing the polyol modifier, and the amount of repellent added and the composition of the repellent may be adjusted so that each component is present in a desired amount. Each component that may be contained in the repellent may be added to the pulp composition as a separate additive.

[0197] The pulp composition of the present disclosure may not contain any compound selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The pulp composition of the present disclosure can impart liquid repellency to a substrate even without containing these fluorine compounds.

[0198] The pH of the pulp composition may be 3 to 10, for example 5 to 9, particularly 6 to 8, and the amounts of the components may be adjusted to achieve such a pH.

[0199] [Pulp Base Material] The pulp composition includes a pulp base material. The pulp base material is made of pulp, and the pulp may be wood pulp, non-wood pulp, recycled paper pulp, or the like.

[0200] [Wood Pulp] Wood pulp includes softwood kraft pulp obtained from species such as Abies and Pinus, and hardwood kraft pulp obtained from species such as Acacia, Eucalyptus, Beech, and Populus (e.g., poplar). Examples of softwood kraft pulp include unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), and softwood sulfite pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and hardwood sulfite pulp. The pulps used may be used alone or in combination. In addition to kraft pulp, there are also softwood kraft pulp and hardwood kraft pulp, as well as mechanical pulps such as stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermoground pulp (TGP), chemiground pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc. Furthermore, waste paper pulp includes disintegrated waste paper pulp, disintegrated and deinked waste paper pulp, or disintegrated, deinked and bleached waste paper pulp, which are produced from brown waste paper, recycled kraft envelope paper, recycled magazine paper, recycled newspaper paper, recycled flyer paper, recycled office paper, recycled corrugated cardboard paper, white recycled paper, Kent recycled paper, imitation recycled paper, recycled land paper, etc.

[0201] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, sisal, jute, flax, ganpi, mitsumata, kozo, and the like.

[0202] From the viewpoint of improving oil resistance, the average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, and even more preferably 0.5 mm or more, and from the viewpoint of ease of production, it is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less.

[0203] From the viewpoint of improving oil resistance, the average fiber diameter of the pulp is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less.

[0204] The form of the pulp base material when the polyol-modified compound is added may be pulp alone, a pulp slurry, a pulp product, or the like. Specific examples include pulps such as bleached or unbleached chemical pulps such as kraft pulp and sulfite pulp, bleached or unbleached high-yield pulps such as groundwood pulp, mechanical pulp, and thermomechanical pulp; pulp slurries containing the above pulps; and pulp products such as paper, paper containers, and pulp molded products.

[0205] [Amount of Pulp Base Material] The amount of the pulp base material in the pulp composition may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 75 wt% or more, or 90 wt% or more, and may be 99 wt% or less, 75 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less. Typically, when the pulp composition is prepared by internal addition, the amount of the pulp base material in the pulp composition is 30 wt% or less, and when the pulp composition is prepared by external addition, the amount of the pulp base material in the pulp composition may be 75 wt% or more.

[0206] The amount of the pulp base material may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more in the pulp composition excluding the liquid medium, and may be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less.

[0207] [Liquid Medium] The pulp composition may contain a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent, and is typically an aqueous medium, particularly water. The liquid medium may also contain a liquid medium derived from a repellent agent.

[0208] [Amount of Liquid Medium] The amount of the liquid medium in the pulp composition may be 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 3 wt% or more, 5 wt% or more, 10 wt% or more, 20 wt% or more, 30 wt% or more, 50 wt% or more, 75 wt% or more, 90 wt% or more, or 95 wt% or more, and may be 99 wt% or less, 75 wt% or less, 50 wt% or less, 40 wt% or less, 30 wt% or less, 20 wt% or less, 10 wt% or less, 5 wt% or less, 4 wt% or less, or 3 wt% or less. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium in the pulp composition is 50 wt% or more, particularly 90 wt% or more, and when the pulp composition is prepared by external addition, the amount of the liquid medium in the pulp composition is 30 wt% or less, particularly 10 wt% or less.

[0209] [Polyol Modifier] The pulp composition may contain a polyol modifier (particularly a polyol modifier contained in a repellent). Repellents will be described in detail separately in the section <Repellent>.

[0210] [Amount of Polyol Modifier] The amount of polyol modifier may be 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, relative to 100 parts by weight of the pulp base material, and may be 20 parts by weight or less, 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less. The amount of repellent added to the pulp base material may be adjusted so that the desired amount of polyol modifier is obtained.

[0211] In the external addition treatment, the amount of the polyol modifier contained in the coating layer is 0.01 g / m ２ Above, 0.03g / m ２ Above, 0.05g / m ２ Above, 0.1g / m ２ Above, 0.3g / m ２ Above, 0.5g / m ２ or more, or 1.0 g / m ２or more, and ２ Below, 4.0g / m ２ Below, 3.0g / m ２ Below, 2.0g / m ２ Below, 1.0g / m ２ Below, 0.5g / m ２ Below, 0.3g / m ２ or less, or 0.1 g / m ２ It may be the following:

[0212] [Paper Strength Agent] The pulp composition may contain a paper strength agent. Examples of the paper strength agent include polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; polysaccharide-based paper strength agents such as starch, enzyme-modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber, and pullulan, and modified polysaccharides thereof (e.g., modified polysaccharides into which a hydroxyl group or a cationic group has been introduced); Polyamide-based paper strength agents such as polyamide resins, polyamine resins, polyamide-polyamine resins, polyamide-epichlorohydrin resins, polyamide-polyamine-epichlorohydrin resins, polyamide-polyurea-formaldehyde resins, and epoxidized polyamide resins; urea / melamine-based paper strength agents such as urea resins, melamine resins, urea-formaldehyde resins, and melamine-formaldehyde resins; polyvinyl alcohol-based paper strength agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, and terminally alkyl-modified polyvinyl alcohol; styrene-butadiene copolymers, polyvinyl acetate, vinyl chloride-vinyl acetate copolymers, polyvinyl chloride, polyvinylidene chloride, polyacrylic acid esters, fatty acid diamides, polyethyleneimine resins, and ketone aldehyde resins. The paper strength agent in the present disclosure is preferably a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent, or a polyamide-based paper strength agent.

[0213] [Amount of Paper Strength Agent] The amount of the paper strength agent may be 0.025 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, relative to 100 parts by weight of the pulp base material, and may be 40 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less, preferably 5.0 parts by weight or less.

[0214] The amount of the paper strength agent may be 0.5 parts by weight or more, 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7.5 parts by weight or more, 15 parts by weight or more, or 25 parts by weight or more, preferably 2 parts by weight or more, and may be 500 parts by weight or less, 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, or 50 parts by weight or less, preferably 200 parts by weight or less, per 100 parts by weight of the polyol modified product.

[0215] [Sizing Agent] The pulp composition may contain a sizing agent. Examples of the sizing agent include cationic sizing agents, anionic sizing agents, neutral sizing agents, and amphoteric sizing agents, such as rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents), alkyl ketene dimers, and alkenyl succinic anhydrides.

[0216] [Amount of Sizing Agent] The amount of the sizing agent may be 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.5 parts by weight or more, 0.75 parts by weight or more, 1.0 parts by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, relative to 100 parts by weight of the pulp base material, and may be 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 parts by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less.

[0217] The amount of sizing agent may be 0.5 parts by weight or more, 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7.5 parts by weight or more, 15 parts by weight or more, or 25 parts by weight or more, preferably 2 parts by weight or more, and may be 500 parts by weight or less, 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, or 50 parts by weight or less, preferably 200 parts by weight or less, per 100 parts by weight of the modified polyol.

[0218] [Other Additives] In addition to the above, the pulp composition may contain additives used in the production of pulp products, such as fixing agents (aluminum sulfate, etc.), organic acids (formic acid, acetic acid, etc.), coagulants / flocculants, retention aids, dyes, fluorescent dyes, slime control agents, and defoamers. The pulp composition contains components derived from the repellent, but each of the components that can be contained in the above-mentioned repellent may also be added to the pulp composition as an additive. The pulp composition does not have to contain a colorant (e.g., a dye).

[0219] [Amount of Other Additives] The amount of each of the other additives may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, or 5 parts by weight or more relative to 100 parts by weight of the pulp base material, and may be 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less relative to the pulp base material.

[0220] The amount of other additives may be 0.5 parts by weight or more, 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7.5 parts by weight or more, 15 parts by weight or more, or 25 parts by weight or more, preferably 2 parts by weight or more, and may be 500 parts by weight or less, 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, or 50 parts by weight or less, preferably 200 parts by weight or less, per 100 parts by weight of the modified polyol.

[0221] <Manufacturing method of pulp products>

[0222] The pulp composition of the present disclosure can be obtained by treating a pulp substrate with a repellent agent comprising a modified polyol.

[0223] The resulting pulp composition can be subjected to treatment steps such as drying, heating, molding, etc., as required, to obtain a pulp product.

[0224] The method for producing a pulp product according to the present disclosure may include a step of treating a pulp base material with a repellent (a polyol modifier addition step). The pulp base material is treated with the repellent to obtain a pulp composition. The pulp composition may be produced by a polyol modifier addition step of adding a polyol modifier to the pulp base material, and a strength agent addition step of adding a strength agent to the pulp base material. The polyol modifier addition step and the strength agent addition step may be carried out separately or simultaneously. The obtained pulp composition may be subjected to treatment steps such as drying, heating, and molding, as necessary, to obtain a pulp product.

[0225] The above description of the "pulp composition" is used to refer to the type and composition of the pulp substrate and repellent. The repellent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the repellent of the present disclosure in an organic solvent or water, as necessary, and applying it to the interior and / or surface of the pulp substrate by a known method such as dip coating, spray coating, foam coating, or the like, followed by drying. After drying, a pulp product is obtained to which the solid components of the repellent are attached. If necessary, the repellent may be applied together with an appropriate crosslinking agent and cured. The concentration of the repellent in the treatment agent to be contacted with the pulp substrate may be varied depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0226] The repellent agent of the present disclosure can be applied to a pulp substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. The treatment method may involve dispersing and diluting the repellent agent of the present disclosure in an organic solvent or water, as necessary, and applying it to the interior and / or surface of the pulp substrate by a known method such as dip coating, spray coating, or foam coating, followed by drying. The dilution ratio may be varied as appropriate depending on the concentration and application of the repellent agent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product is obtained to which the solid components of the repellent are attached. If necessary, the repellent agent may be applied together with an appropriate crosslinking agent, followed by curing.

[0227] The repellent agent can be applied to the pulp substrate by any of the known methods for treating a pulp substrate with a liquid. The pulp substrate may be immersed in the repellent agent, the pulp substrate and the repellent agent may be mixed, or the solution may be applied or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0228] Pulp substrate treatment methods can include internal treatment methods in which a repellent is added to pulp (e.g., pulp slurry) before papermaking, or external treatment methods in which a repellent is applied to pulp (e.g., pulp products) after papermaking. Examples of internal treatment methods include mixing and immersion, and may include a step of adding a repellent to pulp slurry and stirring and mixing. Examples of external treatment methods include spraying, coating, immersion, and foam application, and specific examples include pond-type two-roll size presses, gate-roll type, and rod-metering size presses. The treatment may be either an external or internal treatment. For example, when the pulp substrate is paper, the repellent may be coated on the paper, or a solution may be attached or sprayed onto the paper, or the repellent may be mixed with the pulp slurry before papermaking. When the pulp substrate is a fibrous material, treatment methods include padding, immersion, spraying, and coating. Examples of padding treatments include methods using padding devices described on pages 396-397 of "Textile Dyeing and Processing Dictionary" (published by Nikkan Kogyo Shimbun, 1963) and pages 256-260 of "Color Dyeing Chemistry III" (published by Jikkyo Publishing Co., Ltd., 1975). Examples of coating treatments include methods using coating machines described on pages 473-477 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of immersion treatments include methods using batch dyeing machines described on pages 196-247 of "Dyeing and Finishing Equipment Directory" (published by Sen-sha, 1981). Examples of suitable dyeing machines include liquid jet dyeing machines, air jet dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, and cheese dyeing machines. Examples of spray treatments include methods using air sprayers that spray the treatment solution in a mist using compressed air, and hydraulic atomization air sprayers.

[0229] The treatment method may be an internal addition treatment in which a repellent is added to the pulp slurry before papermaking. A pulp product manufacturing method including internal addition treatment may include one or more of the following steps: adding a repellent to the pulp slurry and stirring and mixing it; suction-dewatering the pulp composition prepared in the above step through a mesh of a predetermined shape to deposit the pulp composition and form a molded pulp product intermediate; and molding and drying the molded pulp product intermediate in a heated mold to obtain a molded pulp product. After the treatment, the pulp may be simply dried at room temperature or at a high temperature, and then optionally subjected to a heat treatment depending on the properties of the pulp. The heat treatment temperature may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, and particularly 80°C to 180°C. By performing heat treatment within this temperature range, excellent oil resistance, water resistance, etc. can be exhibited. The internally treated pulp substrate may be treated with a repellent by external addition, and an additional polyol modifier and / or additional paper strength agent may be attached to the surface. Examples of the additional polyol modifier and additional paper strength agent are as described above, but are not limited thereto.

[0230] The treatment method may be an external addition treatment in which a repellent agent is applied to the pulp base material after papermaking. Size presses for external addition treatment can also be divided into the following categories based on the application method. One application method is the so-called pond-type two-roll size press, in which a coating liquid (size liquid) is supplied to the nip formed by passing paper between two rubber rolls, creating a coating liquid pool called a pond, and the paper is passed through this coating liquid pool to apply the size liquid to both sides of the paper. Other application methods include the gate roll type, in which the size liquid is applied using a surface transfer method, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates into the paper, while in the surface transfer type, the size liquid components tend to remain on the paper surface. In the surface transfer type, the coating layer tends to remain on the paper surface compared to the pond-type two-roll size press, and a larger coating layer is formed on the surface than in the pond-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pond-type two-roll size press is used. Papers treated in this way may exhibit excellent oil and water resistance etc., after simple drying at room temperature or at elevated temperatures, optionally followed by a heat treatment which may range in temperature up to 300°C, for example up to 200°C, especially between 80°C and 180°C, depending on the properties of the paper.

[0231] Specific examples of pulp products include paper, paper containers, pulp molded products, food packaging materials, food containers, gypsum board base paper, coated base paper, medium paper, general liners and corrugating media, neutral white roll paper, neutral liners, rust-proof liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, and neutral information paper, etc. Suitable examples of pulp products include food packaging materials and food containers, and particularly pulp molded products for food contact applications.

[0232] <Strength of pulp molded product> [Dry strength] The dry strength of the pulp molded product of the present disclosure is not particularly limited, but is evaluated by the specific tensile strength in a dry state measured in accordance with JIS P 8113: 2006. The specific dry tensile strength is obtained by dividing the dry tensile strength by the density.

[0233] The dry strength (specific dry tensile strength) of the pulp molded product of the present disclosure is preferably 20.0 Nm / g or more, 25.0 Nm / g or more, 30.0 Nm / g or more, more preferably 35.0 Nm / g or more, and even more preferably 40.0 Nm / g or more, and from the viewpoint of ease of production, it may be 200 Nm / g or less, more preferably 100 Nm / g or less, and even more preferably 50 Nm / g or less.

[0234] Adding a polyol modifier to a pulp base material reduces the dry strength of the resulting pulp product. While not limited to the addition method, the internal addition treatment, in which a polyol modifier is added to a pulp slurry before papermaking, and the external addition treatment, in which a polyol modifier is applied to paper after papermaking, result in a greater reduction in dry strength. In the present disclosure, it has been discovered that by employing a specific composition, the reduction in dry strength can be suppressed even when a polyol modifier is used.

[0235] [Wet Strength] The wet strength of the pulp molded product of the present disclosure is not particularly limited, but is evaluated by the specific wet tensile strength measured in accordance with JIS P 8135: 0998. The specific wet tensile strength is obtained by dividing the wet tensile strength by the density.

[0236] The wet strength (specific wet tensile strength) of the pulp molded product of the present disclosure may be 3.0 Nm / g or more, 6.0 Nm / g or more, 8.0 Nm / g or more, 10.0 Nm / g or more, 12.0 Nm / g or more, or 14.0 Nm / g or more, preferably 3.0 Nm / g or more, more preferably 4.0 Nm / g or more, even more preferably 5.0 Nm / g or more, and still more preferably 8.0 Nm / g or more. From the viewpoint of ease of production, the wet strength (specific wet tensile strength) may be 20 Nm / g or less, 18 Nm / g or less, 16 Nm / g or less, or 15 Nm / g or less, preferably 16 Nm / g or less, for example 14 Nm / g or less.

[0237] Adding a polyol modifier to a pulp base material reduces the wet strength of the resulting pulp product. While not limited to the addition method, the internal treatment method, in which an oil-proofing agent is added to a pulp slurry before papermaking, and the external treatment method, in which an oil-proofing agent is applied to paper after papermaking, result in a greater reduction in wet strength than the internal treatment method. In the present disclosure, we have found that by adopting a specific composition, the reduction in wet strength can be suppressed even when a polyol modifier is used.

[0238] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0239] <Test Method> The test procedure is as follows.

[0240] [Preparation of Pulp Mold] A pulp mold was prepared using an automatic molding machine. A mesh-like body was placed on a metal pulp mold die with numerous suction holes at the bottom, and a metal tank was placed on top, with pulp slurry being placed in the upper metal tank. A vacuum pump was used to suck and dehydrate the pulp-containing aqueous composition through the pulp mold die and mesh-like body from the side opposite the side where the mesh-like body was placed in the pulp mold die, at 0.1 to 1 MPa, and the solids (pulp, etc.) contained in the pulp-containing aqueous composition were deposited on the mesh-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried from above and below in a metal male-female mold heated to 60 to 200°C under a pressure of 0.1 to 1 MPa. This produced a pulp mold formed into the shape of a container.

[0241] [Practical oil resistance test at 65°C] The pulp mold was pretreated by storing it under conditions of 23°C and 50% humidity for 12 hours. 100 ml of corn oil at 65°C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the corn oil was removed from the pulp mold and the degree of oil staining of the pulp mold was evaluated. The following evaluation values ​​were set depending on the degree of staining: 5: No staining on the inside 4: Stained on the inside. No staining on the backside 3: Stained on the inside. Slight staining on the backside 2: Stained on the inside. Staining on the backside was less than 50% of the area 1: Stained on the inside. Staining on the backside was 50% or more but less than 100% of the area 0: Stained on the entire backside

[0242] [HD Contact Angle] A solution (or dispersion) of a liquid-repellent compound with a solids concentration of 1.0% was spin-coated onto a silicon wafer at 2500 rpm for 25 seconds to obtain a smooth spin-coated film. This was then heated at 140°C for 1 minute to produce a compound-treated silicon wafer. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the compound-treated silicon wafer, and the static contact angle 1 second after the drop landed was taken as the HD contact angle of the liquid-repellent compound.

[0243] [Tensile Strength of Pulp Molded Products] The tensile strength of the pulp mold was not particularly limited, but was evaluated by the tensile strength index in a dry state measured in accordance with JIS P 8113:2006. Test pieces 15 mm wide, 50 mm long, and 0.8 mm thick were cut out from the bottom of the pulp mold and used. An autograph manufactured by Shimadzu Corporation was used as the equipment, and the test was carried out under the conditions of a pulling interval of 30 mm and a pulling speed of 10 mm / min. The strength per unit area was calculated from the results of the tensile test. [Strength per unit area] = Breaking stress (N) / [Thickness (mm) * Test piece width (mm)] [Tensile strength index] = Breaking stress (N) / [Test piece width (m) * Basis weight (g / m ２ )]

[0244] Preparation Example 1: Preparation of decaglycerol dodecabehenyl ester dispersion 2 g of decaglycerol dodecabehenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 12 / 12*100 [100%], biobased ratio: 100%) as a polyol modification product, 0.2 g of polyethylene oxide trimethyl nonyl ether (HLB: 13), and 17.8 g of water were mixed to obtain a water-dispersible repellent precursor A. This water-dispersible repellent precursor A was heated to 80°C and then stirred at 7000 rpm for 20 minutes using a homogenizer to obtain a water-dispersible repellent. The volume fraction of particles of 100 μm or larger in the obtained water-dispersible repellent was 0%, and the median diameter D50 was 19.8 μm.

[0245] Preparation Example 2: Preparation of decaglycerol heptabehenyl ester dispersion 2 g of decaglycerol heptabehenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 7 / 12*100 [58%], biobased ratio: 100%) as a polyol modification product, 0.2 g of polyethylene oxide trimethyl nonyl ether (HLB: 13), and 17.8 g of water were mixed to obtain precursor A of a water-dispersible repellent. This precursor A of a water-dispersible repellent was heated to 80°C and then stirred at 7000 rpm for 20 minutes using a homogenizer to obtain a water-dispersible repellent. The volume fraction of particles of 100 μm or larger in the obtained water-dispersible repellent was 0%, and the median diameter D50 was 20.6 μm.

[0246] Evaluation Example 1 A biodegradability test was conducted on decaglycerol dodecabehenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 12 / 12*100 [100%], biobased ratio: 100%) in accordance with JIS K 6953-1:2011. The biodegradability was 36% after 30 days of testing, and 62% after 60 days of testing.

[0247] Evaluation Example 2: A biodegradability test was conducted on decaglycerol heptabehenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 7 / 12*100 [58%], biobased ratio: 100%) in accordance with JIS K 6953-1:2011. The biodegradability was 40% after 30 days of testing, and 60% after 60 days of testing.

[0248] Evaluation Example 3 The hexadecane contact angles of decaglycerol dodecabehenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 12 / 12*100 [100%], biobased ratio: 100%) and decaglycerol heptabehenyl ester (degree of polymerization: 10, hydroxy group substitution rate: 7 / 12*100 [58%], biobased ratio: 100%) were measured.

[0249]

[0250] Example 1 The decaglycerol dodecabehenyl ester dispersion of Preparation Example 1 was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio relative to the pulp was 5 wt % in terms of solid content, and the mixture was stirred for 30 seconds. After that, a polyacrylamide-based paper strength agent was added at a ratio relative to the pulp of 0.1% and the mixture was stirred for 30 seconds to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The pulp mold had a basis weight of 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0251] Example 2 The decaglycerol dodecabehenyl ester dispersion of Preparation Example 1 was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio relative to the pulp was 5 wt % in terms of solid content, and the mixture was stirred for 30 seconds. After that, a polyacrylamide-based paper strength agent was added at a ratio relative to the pulp of 0.5% and the mixture was stirred for 30 seconds to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The pulp mold had a basis weight of 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0252] Example 3 The decaglycerol dodecabehenyl ester dispersion of Preparation Example 1 was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio relative to the pulp was 5 wt % in terms of solid content, and the mixture was stirred for 30 seconds. After that, a polyacrylamide-based paper strength agent was added at a ratio relative to the pulp of 1.1% and the mixture was stirred for 30 seconds to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The pulp mold had a basis weight of 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0253] Example 4 The decaglycerol dodecabehenyl ester dispersion of Preparation Example 1 was added to a 0.5 wt% pulp slurry to a ratio of 5 wt% of the pulp in terms of solids content, and the mixture was stirred for 30 seconds. A polyamide-based strength agent was then added at a ratio of 0.6% of the pulp, and the mixture was stirred for 30 seconds to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m2. An oil resistance test was conducted on the produced pulp mold, and the oil resistance was rated at 4 points. The results of the tensile test are shown in Table 1.

[0254] Example 5 The decaglycerol dodecabehenyl ester dispersion of Preparation Example 1 was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio relative to the pulp was 5 wt % in terms of solid content, and the mixture was stirred for 30 seconds. After that, a polyamide-based paper strength agent was added at a ratio relative to the pulp of 0.9% and the mixture was stirred for 30 seconds to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The pulp mold had a basis weight of 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0255] Example 6 The decaglycerol heptabehenyl ester dispersion of Preparation Example 2 was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio relative to the pulp was 5 wt % in terms of solid content, and the mixture was stirred for 30 seconds. After that, a polyacrylamide-based paper strength agent was added at a ratio relative to the pulp of 1.1% and the mixture was stirred for 30 seconds to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The pulp mold had a basis weight of 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0256] Example 7 The decaglycerol heptabehenyl ester dispersion of Preparation Example 2 was added to a pulp slurry having a concentration of 0.5 wt % so that the ratio relative to the pulp was 5 wt % in terms of solid content, and the mixture was stirred for 30 seconds. After that, a polyamide-based paper strength agent was added at a ratio relative to the pulp of 0.9% and the mixture was stirred for 30 seconds to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The pulp mold had a basis weight of 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0257] Example 8 A sugar fatty acid ester water dispersion (polysoybean oil fatty acid sucrose SEFOSE) was added to a pulp slurry with a concentration of 0.5 wt % so that the ratio relative to the pulp was 7 wt % in terms of solid content, and the mixture was stirred for 30 seconds. After that, a polyacrylamide-based paper strength agent was added at a ratio relative to the pulp of 1.1% and the mixture was stirred for 30 seconds to prepare a pulp-containing water-dispersed repellent. The pulp-containing water-dispersed repellent was placed in an automatic molding machine to produce a pulp mold. The pulp mold had a basis weight of 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0258] Comparative Example 1 A pulp-containing water-dispersed repellent was prepared by adding the decaglycerol dodecabehenyl ester dispersion of Preparation Example 1 to a pulp slurry having a concentration of 0.5 wt % without adding any paper strength agent, so that the ratio of the solid content to the pulp was 5 wt %, and stirring was carried out for 30 seconds. The pulp-containing water-dispersed repellent was then placed in an automatic molding machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0259] Comparative Example 2 A pulp-containing water-dispersed repellent was prepared by adding the decaglycerol heptabehenyl ester dispersion of Preparation Example 2 to a pulp slurry having a concentration of 0.5 wt % without adding any paper strength agent, so that the ratio of the solid content to the pulp was 5 wt %, and stirring was carried out for 30 seconds. The pulp-containing water-dispersed repellent was then placed in an automatic molding machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m. ２ An oil resistance test was conducted on the prepared pulp mold, and the oil resistance was 4 points. The results of the tensile test are shown in Table 1.

[0260] Comparative Example 3 A pulp mold was prepared without adding the polyol-modified dispersion or the paper strength agent. A pulp slurry with a concentration of 0.5 wt % was charged into an automatic molding machine to prepare a pulp mold. The basis weight of the pulp mold was 500 g / m ２ When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 0 points. The results of the tensile test are shown in Table 1.

[0261] [Table 1. Evaluation results of tensile test of pulp mold]

Claims

1. A pulp composition comprising a polyol modifier, a pulp base material, and a paper strength agent, wherein the paper strength agent is at least one selected from the group consisting of polyacrylamide-based paper strength agents, polysaccharide-based paper strength agents, and polyamide-based paper strength agents, and the amount of the polyol modifier is 0.2 parts by weight or more and 30 parts by weight or less per 100 parts by weight of the pulp base material.

2. The pulp composition described in claim 1, wherein the polyol modification product is a compound obtained by modifying a polyol with a monovalent hydrocarbon group having 1 to 40 carbon atoms, which may have a substituent, or a monovalent polysiloxane group.

3. A pulp composition according to claim 1 or 2, wherein the modified polyol has an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent.

4. The polyol modification product is a compound in which one or more hydroxy groups of the polyol are replaced with a compound represented by the following formula: -Y Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ Is Y Ｏ１ and Y Ｏ２ Y is a 1+n valent group consisting of one or more selected from the group consisting of Ｏ１ is a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein, R′ is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (e.g., 1 to 20, 1 to 10, or 1 to 4 carbon atoms), Ｏ２ is a group consisting of one or more members selected from the group consisting of optionally substituted di- to tetravalent aliphatic hydrocarbon groups having 1 to 40 carbon atoms, optionally substituted di- to tetravalent aromatic hydrocarbon rings, and optionally substituted di- to tetravalent heterocycles; Z Ｏ is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, and n is an integer of 1 to 3.

5. Y Ｏ -O-Y Ｏ１１ - or -O-Y Ｏ１１ -Y Ｏ２１ -Y Ｏ１２ wherein each symbol represents independently at each occurrence: Y Ｏ１１ is a direct bond, —C(═O)—, —C(═O)—NR′—, or —C(═S)—NR′—; Y Ｏ２１ is a hydrocarbon group having 1 to 40 carbon atoms; Ｏ１２ is -O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-NR'-, -OC(=O)-NR'-, -NR'-, -NR'-C(= O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ The pulp composition of claim 4, wherein:

6. A pulp composition described in any one of claims 1 to 5, wherein the polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and hydroxy group-containing compound polymers.

7. The polyol is selected from the group consisting of glucose, fructose, galactose, xylose; sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose, sucralose; sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan, lactitol; starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, gellan gum, tamarind seed gum; ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; glucosamine; ascorbic acid, inositol; catechin, quercetin, anthocyanin; The pulp composition according to any one of claims 1 to 6, which is at least one selected from the group consisting of glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, and trimethylolethane; polyglycerin, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymers, hydroxypropyl (meth)acrylate polymers, and hydroxybutyl (meth)acrylate polymers.

8. A pulp composition according to any one of claims 1 to 7, wherein the polyol modified product has a hexadecane contact angle of 30° or more.

9. A pulp composition according to any one of claims 1 to 8, wherein the modified polyol is a modified polyglycerol.

10. The pulp composition according to claim 9, wherein the hydroxyl group substitution rate of the modified polyglycerol is 40% or more.

11. A pulp composition according to any one of claims 1 to 10, wherein the amount of the paper strength agent is 2 parts by weight or more and 200 parts by weight or less per 100 parts by weight of the polyol modified product.

12. The polyol modification product is a compound in which a hydroxy group of a monosaccharide or polyglycerin is replaced with a compound represented by the following formula: -O-C(=O)-Z Ｏ [In the formula, Z Ｏ is an aliphatic hydrocarbon group having 14 to 24 carbon atoms.], and the hydroxyl group substitution rate in the modified polyol is 40% or more.

13. A molded pulp product formed from the pulp composition according to any one of claims 1 to 12.

14. The molded pulp product according to claim 13, having a further modified polyol and a further strength agent attached to the surface thereof.

15. The pulp molded product according to claim 13 or 14, which is for use in contact with food.

16. A method for producing a pulp composition according to any one of claims 1 to 12, comprising a polyol modifier adding step of adding the polyol modifier to the pulp base material, and a strength agent adding step of adding the strength agent to the pulp base material.

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