EP4610425A1

EP4610425A1 - Pulp composition

Info

Publication number: EP4610425A1
Application number: EP24883543.1A
Authority: EP
Inventors: Ryo AKUTA; Shun Shibata
Original assignee: Daikin Industries Ltd
Current assignee: Daikin Industries Ltd
Priority date: 2023-11-21
Filing date: 2024-10-29
Publication date: 2025-09-03
Also published as: WO2025109962A1; JP7824535B2; JP2025083906A

Abstract

A novel pulp composition with which a pulp formed article having improved strength is provided by a pulp composition comprising a modified body of polyol, a pulp substrate and a paper strength agent, wherein the paper strength agent is at least one selected from the group consisting of a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent and a polyamide-based paper strength agent, and an amount of the modified body of polyol is 0.2 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the pulp substrate.

Description

Technical Field

The present disclosure relates to a pulp composition.

Background Art

Patent Literature 1 discloses a water-repellent agent comprising glycerol fatty acid ester with a content of monoester of 1 to 50%.

Citation List

Patent Literature

Patent Literature 1: JP 2020-54393 A

Summary of Invention

Technical Problem

Patent Literature 1 does not describe or suggest a paper strength agent, nor does it describe or suggest the strength of pulp products.
An object of the present disclosure is to provide a novel pulp composition with which a pulp formed article having improved strength can be produced.

Solution to Problem

The present disclosure includes the following embodiments.

[Item 1] A pulp composition comprising a modified body of polyol, a pulp substrate and a paper strength agent, wherein
- the paper strength agent is at least one selected from the group consisting of a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent and a polyamide-based paper strength agent, and
- an amount of the modified body of polyol is 0.2 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the pulp substrate.
[Item 2] The pulp composition according to item 1, wherein the modified body of polyol is a compound formed by modifying polyol with a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or with a monovalent polysiloxane group.
[Item 3] The pulp composition according to item 1 or 2, wherein the modified body of polyol has an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.
[Item 4] The pulp composition according to any one of items 1 to 3, wherein the modified body of polyol is a compound formed by replacing one or more hydroxy groups of polyol with a group represented by the following formula:

-Y^O-Z^O _n
- wherein Y^O is a 1+n valent group composed of one or more selected from the group consisting of Y^O1 and Y^O2,
- Y^O1 is a group composed of one or more selected from the group consisting of 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, for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms,
- Y^O2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent,
- Z^O is a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or a monovalent polysiloxane group, and
- n is an integer of 1 or more and 3 or less.
[Item 5] The pulp composition according to item 4, wherein
- Y^O is
- -O-Y^O11- or
- -O-Y^O11-Y^O21-Y^O12-
- wherein, 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-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO₂-, - SO₂NR'-, -C(OR')R'-, or -C(OR')(-)₂.
[Item 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 a monosaccharide, an oligosaccharide, a polysaccharide, a sugar alcohol (reducing sugar), a hydroxy acid, an amino acid, vitamin, flavonol, hydroxyhydrocarbon and a polymer of a hydroxy group-containing compound.
[Item 7] The pulp composition according to any one of items 1 to 6, wherein the polyol is at least one 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;
- glycerol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane;
- polyglycerol, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer and hydroxybutyl (meth)acrylate polymer.
[Item 8] The pulp composition according to any one of items 1 to 7, wherein the modified body of polyol 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 modified body of polyol is a modified body of polygrycerol.
[Item 10] The pulp composition according to item 9, wherein the modified body of polyglycerol has a hydroxy group substitution ratio of 40% or more.
[Item 11] The pulp composition according to any one of items 1 to 10, wherein an amount of the paper strength agent is 2 parts by weight or more and 200 parts by weight or less based on 100 parts by weight of the modified body of polyol.
[Item 12] The pulp composition according to item 1 or 2, wherein
- the modified body of polyol is a compound formed by replacing a hydroxy group of monosaccharide or polyglycerol with a group represented by the following formula:
  -O-C(=O)-Z^O
- wherein Z^O is an aliphatic hydrocarbon group having 14 or more and 24 or less carbon atoms, and
- the modified body of polyol has a hydroxy group substitution ratio of 40% or more.
[Item 13] A pulp formed article formed from the pulp composition according to any one of items 1 to 12.
[Item 14] The pulp formed article according to claim 13, comprising a further modified body of polyol and a further paper strength agent adhered to the surface.
[Item 15] The pulp formed article according to item 13 or 14, which is for food contact.
[Item 16] A method for producing the pulp composition according to any one of items 1 to 12, comprising a modified body of polyol -addition of adding the modified body of polyol to the pulp substrate, and a paper strength agent-addition of adding the paper strength agent to the pulp substrate.

Advantageous Effect of Invention

The present disclosure can provide a pulp formed article having improved strength.

Description of Embodiments

The pulp composition of the present disclosure includes a repellent component and a pulp formed article formed from the pulp composition has not only excellent strength but also excellent liquid repellency.

As used herein, the "n valent group" refers to a group having n bonds, i.e., a group forming n bonds. The "n valent organic group" refers to a n valent group containing carbon. Such organic groups are not limited, but can be hydrocarbon groups or derivatives thereof. The derivative of the hydrocarbon group refers to a group that has one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen and the like at the end or in the molecular chain of a hydrocarbon group.
As used herein, the "hydrocarbon group" refers to a group containing carbon and hydrogen and a group in which a hydrogen atom is removed from the hydrocarbon. Such hydrocarbon groups are not limited, but include C_1-20 hydrocarbon groups, such as an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The above "aliphatic hydrocarbon group" may be either linear, branched, or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may include one or more ring structures. In an explicit term, the hydrocarbon group may be substituted by one or more substituents.
Whether or not the phrases "independently at each occurrence", "independently with each other", "each independently" or similar expressions are explicitly described herein, unless otherwise described that they are exceptions, when a plurality of terms (symbols) that can occur in a chemical structure is defined, such definition is applied independently to each occurrence.
The chemical structures described herein should be understood not to encompass chemical structures that are recognized by those skilled in the art as being chemically impossible or extremely unstable.

The repellent in present disclosure adheres to a substrate (in particular, a pulp substrate) and imparts liquid-repellency, for example, water resistance, oil resistance, water-repellency, oil-repellency and/or antifouling properties to the substrate, and may function as a water-resistant agent, an oil-resistant agent, a water-repellent agent, an oil-repellent agent and/or an antifouling agent.
The repellent in the present disclosure may include a modified body of polyol as an active ingredient (the modified body of polyol will be described in detail separately in {Modified body of polyol}). The modified body of polyol itself may be used as a repellent or may be used as a repellent in combination with other components described below.
The repellent of the present disclosure may not include one 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 of the present disclosure can impart liquid-repellency to a substrate without these fluorine compounds.
The volume abundance ratio of particles with a size of 100 µm or larger in the repellent of the present disclosure may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, and preferably 20% or less, and particularly preferably less than 10%, as measured by laser diffraction scattering. The method for setting the volume abundance ratio of particles with a size of 1 µm or larger as measured by laser diffraction scattering to the above range is not limited, and for example, particles in the raw material and/or dispersion may be formed into fine particles using a pulverizer or a homogenizer.
The repellent in the present disclosure may have a volume median diameter as measured by laser diffraction scattering of 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, and 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 preferably 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 by laser diffraction scattering.
The repellent in the present disclosure may have an ionic charge density of -1,000 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, and is preferably -600 µeq/g or more, and may be, for example, -400 µeq/g or more, -200 µeq/g or more, -50 µeq/g or more, and 5,000 µeq/g or less, 2,500 µeq/g or less, 1,000 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, and is preferably 1,000 µeq/g or less, more preferably 500 µeq/g or less, and for example, 300 µeq/g or less. In particular, it is preferable that the repellent in the present disclosure has an ionic charge density of -600 µeq/g or more and 100 µeq/g or less. The ionic charge density of the repellent in the present disclosure may be measured by, for example, the following method.
The anion requirement of a sample solution having a solid content of 0.1 g/L is measured by a particle charge meter (MUTEK PCD-04 manufactured by BTG) using a 1/1,000 N potassium polyvinylsulfonate solution to calculate the ionic charge density (cationic charge density) by the following equation (1). Alternatively, the cation requirement is measured in the same manner by using poly(diallyldimethylammonium chloride) solution instead of the potassium polyvinylsulfonate solution to calculate the ionic charge density (anionic charge density) by the following equation (1). $Ionic charge density (μeq / g) = A / B$

A: cation requirement or anion requirement (µeq/L)
B: Concentration of sample solution (g/L)

{Modified body of polyol}

The modified body of polyol in present disclosure adheres to a substrate (in particular, a pulp substrate) and imparts liquid-repellency, for example, water resistance, oil resistance, water-repellency, oil-repellency and/or antifouling properties to the substrate, and may function as a liquid-repellent compound.

[Characteristics]

Characteristics that the modified body of polyol may have will be described below. These characteristics may vary depending on the type of the compound.
The modified body of polyol may have a HD (n-hexadecane) contact angle of 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, and is preferably 25° or more, more preferably 30° or more, and may have a HD (n-hexadecane) contact angle of 100° or less, 90° or less, or 75° or less. A HD contact angle of the modified body of polyol of the lower limit or more can impart good liquid-repellency (in particular oil-repellency) to a substrate. The HD contact angle is a static contact angle of the modified body of polyol to a spin-coated film, which is obtained by dropping 2 µL of HD on a spin-coated film and measuring the contact angle one second after the droplet reaches the film.
The modified body of polyol has a water contact angle of 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 have 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less or 90° or less. A water contact angle of the modified body of polyol of the lower limit or more can impart good liquid-repellency (in particular water-repellency) to a substrate. The water contact angle is a static contact angle of a modified body of polyol to a spin-coated film, which is obtained by dropping 2 µL of water on a spin-coated film and measuring the contact angle one second after the droplet reaches the film.
The modified body of polyol is preferably a biobased compound with carbon of biobased origin. A 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, still more preferably 70% or more, and most preferably 80% or more or 90% or more, and for example, 100%. A high biobased content means that the amount of use of fossil resource materials, which are typically petroleum, is small, and a higher biobased content of the modified body of polyol is preferred from that point of view.
The modified body of polyol has a biodegradation as of the 180^th day of preferably 5% or more. A higher biodegradation is preferred because of small environmental load. The modified body of polyol may have a biodegradation as of the 180^th day of, 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, and preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and most preferably 80% or more. The modified body of polyol has a biodegradation as of the 60^th day of preferably 5% or more. A higher biodegradation is preferred because of small environmental load. The modified body of polyol may have a biodegradation as of the 60^th day of, 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, and preferably 10% or more, and more preferably 30% or more. This biodegradation refers to the biodegradation specified in JIS K 6953-1 and ASTM D6400.
The modified body of polyol may have a melting point of 30°C or more, 40°C or more, 60°C or more, 80°C or more, 100°C or more, or 120°C or more, and is preferably 40°C or more, and may have a melting point of 250°C or less, 225°C or less, 200°C or less, 150°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 80°C or less, or 50°C or less.

[Structure]

The modified body of polyol in the present disclosure may not have any one 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. The modified body of polyol can impart liquid-repellency without including these fluorine-containing groups to a substrate.
The modified body of polyol may be a compound having a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or a monovalent polysiloxane group. The modified body of polyol may have a hydrocarbon group having 6 or more and 40 or less carbon atoms (e.g., an alkyl group) from the viewpoint of liquid repellency.

(Monovalent hydrocarbon group optionally having a substituent)

The modified body of polyol may have a monovalent hydrocarbon group optionally having a substituent.
The hydrocarbon group may be a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, and for example, an alkenyl group or alkyl group having 1 to 3 double bonds. The hydrocarbon group may be branched, cyclic or linear, and preferably linear.
The hydrocarbon group may have 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 carbon atoms, and 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 carbon atoms.
The hydrocarbon group may have a substituent, but is preferably non-substituted. Examples of substituents include -OR', -N(R')₂, -COOR', and a halogen atom (wherein R' is independently at each occurrence 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 hydrocarbon group having a substituent, the amount of carbon atom relative to the carbon atom and the heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and 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. The hydrocarbon group may have 1 to 3 (for example, 1) -OR' (in particular, - OH) as a substituent (for example at a site other than the end).

(Monovalent polysiloxane group)

The modified body of polyol may have a monovalent polysiloxane group. A (monovalent) polysiloxane group can impart liquid-repellency to the substrate as the (monovalent) hydrocarbon group does.
The polysiloxane group may also be represented by the following formula:

-[-Si(R^s)₂-O-]_a-

[wherein R^s is independently at each occurrence a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, and
a is an integer of 5 or more and 10,000 or less].

R^s is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.
Examples of hydrocarbon groups having 1 to 40 carbon atoms include a hydrocarbon group having 1 to 5 carbon atoms and a hydrocarbon group having 6 to 40 carbon atoms.
Examples of hydrocarbon groups having 1 to 5 carbon atoms include a hydrocarbon group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group (in particular an aliphatic hydrocarbon group, in particular an alkyl group, for example, a methyl group or an ethyl group, and in particular a methyl group).
The hydrocarbon group having 6 to 40 carbon atoms may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, and in particular a saturated aliphatic hydrocarbon group (an alkyl group). The hydrocarbon group may be cyclic, linear or branched, and is preferably linear. The hydrocarbon group may have 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and has preferably 10 or more, more preferably 12 or more carbon atoms, and may have 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, and has preferably 30 or less, and more preferably 25 or less carbon atoms.
Examples of reactive groups include a group having a functional group (for example, a hydroxy group, an amino group, a mercapto group, an epoxy group, a carboxyl group, a halogen-substituted alkyl group, a vinyl group, a (meth)acrylic group, a (meth)acryloyloxy group, a (meth)acrylamide group, and a hydrogen atom directly bonded to a silicon atom). These functional groups may be directly bonded to a silicon atom, or may be bonded to an organic group directly bonded to a silicon atom. The organic group may be a hydrocarbon group, and for example, an alkylene group or a divalent aromatic group. The hydrocarbon group may have 2 or more and 12 or less carbon atoms. An alkylene group having 2 or more and 10 or less carbon atoms is preferred. A divalent aromatic group having 6 or more and 12 or less carbon atoms is preferred. 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 for example, may be at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group and a carboxyl group.
a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1,000 or more, 2,000 or more, or 3,000 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.
In the polysiloxane group, the amount of R^s which is a hydrocarbon group having 1 to 5 carbon atoms may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, and is 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 relative to the total amount of R^s. For example, 50 mol% or more of the total amount of the R^s group may be a methyl group or an ethyl group (in particular, a methyl group).
In the polysiloxane group, the amount of R^s which is a hydrocarbon group having 6 to 40 carbon atoms may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less relative to the total amount of R^s.
In the polysiloxane group, the amount of R^s which is a reactive group may be 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less relative to the total amount of R^s.
The R^s group may be introduced randomly or in block, and is preferably randomly.
The end structure of the polysiloxane group is not limited, and may be -OR^s, -Si(R^S)₃ and the like. R^s in the end structure may have one or more reactive groups. Examples of reactive groups are as described above, and may be at least one selected from the group consisting of an epoxy ring, a hydroxy group, a (meth)acrylic group and a carboxyl group.
The polysiloxane group may have a linker. The matrix compound and the polysiloxane group may be linked by a linker, and examples of linkers are not limited, and include a hydrocarbon group having 1 to 40 (for example, 1 to 20) carbon atoms optionally disconnected via an oxygen atom, and may be, for example, a (poly)oxyalkylene group having 1 to 40 (for example 1 to 20) carbon atoms.
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-L^s1-[-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, and

-L^s1-[-Si(R^s)₂-O-]_a-R^s

[wherein R^s is independently at each occurrence a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, R^s at the end has one or more reactive groups,
methyl groups account for 50 mol% or more of the total amount of the R^s group,
L^s1 is a hydrocarbon group having 1 to 20 carbon atoms, and
a is 5 or more and 10,000 or less]
[wherein a is an integer of 0 to 150, b is an integer of 1 to 150, (a + b) is 5 to 200 and n is an integer of 0 to 36].

[Embodiments of structure of modified body of polyol]

Examples of modified bodies of polyol include a compound having a hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent, and a monovalent polysiloxane group (e.g., a hydrocarbon group having 6 or more and 40 or less carbon atoms, for example, an alkenyl group or an alkyl group having 1 to 3 double bonds. Examples of hydrocarbon groups and preferred ranges are as described above.
The modified body of polyol 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 sulfone amide group, a sulfone urea group, a sulfone urethane group or a sulfone imide group (e.g., an ester group, an amide group, a urethane group, a urea group, an imide group). For example, the modified body of polyol may include - C(=O)-O-, -O-C(=O)-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'- wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms. The modified body of polyol may be a compound in which a raw material compound and a modifying group (in particular the above monovalent hydrocarbon group optionally having a substituent) are bonded through at least one of the above groups. The modified body of polyol may include an amide structure. Inclusion of at least the amide structure in the modified body of polyol may improve liquid repellency. Herein the amide structure may be an amide structure in the broad sense, and may be selected from the amide structure in an amide (acid amide) group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urethane group, a sulfone urea group and a sulfone imide group. The amide structure may be selected from the group consisting of -(C=O)N(-)₂, - (C=S)N(-)₂ and -S(=O)₂N(-)₂ (each group may be left-right inverted). In this regard, of the bonds possessed by N in the amide structure, at least one 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.
A modified body of polyol may be a compound prepared by chemically modifying polyol so that the polyol can exhibit liquid repellency. The modified body of polyol may be a polymer having a degree of polymerization of 1 or more. The modified body of polyol may have a degree of polymerization of 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and further preferably 9 or more from the viewpoint of the improvement in the liquid-repellency. The modified body of polyol may have a degree of polymerization of 100 or less, preferably 50 or less, more preferably 30 or less, further preferably 15 or less from the viewpoint of the improvement in handling properties of the repellent. The degree of polymerization means the repeating number of monomer units constituting the polymer.
The degree of polymerization in the present disclosure means an average degree of polymerization. The average degree of polymerization in the present disclosure is measured under the following conditions.
When the modified body of polyol in the present disclosure is a modified body of polyglycerol obtained by modifying polyglycerol, the degree of polymerization of the modified body of polyol means the average degree of polymerization of the polyglycerol. The average degree of polymerization of polyglycerol refers to an average degree of polymerization (n) calculated from the hydroxyl number determined by the end group analysis. More specifically, the average degree of polymerization and the average molecular weight are calculated from the following (Formula 1) and (Formula 2). $Average molecular weight = 74 n + 18$ Hydroxyl number = 56110 (n+2) / average molecular weight
The hydroxyl number in the above (Formula 2) indicates the number of hydroxyl groups in polyglycerol. The hydroxyl number is calculated from the amount of potassium hydroxide necessary for neutralizing acetic acid used for acetylation of free hydroxyl groups contained in 1 g of polyglycerol, which is determined according to The JOCS Standard Methods for the Analysis of Fats, Oils and Related Materials (I), 2003, edited by Japan Oil Chemists' Society. The hydroxyl number of polyglycerol, which is the raw material, is actually measured by the above Standard Methods for the Analysis of Fats, Oils and Related Materials, and the average degree of polymerization and the average molecular weight of polyglycerol may be calculated by the above relational expression.
When the modified body of polyol in the present disclosure is a modified body of polyvinyl alcohol obtained by modifying polyvinyl alcohol, the degree of polymerization of the modified body of polyol means the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol may be measured according to JIS K 6726, Testing Methods for Polyvinyl Alcohol.
When the modified body of polyol in the present disclosure is a modified body of polysaccharide obtained by modifying polysaccharide, the degree of polymerization of the modified body of polyol means the average degree of polymerization of the polysaccharide. The average degree of polymerization of polysaccharide may be analyzed as follows. The degree of polymerization refers to the number of monosaccharide units in polysaccharide (fructose and glucose units), and the average degree of polymerization means the maximum of the peaks in the results of analysis obtained by a common analytical method such as HPLC, GC or HPAEC as described below. The average degree of polymerization may be measured by using ULTRON PS-80N made by Shinwa Chemical Industries Ltd. (8 × 300 mm) (solvent: water, flow rate: 0.5 ml/ minute, temperature: 50°C) or TSK-GEL G30000 PWXL made by Tosoh Corporation (7.8 × 300 mm) (solvent: water, flow rate: 0.5 ml/ minute, temperature: 50°C) as the column, and a differential refractometer as the detector.
The modified body of polyol may be a low molecular weight compound (having a weight average molecular weight of less than 1,500, less than 1,000 or 500 or less) and/or a high molecular weight compound. The modified body of polyol may have a weight average molecular weight of 100 or more, 200 or more, 300 or more, 400 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, and may have a weight average molecular weight of 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.
The hydroxy group substitution ratio of the modified body of 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 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, and for example, 95% or less. The "substitution ratio" means the proportion (mol%) of modified hydroxy groups out of the hydroxy groups derived from polyol, and may mean the proportion (mol%) of hydroxy groups modified by a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or a monovalent polysiloxane group.
The residual ratio of hydroxyl groups in the modified body of 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, and for example, is 5% 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, or 5% or less, preferably 60% or less, and for example, 50% or less, 30% or less, or 10% or less. In this regard, the "residual ratio" means the proportion (mol%) of hydroxyl groups without modification, out of the hydroxy groups derived from the polyol.
The number of modifying groups that the modified body of polyol has 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 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. In this regard, the modifying group is preferably a monovalent hydrocarbon group optionally having a substituent or a monovalent polysiloxane group.
The modifying group equivalent of the modified body of polyol may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1,000 or more, and 2,500 or less, 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, 500 or less, or 400 or less. The modifying group equivalent is obtained by dividing the weight average molecular weight of modified body of polyol by the number of modifying groups. In this regard, the modifying group is preferably a monovalent hydrocarbon group optionally having a substituent or a monovalent polysiloxane group.
In the modified body of polyol, one or more of hydroxy groups in polyol are substituted by a modifying group. The modifying group is preferably a monovalent hydrocarbon group optionally having a substituent or a monovalent polysiloxane group. The modified body of polyol may have a structure in which polyol is modified by an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms, for example, an alkenyl group or an alkyl group having 1 to 3 double bonds from the viewpoint of the improvement in liquid-repellency.
Details of the monovalent hydrocarbon group optionally having a substituent and a monovalent polysiloxane group are as described in the above (Monovalent hydrocarbon group optionally having a substituent) and (Monovalent polysiloxane group).

(-Y^O-Z^O _n)
In the modified body of polyol in the present disclosure, one or more hydroxy groups in polyol are optionally substituted by a group represented by the following formula:

-Y^O-Z^O _n

[wherein Y^O is a 1+n valent group composed of one or more selected from the group consisting of Y^O1 and Y^O2,

Y^O1 is a group composed of one or more selected from the group consisting of 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 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms),
Y^O2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent,
Z^O is a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or a monovalent polysiloxane group, and
n is an integer of 1 or more and 3 or less].

^O

Y^O is a 1+n valent group composed of one or more selected from the group consisting of Y^O1 and Y^O2,
Y^O1 is a group composed of one or more selected from the group consisting of 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 hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms),
Y^O2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent.

n is the number of Z^O bonded to Y^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 3 or less, 2 or less, or 1 or less, and for example, 2 or less.
Y^O may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and 3,000 or less, 2,500 or less, 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.
Y^O may include 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 sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^O may include -C(=O)-NR'-, -C(=S)-NR'-, -O-C(=O)-NR'-, - NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^O may improve liquid repellency.

o Y^O1

Y^O1 is a non-hydrocarbon linker.
Y^O1 is a direct bond or a divalent or higher valent group. Y^O1 may have a valence of 2 to 4, 2 or 3, or 2. It is preferable that Y^O1 is not limited to direct bond.
Y^O1 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, or 500 or less.
Y^O1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, - S(=O)₂-, -NR'-, -C(OR')R'- and -C(OR')(-)₂ (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms).
Examples of Y^O1 include:
a direct bond,

-O-,

-O-C(=O)-,

-O-C(=O)-O-,

-O-C(=O)-NR'-,

-NR'-,

-NR'-C(=O)-,

-NR'-C(=O)-O-,

-NR'-C(=O)-NR'-,

-C(=O)-,

-C(=O)-O-,

-C(=O)-NR'-,

-SO₂-,

-SO₂NR'-,

-C(OR')R'-, and

-C(OR')(-)₂

(wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms).
Y^O1 may include 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 sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^O2 may include -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^O1 may improve liquid repellency.

o Y^O2

Y^O2 is a hydrocarbon optionally having a substituent, a hydrocarbon aromatic ring optionally having a substituent or a heterocyclic linker optionally having a substituent.
Y^O2 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y^O2 may be aliphatic or aromatic. Y^O2 may be linear, branched or cyclic.
Y^O2 is a divalent or higher valent group. Y^O2 may have a valence of, for example, 2 to 4, 2 or 3, or 2.
Y^O2 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 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 carbon atoms.
Y^O2 is composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent.
The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched or linear hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 40 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more carbon atoms, and 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms. The aliphatic hydrocarbon group may have a valence of 2 or more, 3 or more, or 4, and 4 or less, 3 or less, or 2.
The aliphatic hydrocarbon group may have a substituent. Examples of substituents include -OR', - N(R')₂, -COOR', and a halogen atom (wherein R' is independently at each occurrence 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 have or be free of 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 aliphatic hydrocarbon group having a substituent, the amount of carbon atom relative to the amount of carbon atom and heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is 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.
Examples of the divalent to tetravalent hydrocarbon aromatic ring 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 hydrocarbon aromatic ring may have a valence of 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.
The hydrocarbon aromatic ring may have a substituent. Examples of substituents include -R', -OR', -N(R')₂, -COOR' and a halogen atom (wherein R' is independently at each occurrence 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 have or be free of 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 hydrocarbon aromatic ring having a substituent, the amount of carbon atom relative to the amount of carbon atom and heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is 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.
The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic rings 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, and the like. The number of ring constituting atom of the heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12 and preferably 5 to 12. A valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.
The heterocyclic ring may have a substituent. Examples of substituents include -R', -OR', -N(R')₂, - COOR' and a halogen atom (wherein R' is independently at each occurrence 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 heterocyclic ring having a substituent, the amount of carbon atom relative to the carbon atom and the heteroatom 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, and 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.

Examples of Y^O2 include

-Ali-,

-Cy-,

-Ali(-)₂,

-Cy(-)₂,

(-)₂Ali-,

(-)₂Cy-,

(-)₂Ali(-)₂,

(-)₂Cy(-)2,

-Ali-Cy-,

-Cy-Ali-,

-Cy-Ali-Cy-, and

-Ali-Cy-Ali-

[wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and Cy is a hydrocarbon aromatic ring or a heterocyclic ring].
Specific examples of Y^O2 include:

(CH₂)_p- (p is 1 to 40, 1 to 20, or 1 to 10),
- a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond,
- a branched hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, and
(CH₂)_q-Cy-(CH₂)_r- (q and r are each independently 0 to 20, for example, 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring).

(Example of Y^O)

Examples of Y^O will be described. In the following, R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms.
When Y^O is divalent, examples of Y^O include -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- and -Y^O2-Y^O1-Y^O2-Y^O1-.
When Y^O is trivalent, examples of Y^O include -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- ₂, -Y^O1-Y^O2-Y^O1-Y^O2(-)₂, -Y^O1-Y^O2-Y^O1-(Y^O2-)₂, -Y^O1-Y^O2-(Y^O1-Y^O2-)₂, -Y^O1-(Y^O2-Y^O1-Y^O2-)₂;
-Y^O2(-)₂, -Y^O2-Y^O1(-)₂, -Y^O2-(Y^O1-)₂, -Y^O2-Y^O1-Y^O2(-)₂, -Y^O2-Y^O1(-Y^O2-)₂, -Y^O2-(Y^O1-Y^O2-)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, and -Y^O2-(Y^O1-Y^O2-Y^O1-)₂.
When Y^O is tetravalent, examples of Y^O include - Y^O1(-)₃, -Y^O1-Y^O2(-)₃, -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^O1-)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, and -Y^O2-(Y^O1-Y^O2-Y^O1-)₃.
Preferred examples of Y^O include -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-, and -Y^O2-Y^O1(-)₂.

(Preferred example of Y^O)

Y^O is preferably

-O-Y^O11- or

-O-Y^O11-Y^O21-Y^O12-

[wherein, 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-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO₂-, - SO₂NR'-, -C(OR')R'-, or -C(OR')(-)₂].

Y^O11 is a non-hydrocarbon linker, and is a direct bond or divalent or higher valent group.
Y^O11 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, or 500 or less.
Y^O11 is a direct bond, -C(=O)-, -C(=O)-NR'- or - C(=S)-NR'-.
Y^O21 is a divalent hydrocarbon linker, and may be a hydrocarbon group having 1 to 40 carbon atoms.
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, and 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 carbon atoms.
The hydrocarbon group having 1 to 40 carbon atoms may be cyclic, branched or linear, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.
Specific examples of Y^O21 include:

Y^O12 may be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO₂-, -SO₂NR'-, - C(OR')R'- or -C(OR')(-)₂.
Y^O12 may include 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 sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^O12 may be -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^O12 may improve liquid repellency.

(Z^O)

Z^O is a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or a monovalent polysiloxane group. The same explanation in the above (a monovalent hydrocarbon group optionally having a substituent) and (a monovalent polysiloxane group) applies.

(Other modifying groups)

The hydroxy group of polyol may be substituted by a modifying group other than -Y^O-Z^O _n. Examples of modifying groups include an anionic group and/ or a cationic group.
Examples of anionic groups include a monomer having a carboxyl group, a sulfonic acid group or a phosphoric acid group.
Examples of salts of the anionic group include alkaline metal salt, alkaline earth metal salt, or an ammonium salt such as methyl ammonium salt, ethanol ammonium salt and triethanol ammonium salt.
Examples of cationic groups include an amino group, which is preferably a tertiary amino group and a quaternary amino group. It is preferable that in the tertiary amino group, two groups bonded to a nitrogen atom, which are the same or different, are an aliphatic group having 1 to 5 carbon atoms (in particular alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (in particular an aralkyl group, e.g., a benzyl group (C₆H₅-CH₂-)). It is preferable that in the quaternary amino group, three groups bonded to a nitrogen atom, which are the same or different, are an aliphatic group having 1 to 5 carbon atoms (in particular alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (in particular an aralkyl group, e.g., benzyl group (C₆H₅-CH₂-)). In the tertiary amino group and the quaternary amino group, the last group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of salt.
The cationic group in the form of salt is a salt with an acid (an organic acid or an inorganic acid). An organic acid such as a carboxylic acid having 1 to 20 carbon atoms (in particular, a monocarboxylic acid such as acetic acid, propionic acid, butyric acid and stearic acid) are preferred.

[Production Method of Modified Body of Polyol]

The modified body of polyol may be produced by reacting a modifying agent including a modifying group (or a precursor structure of the modifying group) with the hydroxy group of polyol.

(Polyol)

Polyol has two or more hydroxy groups and is a raw material of the modified body of polyol. Polyol has two or more hydroxy groups in the molecule. Polyol may be aliphatic or aromatic, and is preferably aliphatic.
Polyol may have an ether bond. Preferably polyol may have two or more ether bonds. More specifically, polyol is preferably a compound having two or more hydroxy groups and two or more ether bonds. In other words, polyol is preferably polyether having two or more hydroxy groups.
When polyol is a polymer, polyol may have a hydroxy group and an ether bond in the repeating structure of the monomer unit.
Polyol may be a low molecular weight compound (having a weight average molecular weight of, for example, less than 1,000 or 500 or less) and/or a high molecular weight compound. Polyol has a weight average molecular weight of 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, and 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.
Polyol may have 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 hydroxy groups, and 3,000 or less, 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less hydroxy groups.
The hydroxy group equivalent of 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 1,000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. Dividing the weight average molecular weight of polyol by the number of hydroxyl groups gives the hydroxy group equivalent of polyol.
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 product also includes a compound converted from microorganisms. Examples of polyol include a monosaccharide, an oligosaccharide, a polysaccharide, a sugar alcohol (reducing sugar), a hydroxy acid, an amino acid, vitamin, flavonol, hydroxyhydrocarbon, a polymer of a hydroxy group-containing compound, polyether polyol, polymer polyol, polyester polyol and other polyols.
Examples of monosaccharides include glucose, fructose, galactose and xylose.
Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose and sucralose.
Examples of sugar alcohols (reducing sugar) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan and lactitol.
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.
Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid and gluconic acid.
Examples of amino acids include glucosamine.
Examples of vitamins include ascorbic acid and inositol.
Examples of flavonols include catechin, quercetin and anthocyanin.
Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, trimethylolpropane and trimethylolethane. The hydroxyhydrocarbon are a hydrocarbon having a hydroxy group, and may be aliphatic or aromatic, and is preferably aliphatic. The term "hydroxyhydrocarbon" may also mean a hydroxyhydrocarbon other than the compounds included in a different group, such as polysaccharide (other hydroxyhydrocarbons).
Examples of polymers of a hydroxy group-containing compound include polyglycerol, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer and hydroxybutyl (meth)acrylate polymer.
Polyether polyol may be a compound obtained by addition polymerization of alkylene oxide onto an initiator. Examples of initiators include a bifunctional or higher functional compound having a hydroxyl group. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, trimethylol propane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol and sucrose. Alkylene oxide include ethylene oxide and propylene oxide. The polyether polyol, which is obtained by addition polymerization of alkylene oxide onto the initiator, is also referred to as polyoxyalkylene polyol, or an oxyalkylene derivative of polyol. Typical examples of polyether polyol include polyoxypropylene triol obtained by addition polymerization of propylene oxide onto glycerol and polyoxypropylene polyglyceryl ether obtained by addition polymerization of propylene oxide onto polyglycerol.
An example of polymer polyol is a compound obtained by polymerizing at least a moiety of polyether polyol in the polyether polyol with an ethylenically unsaturated monomer. Examples of ethylenically unsaturated monomers include acrylonitrile and styrene.
An example of polyester polyol may be a compound obtained by dehydration condensation of a difunctional or higher functional compound having a carboxyl group and a difunctional or higher functional compound having a hydroxyl group. Examples of difunctional or higher functional compounds having a 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 an acid anhydride thereof. Examples of difunctional or higher functional compounds having a hydroxyl group include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol and a polymer thereof.

(Modifying agent)

The modifying agent is preferably a compound which is reactive to polyol and comprises the above monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or a monovalent polysiloxane group.

Examples of modifying agents are as follows:

Acid halide	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	(CH₂OCH)CH₂O-Z^O
Halide	G-Z^O
Amine	H₂N-Z^O
Hydroxy	HO-Z^O

[In the formula, Z^O is as described above, and G is a halogen atom (e.g., F, Cl, Br or I)].

Z^O in the structure of the above modifying agent may be replaced with any group constituting the modifying group. For example, Z^O may be a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or a group having a monovalent polysiloxane group, and Z^O may be -Y^O-Z^O _n.
The modified body of polyol may also be synthesized by reacting polyol and a modifying agent. For example, the modified body of polyol may be synthesized by forming an ester bond by reacting a modifying agent, which is an acid halide compound, acid anhydride or carboxylic acid, with the hydroxy group of polyol. Alternatively, the modified body of polyol may be produced by forming an ether bond by reacting a modifying agent, which is a halide compound or an epoxy compound, with the hydroxy group of polyol. Conditions of the reaction between polyol and the modifying agent may be suitably designed by a person skilled in the art, including use of a catalyst (e.g., acid catalyst and base catalyst) and use of a condensing agent depending on the intended product.

[Amount of modified body of polyol]

The amount of the modified body of polyol may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 70% by weight or more, or 80% by weight or more, and 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less in the repellent. The modified body of polyol may be singly used as a repellent.

{Dispersant}

The repellent of the present disclosure may comprise 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.
An organic dispersant and an inorganic dispersant may be used as the dispersant, respectively, or an organic dispersant and an inorganic dispersant may be used in combination.
An organic dispersant may be used as the dispersant. The organic dispersant may be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant and an amphoteric dispersant. The organic dispersant may mean a surfactant.
The dispersant may have no fluorine.

[Nonionic dispersant]

The dispersant may comprise a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.
The nonionic dispersant may be of low molecular weight or high molecular weight. The nonionic dispersant may have a molecular weight of 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 1,000 or less, 750 or less, or 250 or less.
Examples of nonionic dispersant include ether, ester, ester ether, alkanolamide, polyol and amine oxide.
The ether is, for example, a compound having an oxyalkylene group (preferably a polyoxyethylene group).
The ester is, for example, an ester of an alcohol and a fatty acid. The alcohol is, for example, an alcohol which is 1 to 30 hydric (particularly dihydric to decahydric) and has 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms) (for example, an aliphatic alcohol). Examples of the fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
The ester ether is, for example, a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. The alcohol is, for example, an alcohol which is 1 to 30 hydric (particularly dihydric to decahydric) and has 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, an aliphatic alcohol). Examples of the fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.
The alkanolamide is formed of for example, a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of the fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol with 1 to 3 amino groups and 1 to 5 hydroxyl groups, having 2 to 50, particularly 5 to 30 carbon atoms.
The polyol may be, for example, a dihydric to pentahydric 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).
The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.
The nonionic dispersant is selected from the group consisting of an ether, an ester, an ester ether, an alkanolamide, a polyol, or an amine oxide, and is preferably a nonionic dispersant having an oxyalkylene group.
The nonionic dispersant may be, for example, 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 polyglycerol 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), and an alkylene oxide adduct of acetylene glycol. Among them, the nonionic dispersant is preferably a dispersant such that the structures of the alkylene oxide addition moiety and polyalkylene glycol moiety are polyoxyethylene (POE) or polyoxypropylene (POP) or POE/POP copolymer (which may be a random or block copolymer, for example.).
Furthermore, the nonionic dispersant may not include an aromatic group.
The nonionic dispersant may be the compound represented by the formula:

R¹O-(CH₂CH₂O)_p-(R²O)_q-R³

[wherein R¹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an acyl group, having 2 to 22 carbon atoms,
R² is each independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10),
R³ 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 numeral of 2 or more,
q is 0 or a numeral of 1 or more.].

R¹ preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferred examples of R¹ include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group and a stearyl group.
R² is, for example, a propylene group and a butylene group.
In the nonionic dispersant, for example, p may be a numeral of 3 or more (for example, 5 to 200) and q may be a numeral of 2 or more (for example, 5 to 200). Namely, -(R²O)_q- may form, for example, a polyoxyalkylene chain.
The nonionic dispersant may be, for example, a polyoxyethylene alkylene alkyl ether comprising a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. The hydrophobic oxyalkylene chain includes, for example, an oxypropylene chain, an oxybutylene chain, and a styrene chain. The oxypropylene chain is preferred among them.
Specific examples of the nonionic dispersants include a condensation product of ethylene oxide with hexylphenol, isooctatylphenol, hexadecanol, oleic acid, an alkane (C₁₂-C₁₆) thiol, a sorbitan monofatty acid (C₇-C₁₉), an alkyl (C₁₂-C₁₈) amine, or the like, and a sorbitan fatty acid ester, a glycerin fatty acid ester, a polyglycerin fatty acid ester, a sucrose fatty acid ester, a propylene glycol fatty acid ester, a polyoxyethylene alkyl ether, a polyoxyethylene polyoxypropylene alkyl ether, a polyoxyethylene glycerin fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, and a lecithin derivative. Examples of nonionic dispersants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxybutylene alkyl ether, polyoxyethylene polyoxypropylene glycol and polyethyleneimine ethoxylate.
The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight, based on a 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.
For example, the nonionic dispersant may be used singly or in admixture of two or more. The nonionic dispersant may be a mixture of a compound with an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound with an HLB of 15 or more. More specifically, it is preferable to select the nonionic dispersant from polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene and polyoxypropylene having an HLB of 1 to 18, sorbitan fatty acid ester, glycerol fatty acid ester, polyglycerol fatty acid ester, sucrose fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene glycerol fatty acid ester and polyoxyethylene sorbitan fatty acid ester having an HLB of less than 7.

[Cationic dispersant]

The dispersant may comprise a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound not having an amide group.
The cationic dispersant may be of low molecular weight (with a molecular weight of 2,000 or less, in particular, 1,000 or less) or of high molecular weight (with a molecular weight of, for example, 2,000 or more). The cationic dispersant may have a molecular weight of 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 1,000 or less, 750 or less, or 250 or less.
The cationic dispersant may be aliphatic or aromatic, and examples thereof include an ammonium salt (e.g., quaternary ammonium salt). The cationic dispersant may be oxyethylene-added ammonium salt. Specific examples thereof include an amine salt dispersant such as alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative and imidazoline; a quaternary ammonium salt dispersant such as alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, pyridinium salt, alkyl isoquinolinium salt, benzalkonium chloride and benzethonium chloride; and a polymer cationic dispersant such as polyquaternium-1 to 47. Examples of cationic dispersants include alkyl amine salt and quaternary ammonium salt.
The low molecular weight cationic dispersant may be a compound represented by the formula:

R²¹-N⁺(-R²²)(-R²³)(-R²⁴)X^-

wherein R²¹, R²², R²³ and R²⁴ are a hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and
X is an anionic group. Specific examples of R²¹, R²², R²³ and -R²⁴ include an alkyl group (e.g., a methyl group, a butyl group, a stearyl group, a palmityl group) and an aromatic group (e.g., a benzyl group, phenyl group). Specific examples of X include a halogen (e.g., chlorine) and an acid (e.g., hydrochloric acid and acetic acid). The cationic dispersant may be monoalkyltrimethylammonium salt (in which alkyl has 4 to 40 carbon atoms) and benzalkonium chloride.

More specifically, the low molecular weight cationic dispersant may be an ammonium salt represented by the formula:

R¹ _p-N⁺-R² _qX^-

[wherein R¹ is a C12 or higher (e.g., C₁₂ to C₅₀) linear and/or branched aliphatic (saturated and/or unsaturated) group,

R² is H or a C1 to 4 alkyl group, a benzyl group, a polyoxyethylene group (in which the number of oxyethylene groups is for example, 1 (in particular 2, and especially 3) to 50) (particularly preferably CH₃, C₂H₅),
X is a halogen atom (e.g., chlorine) or a C₁ to C₄ fatty acid salt or a C₁ to C₄ sulfonate,
p is 1 or 2, q is 2 or 3 and p + q = 4.]
R¹ may have 12 to 50, and for example 12 to 30 carbon atoms.

Examples of the low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydropolyoxyethylene) ammonium chloride, benzyldodecyl di(hydropolyoxyethylene) ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.
The high molecular weight cationic dispersant may be a polymer having a cationic group (for example, an ammonium group, a quaternary ammonium group) (for example, polypolyquaternium-1 to 47). Examples of high molecular weight cationic dispersants include a cationic natural product (in particular, cationic sugar) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl)hydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum and chitosan; a polymer of a cationic group-containing monomer such as aziridine, vinyl imidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternary dimethyl ammonium ethyl methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine and quaternary vinyl imidazole.

[Anionic dispersant]

The dispersant may comprise an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not include an anionic dispersant.
The anionic dispersant may be of low molecular weight or high molecular weight. The anionic dispersant may have a molecular weight of 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 1,000 or less, 750 or less, or 250 or less.
Examples of the anionic dispersant include an alkyl ether sulfate, an alkyl sulfate, an alkenyl ether sulfate, an alkenyl sulfate, an olefin sulfonate, an alkanesulfonate, a saturated or unsaturated fatty acid salt, an alkyl or alkenyl ether carbonate, an α-sulfone fatty acid salt, a N-acylamino acid dispersant, a phosphate mono- or diester dispersant, and a sulfosuccinic acid ester. Examples of anionic dispersants include a carboxylic acid salt (e.g., fatty acid salt).

[Amphoteric dispersant]

The dispersant may comprise an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.
The amphoteric dispersant may be of low molecular weight or high molecular weight. The amphoteric dispersant may have a molecular weight of 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 2,500 or less, 1,000 or less, 750 or less, or 250 or less.
Examples of the amphoteric dispersants include, for example, alanines, imidazolinium betaines, amidobetaines, and acetic acid betaine, and specific examples of the amphoteric dispersants include, for example, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[Inorganic dispersant]

The dispersant may comprise an inorganic dispersant.
The inorganic dispersant has an average primary particle size of 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 µm or larger, 10 µm or larger, or 25 µm or larger, and 100 µm or smaller, 50 µm or smaller, 10 µm or smaller, 1 µm or smaller, 500 nm or smaller, or 300 nm or smaller. The average primary particle size may be measured by a microscope, for example, a scanning electron microscope or a transmission electron microscope. The inorganic dispersant may be hydrophilic particles.
Examples of inorganic dispersants include polyvalent metal phosphate such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate and hydroxyapatite; carbonate such as calcium carbonate and magnesium carbonate; silicate such as calcium metasilicate; sulfate such as calcium sulfate and barium sulfate; and hydroxide such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide.

[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, 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, 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 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, relative to 100 parts by weight of the modified body of polyol.

{Liquid medium}

The repellent in the present disclosure may comprise a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent in the present disclosure may include at least water.
Examples of the organic solvents include esters (for example, esters having 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (for example, ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (for example, alcohols having 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (for example, toluene and xylene), petroleum-based solvents (for example, 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 include a compound having at least one hydroxy group (for example, polyol such as alcohol and glycol solvent, and an ether form of polyol (for example, a monoether form)). These may be used alone, or two or more of them may be used in combination.

[Amount of liquid medium]

The amount of 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, or 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 1,000 parts by weight or more, and 3,000 parts by weight or less, 2,000 parts by weight or less, 1,000 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 relative to 1 part by weight of the modified body of polyol.
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 1,000 parts by weight or more, and 3,000 parts by weight or less, 2,000 parts by weight or less, 1,000 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 based on 1 part by weight of the modified body of polyol.
The amount of the 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 1,000 parts by weight or more, and 3,000 parts by weight or less, 2,000 parts by weight or less, 1,000 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 relative to 1 part by weight of the modified body of polyol.

{Silicone}

The repellent in the present disclosure may include silicone (polyorganosiloxane). Containing the silicone enables providing favorable texture and durability in addition to favorable liquid-repellency.
As the silicone, a known silicone can be used, and examples of the silicone include a polydimethylsiloxane and modified silicones (for example, amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and methylhydrogen silicone). For example, the silicone may be silicone wax having waxy properties. These may be used singly or in combination of two or more thereof.
A 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.

[Amount of Silicone]

The amount of silicone is 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, 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, relative to 100 parts by weight of the modified body of polyol.

{Organic Acid}

The repellent of the present disclosure may contain an organic acid. As the organic acid, a known organic acid can be used. Examples of the organic acid preferably include, for example, a carboxylic acid, a sulfonic acid, and a sulfinic acid, with the carboxylic acid being particularly preferred. Examples of the carboxylic acid include, for example, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, and citric acid, with the formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more thereof may be combined for use. For example, formic acid and acetic acid may be combined for use.

[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, 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, relative to 100 parts by weight of the modified body of polyol. The amount of organic acid may be adjusted so that a pH of the repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. For example, the repellent may be acidic (pH of 7 or less, for example 6 or less).

{Inorganic acid}

The repellent in the present disclosure may comprise an inorganic acid. As the inorganic acid, a known inorganic acid 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 inorganic acid may be used, or two or more of them may be used in combination. The addition of inorganic acid can improve the stability of the aqueous dispersion.

[Amount of inorganic acid]

The amount of the 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, and 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 based on 100 parts by weight of the modified body of polyol. The amount of the inorganic acid may be adjusted so that the repellent has a pH of 3 to 10, for example, 5 to 9, and in particular, 6 to 8. The repellent may be acidic (may have a pH of 7 or less, for example, 6 or less).

{Curing Agent}

The repellent of the present disclosure may contain a curing agent (active hydrogen-reactive compound or active hydrogen-containing compound).
The curing agent (cross-linking agent) in the repellent can effectively cure the repellent. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound, which reacts with an active hydrogen or an active hydrogen-reactive group. Examples of the active hydrogen-reactive compound include an isocyanate compound, epoxy compound, chloromethyl group-containing compound, carboxyl group-containing compound, and hydrazide compound. Examples of the active hydrogen-containing compound include a hydroxyl group-containing compound, an amino group-containing compound and a carboxyl group-containing compound, a ketone group-containing compound, a hydrazide compound, and a melamine compound.
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 serves as a cross-linking agent. Examples of the polyisocyanate compound include, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, 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 an isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.
Examples of the aliphatic polyisocyanates are aliphatic triisocyanates such as 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, an aliphatic diisocyanate of 2,6-diisocyanatomethylcaproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanateoctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used singly or in combination of two or more thereof.
Examples of the alicyclic polyisocyanates include, for example, an alicyclic diisocyanate and an alicyclic triisocyanate. Specific examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used singly or in combination of two or more thereof.
Examples of the aromatic-aliphatic polyisocyanate include an araliphatic diisocyanate and aromatic-aliphatic triisocyanate. Specific examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethyl xylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used singly or in combination of two or more thereof.
Examples of the aromatic polyisocyanates include an aromatic diisocyanate, aromatic triisocyanate, and aromatic tetraisocyanate. Specific examples of the aromatic polyisocyanate include, for example, 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 singly or in combination of two or more thereof.
Examples of the derivative of the polyisocyanate include various derivatives such as a dimer, trimer, biuret, allophanate, carbodiimide, urethodione, urethoimine, isocyanurate, and iminooxadiazinedione of the aforementioned polyisocyanate compounds. These may be used singly or in combination of two or more thereof.
These polyisocyanates can be used singly or in combination of two or more thereof.
As the polyisocyanate compound, a blocked polyisocyanate compound (blocked isocyanate), which is a compound obtained by blocking isocyanate groups of the polyisocyanate compound with a blocking agent, is preferably used. The blocked polyisocyanate compound is preferably used because it is relatively stable even in solution and can be used in the same solution as solution of the repellent.
The blocking agent is an agent that blocks free isocyanate groups. The blocked polyisocyanate compound, for example, can be heated 100°C or higher, for example, 130°C or higher to regenerate isocyanate groups, facilitating a reaction with hydroxyl groups. Examples of the blocking agent include, for example, a phenolic compound, lactam-based compound, aliphatic alcohol-based compound, and oxime-based compound. The polyisocyanate compound may be used singly or in combination of two or more thereof.
The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as a polyglycerol polyglycidyl ether and a polypropylene glycol diglycidyl ether; as well as a sorbitol polyglycidyl ether.
The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include, for example, a chloromethyl polystyrene.
The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include, for example, a (poly)acrylic acid, and a (poly)methacrylic acid.
Specific examples of the ketone group-containing compound include, for example, a (poly)diacetone acrylamide, and diacetone alcohol.
Specific examples of the hydrazide compound include, for example, hydrazine, a carbohydrazide, and adipic acid hydrazide.
Specific examples of the melamine compound include, for example, a melamine resin and a methyl etherified melamine resin.

[Amount of Curing Agent]

The amount of the 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, 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, and 5 parts by weight or less, relative to 100 parts by weight of the modified body of polyol.

{Other Component}

The repellent may contain a component other than the aforementioned components. Examples of the other components include, for example, polysaccharides, a paper strengthening agent, an agglomerating agent, a yield improver, a coagulant, a binder resin, an anti-slip agent, a sizing agent, a paper strengthening agent, a filler, an antistatic agent, an antiseptic agent, an ultraviolet absorber, an antibacterial agent, a deodorant, and a fragrance. These may be used singly or in combination of two or more thereof.
In addition to the above components, as other components, for example, other water-repellent and/or oil-repellent agents, a dispersant, a texture modifier, a softening agent, a flame retarder, a coating material fixing agent, a wrinkle-resistant agent, a drying rate adjuster, a cross-linking agent, a film formation agent, a compatibilizer, an antifreezing agent, a viscosity adjuster, an ultraviolet absorber, an antioxidant, a pH adjuster, an insect repellent, an antifoaming agent, an anti-shrinkage agent, a laundry wrinkle-resistant agent, a shape retention agent, a drape retention agent, an ironing improving agent, a brightening agent, a whitening agent, fabric softening clay, a migration-proofing agent such as a polyvinylpyrrolidone, a polymer dispersant, a soil release agent, a scum dispersant, a fluorescent brightening agent such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals Plc), a dye fixing agent, an anti-color fading agent such as 1,4-bis(3-aminopropyl) piperazine, a stain removing agent, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers, a foam inhibitor, and silk protein powder that can impart texture and functions of silk such as moisture absorption and release properties, and surface modified products or emulsified dispersions thereof (for example, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk liquid (Jomo), SILKGEN G Soluble S (ICHIMARU PHARCOS Co., Ltd.)), an antifouling agent (for example, a nonionic polymer compound composed of an alkylene terephthalate and/or an alkylene isophthalate units and a polyoxyalkylene unit (for example, FR627 manufactured by GOO CHEMICAL CO., LTD.), SRC-1 manufactured by Clariant (Japan), K. K.), can be compounded. These may be used singly or in combination of two or more thereof.

[Amount of Other Component]

Each amount or the total amount of 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, 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, relative to 100 parts by weight of the modified body of polyol.

The pulp composition of the present disclosure comprises a modified body of polyol and a pulp substrate. The pulp composition of the present disclosure has excellent oil resistance and/or water resistance, preferably both of the two.
The pulp composition of the present disclosure is obtained by adding the modified body of polyol to a pulp substrate. The pulp composition may also be obtained by treating a pulp substrate with a repellent containing a modified body of polyol. In that case the amount of the repellent added and the composition of the repellent may be adjusted so that the respective components are in desired amounts. The components in the repellent may also be separately added to the pulp composition as an additive.
The pulp composition of the present disclosure may not have any one 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 without including these fluorine compounds.
The pulp composition may have a pH of 3 to 10, for example, 5 to 9, and in particular 6 to 8. The amount of the respective components may be adjusted to achieve such pH.

{Pulp substrate}

The pulp composition comprises a pulp substrate. The pulp substrate is composed of pulp, which may be, for example, wood pulp, non-wood pulp and wastepaper pulp.

[Wood pulp]

Wood pulp includes softwood kraft pulp from the genus Abies, Pinus and the like, and hardwood kraft pulp from the genus Acacia, Eucalyptus, Fagus, and Populus (e.g., poplar). Softwood kraft pulp includes, for example, 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 pulp may be used singly or in combination. Other than kraft pulp, in addition to softwood kraft pulp and hardwood kraft pulp, wood pulp includes stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermo-ground pulp (TGP), chemi-ground pulp (CGP), crushed wood pulp (GP), thermomechanical pulp (TMP), and other mechanical pulps. Furthermore, wastepaper pulp includes a disintegrated wastepaper pulp, a disintegrated and deinked wastepaper pulp or a disintegrated, deinked and bleached wastepaper pulp produced from brown waste paper, kraft envelope wastepaper, wastepaper of magazines, wastepaper of newspapers, wastepaper of flyers, sorted office paper, wastepaper of cardboard, hard white wastepaper, Kent wastepaper, wastepaper of poster paper and bond paper.
Examples of non-wood pulp include pulp prepared from bagass, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, Xyzal hemp, yellow hemp, flax, ganpi, paper bush and kozo (Japanese paper mulberry).
The pulp has an average fiber length of preferably 0.1 mm or more, more preferably 0.3 mm or more and further preferably 0.5 mm or more from the viewpoint of the improvement in oil resistance, and preferably 5.0 mm or less, more preferably 4.0 mm or less, further preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less from the viewpoint of ease of manufacture.
The pulp has an average fiber diameter of preferably 5 µm or more, more preferably 10 µm or more, further preferably 15 µm or more, and preferably 50 µm or less, more preferably 40 µm or less, and further preferably 30 µm or less from the viewpoint of the improvement in oil resistance.
The form of the pulp substrate when the modified body of polyol is added thereto may be pulp alone, pulp slurry, or a pulp product. Specific examples thereof include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp; bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp, or thermomechanical pulp; pulp slurry including the above pulp; and a pulp product such as paper, a paper container and a pulp formed article.

[Amount of pulp substrate]

The amount of pulp substrate may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less in the pulp composition. Typically, when the pulp composition is prepared by internal addition, the amount of pulp substrate is 30% by weight or less in the pulp composition; when the pulp composition is prepared by external addition, the amount of pulp substrate may be 75% by weight or more in the pulp composition.
The amount of the pulp substrate 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, and 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 in the pulp composition excluding liquid medium.

{Liquid medium}

The pulp composition may comprise a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The liquid medium is typically an aqueous medium, and in particular, water. The liquid medium may comprise a liquid medium derived from repellent.

[Amount of liquid medium]

The amount of the liquid medium may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, and 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less in the pulp composition. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium is 50% by weight or more, and in particular 90% by weight or more in the pulp composition; when the pulp composition is prepared by external addition, the amount of the liquid medium is 30% by weight or less, and in particular, 10% by weight or less in the pulp composition.

{Modified body of polyol}

The pulp composition may comprise a modified body of polyol (in particular, a modified body of polyol included in the repellent). The repellent will be separately described in <Repellent>.

[Amount of modified body of polyol]

The amount of the modified body of polyol 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 part by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and 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 part by weight or less, 0.75 part by weight or less, or 0.5 part by weight or less, and is preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less based on 100 parts by weight of the pulp substrate. The amount of the repellent added to the pulp substrate may be adjusted to achieve the desired amount of the modified body of polyol.
In the external addition treatment, the amount of the modified body of polyol contained in the coating layer may be 0.01 g/m² or more, 0.03 g/m² or more, 0.05 g/m² or more, 0.1 g/m² or more, 0.3 g/m² or more, 0.5 g/m² or more or 1.0 g/m² or more, and 5.0 g/m² or less, 4.0 g/m² or less, 3.0 g/m² or less, 2.0 g/m² or less, 1.0 g/m² or less, 0.5 g/m² or less, 0.3 g/m² or less, or 0.1 g/m² or less.

{Paper strength agent}

The pulp composition may comprise a paper strength agent. Examples of paper strength agents include:

a polyacrylamide-based paper strength agent such as cationic polyacrylamide, anionic polyacrylamide and amphoteric polyacrylamide;
a polysaccharide-based paper strength agent such as starch, enzyme modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde starch, cationized starch, starch, xanthan gum, gum karaya, 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 a modified polysaccharide thereof (e.g., a modified polysaccharide prepared by introducing a hydroxyl group or a cationic group thereinto);
a polyamide-based paper strength agent such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epichlorohydrin resin, polyamide-polyamine-epichlorohydrin resin, polyamide-polyurea-formaldehyde resin and epoxidized polyamide resin;
a urea/melamine paper strength agent such as urea resin, melamine resin, urea-formaldehyde resin and melamine-formaldehyde resin;
a polyvinyl alcohol paper strength agent such as polyvinyl alcohol, completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl modified polyvinyl alcohol, silanol modified polyvinyl alcohol, cation modified polyvinyl alcohol and terminal alkyl modified polyvinyl alcohol; and
a styrene butadiene copolymer, polyvinyl acetate, a vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic ester, fatty acid diamide, polyethyleneimine resin and ketone aldehyde resin. A polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent and a polyamide-based paper strength agent are preferred as the paper strength agent in the present disclosure.

[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 part by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and 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 part by weight or less, 0.75 part by weight or less, or 0.5 part by weight or less, and is preferably 5.0 parts by weight or less based on 100 parts by weight of the pulp substrate.
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, and is 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, and is preferably 200 parts by weight or less based on 100 parts by weight of the modified body of polyol.

{Sizing agent}

The pulp composition may comprise a sizing agent. Examples of sizing agents include a cationic sizing agent, an anionic sizing agent, a neutral sizing agent and an amphoteric sizing agent, a rosin-based sizing agent (for example, an acidic rosin-based sizing agent and a neutral rosin-based sizing agent), alkyl ketene dimer and alkenyl succinic anhydride.

[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 part by weight or more, 2.0 parts by weight or more, or 3.0 parts by weight or more, and 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 part by weight or less, 0.75 parts by weight or less, or 0.5 parts by weight or less based on 100 parts by weight of the pulp substrate.
The amount of the 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, and is 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, and is preferably 200 parts by weight or less based on 100 parts by weight of the modified body of polyol.

{Other additives}

The pulp composition may also include an additive used for producing a pulp product in addition to the above components, such as a fixing agent (e.g., aluminum sulfate), an organic acid (e.g., formic acid, acetic acid), a coagulant and an agglomerating agent, a yield improver, a dye, a fluorescent dye, a slime control agent, and an antifoaming agent. While the pulp composition includes a component derived from a repellent, the component contained in the repellent may be added to the pulp composition as an additive. The pulp composition may not include a coloring agent (e.g., a dye).

[Amount of other additives]

The amount of other additives 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, respectively, based on 100 parts by weight of the pulp substrate, and 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, respectively, based on 100 parts by weight of the pulp substrate.
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, and is 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, and is preferably 200 parts by weight or less based on 100 parts by weight of the modified body of polyol.

The pulp composition of the present disclosure may be obtained by treating a pulp substrate with a repellent comprising a modified body of polyol.
A pulp product may be obtained by subjecting the resulting pulp composition to processing such as drying, heating and forming according to need.
The method for producing a pulp product of present disclosure may comprise a step of treating a pulp substrate with a repellent (modified body of polyol-addition step). The pulp substrate is treated with a repellent to give a pulp composition. The pulp composition may also be produced by the modified body of polyol-addition step of adding a modified body of polyol to pulp substrate and a paper strength agent-addition step of adding a paper strength agent to the pulp substrate. The modified body of polyol-addition step and the paper strength agent-addition step may be performed separately or simultaneously. A pulp product may be obtained by subjecting the resulting pulp composition to processing such as drying, heating and forming according to need.
The pulp substrate and the type and the composition of the repellent are as described in the above "Pulp composition". The repellent in the present disclosure can be applied to a substrate as a treatment agent (particularly a surface-treating agent) by a conventionally known method. The treatment method may be a method for dispersing the repellent in the present disclosure in an organic solvent or water, if necessary, to dilute it and allowing it to adhere to an inside of a substrate and/or on a surface thereof by a known method such as dip coating, spray coating, and foam coating and drying. After drying, a pulp product to which a solid component of the repellent has been adhered, is obtained. If necessary, the repellent of the present disclosure may be applied in combination of a suitable cross-linking agent, and curing may be carried out. The concentration of the repellent in the treatment agent to be in contact with the pulp substrate, which may vary depending on the purpose of use, may be 0.01 to 10% by weight, and for example, 0.05 to 5% by weight.
The repellent in the present disclosure can be applied to a pulp substrate as a treatment agent (particularly a surface-treating agent) by a conventionally known method. The treatment method may be a method for dispersing the repellent in the present disclosure in an organic solvent or water, if necessary, to dilute it and allowing it to adhere to an inside of a pulp substrate and/or on a surface thereof and drying by a known method such as dip coating, spray coating, and foam coating. The dilution factor, which may be changed depending on the concentration and the purpose of use of the repellent, may be 3 to 2,000 times, and for example, 10 to 100 times. After drying, a pulp product to which a solid component of the repellent has been adhered, is obtained. If necessary, the repellent of the present disclosure may be applied in combination with a suitable cross-linking agent, and curing may be carried out.
The repellent can be applied to a pulp substrate by any of methods known for treating a pulp substrate with liquid. The pulp substrate may be immersed in the repellent, the pulp substrate and the repellent may be mixed, or solution may be adhered or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating in order 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.
As the method for treating a pulp substrate, an internal addition treatment method in which repellent is added to a pulp before papermaking (e.g., pulp slurry), or an external addition treatment method in which repellent is applied to a pulp after papermaking (e.g., a pulp product), can be employed. Examples of internal addition treatment methods include mixing and dipping, and the internal addition treatment method may include a step of adding a repellent to pulp slurry and mixing it with stirring. Examples of external addition treatment methods include spraying, coating, dipping and foam coating and more specifically a pound-type two-roll size press, a gate roll type size press and a rod metering type size press. The treatment may be external addition treatment or internal addition treatment. For example, when the pulp substrate is paper, the repellent may be applied to paper, or solution may be adhered or sprayed onto paper, or the repellent may be mixed with pulp slurry before papermaking to perform treatment. When the pulp substrate is a fiber material, examples of treatment methods include padding treatment, dip treatment, spray treatment, and coating treatment. Examples of padding treatment include the method involving using the padding apparatus as described on pages 396 to 397 of Seni Sensyoku Kako Jiten (in Japanese; Fiber-dyeing process dictionary) (published by THE NIKKAN KOGYO SHIMBUN, LTD., 1963) and pages 256 to 260 of Irozome Kagaku (in Japanese; dyeing chemistry) III (published by Jikkyo Shuppan Co., Ltd., 1975). Examples of the coating treatment include the method involving using a coating machine as described on pages 473 to 477 of Sensyoku Shiage Kiki Soran (in Japanese; Comprehensive guide to dyeing and finishing machines) (published by Fiber Japan CO., LTD., 1981). Examples of the dip treatment include the method involving using a batch type dyeing machine as described on pages 196 to 247 of Sensyoku Shiage Kiki Soran (in Japanese; Comprehensive guide to dyeing and finishing machines) (published by Fiber Japan CO., LTD., 1981), and for example, a jet dyeing machine, air flow dyeing machine, drum dyeing machine, wince dyeing machine, washer dyeing machine, and cheese dyeing machine can be used. Examples of the spray treatment include a method involving using an air spray that nebulizes and sprays a treatment liquid by compressed air, or an air spray by hydraulic pressure nebulization system.
The method of treatment may be internal addition treatment in which a repellent is added to pulp slurry before papermaking. The method for producing a pulp product including internal addition treatment may include one or more of a step of adding the repellent to pulp slurry and stirring and mixing them; a step of sucking and dehydrating the pulp composition prepared in the step through a net-like body of predetermined shape and depositing the pulp composition then to form a pulp formed article intermediate; and a step of molding and drying the pulp formed article intermediate by using a heated molding mold to obtain a pulp formed article. Following the treatment, after having been lightly dried at room temperature or elevated temperature, the treated paper may be arbitrarily subjected to heat treatment, depending on the nature of the paper. The temperature of the heat treatment 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, particularly 80°C to 180°C. Carrying out the heat treatment in such a temperature range enables exhibiting, for example, excellent oil resistance and water resistance. The pulp substrate which has undergone internal addition treatment may be subjected to external addition treatment to be treated with the repellent, allowing a further modified body of polyol and/or a further paper strength agent to be adhered to the surface. Examples of further modified bodies of polyol and further paper strength agents are as described above, but not limited thereto.
The treatment method may be an external addition treatment in which repellent is applied to a pulp substrate after papermaking. The size press used in external addition treatment may be classified depending on the coating method as follows. One coating method involves supplying a coating liquid (size liquid) to a nip portion formed by passing paper between two rubber rolls, creating a pool of the coating liquid called a pond, and allowing the paper to pass through this pool to coat both sides of the paper with the size liquid, which is a method employed for a so-called pound-type two-roll size press. Another coating method is a method used for a gate roll type size press in which a size liquid is applied by a surface transfer type, and a rod metering type size press. In the pound-type two-roll size press, the size liquid easily penetrates into an inside of paper, and in the surface transfer type, a size liquid component is likely to stay on a surface of the paper. In the surface transfer type, a coating layer is likely to stay on a surface of paper more than in the pound-type two-roll size press, and the amount of coating layer formed on the surface is more than in the pound-type two-roll size press. In the present disclosure, even in the case of using the former pound-type two-roll size press, performance can be imparted to paper. After having been lightly dried at room temperature or elevated temperature, the paper treated in such a manner is arbitrarily accompanied by heat treatment that can have a temperature range of up to 300°C, for example up to 200°C, and particularly the temperature range of 80°C to 180°C, depending on the nature of the paper, as a result of which excellent oil resistance, water resistance, and the like can be exhibited.
Specific examples of the pulp products include, for example, paper, a paper container, a pulp formed article, a food packaging material, a food container, gypsum liner board base paper, coated base paper, medium-quality paper, a general liner and core, neutral pure white roll paper, a neutral liner, a rust-proof liner, and metal pasted paper, kraft paper, neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper. Preferred examples of pulp products include a food packaging material and a food container, and in particular, a pulp formed article for food contact.

{Dry strength}

The dry strength of the pulp formed article of the present disclosure is not limited, and is evaluated based on the specific tensile strength in the dry condition which is measured according to JIS P 8113:2006. The specific dry tensile strength is obtained by dividing the dry tensile strength by the density.
The pulp formed article of the present disclosure may have a dry strength (specific dry tensile strength) of 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 further preferably 40.0 Nm/g or more, and 200 Nm/g or less, more preferably 100 Nm/g or less, and further preferably 50 Nm/g or less from the viewpoint of ease of manufacture.
Adding the modified body of polyol to the pulp substrate reduces the dry strength of the resulting pulp product. Although the method of addition is not limited, reduction in dry strength is larger in internal addition treatment in which the modified body of polyol is added to pulp slurry before papermaking, than that in external addition treatment in which the modified body of polyol is applied to paper after papermaking. In the present disclosure, reduction in dry strength has been found to be prevented by employing a specific composition even when the modified body of polyol is used.

{Wet strength}

The wet strength of the pulp formed article of the present disclosure is not limited, and is evaluated based on the specific wet tensile strength which is measured according to JIS P 8135:0998. The specific wet tensile strength is obtained by dividing the wet tensile strength by the density.
The pulp formed article of the present invention has a wet strength (specific wet tensile strength) of preferably 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, further preferably 5.0 Nm/g or more, and even more preferably 8.0 Nm/g or more, and 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, and for example, 14 Nm/g or less from the viewpoint of ease of manufacture.
Adding the modified body of polyol to the pulp substrate reduces the wet strength of the resulting pulp product. Although the method of addition is not limited, reduction in wet strength is larger in internal addition treatment in which an oil resistant agent is added to pulp slurry before papermaking, than that in external addition treatment in which an oil resistant agent is applied to paper after papermaking. In the present disclosure, reduction in wet strength has been found to be prevented by employing a specific composition even when the modified body of polyol is used.

Examples

Hereinafter, the present disclosure will be described in detail with reference to Examples, but the present disclosure is not limited to these Examples.

The test procedures are as follows.

[Preparation of pulp mold]

Pulp mold was prepared using an automatic mold molding machine. In the lower part thereof, a reticular body was arranged on a pulp mold molding mold made of metal with many suction holes, a metal tank was arranged in the upper part, and the pulp slurry was charged in the upper metal tank. From the opposite side of the pulp mold molding mold to the side where the reticular body was arranged, the pulp-containing aqueous composition was suctioned and dehydrated through the pulp mold molding mold and the reticular body by a vacuum pump at 0.1 to 1 MPa, and solids (pulp, etc.) contained in the pulp-containing aqueous composition were allowed to deposit on the reticular body to obtain a pulp mold intermediate. Next, the resulting pulp mold intermediate was dried by applying pressure of 0.1 to 1 MPa thereto from the tops and bottoms of male and female molding molds made of metal, which have been heated to 60 to 200°C. Thus, a pulp mold formed in the form of a container was produced.

[Oil resistance test at 65°C]

Pulp mold was pre-treated by storing under conditions of 23°C and a humidity of 50% for 12 hours. After pouring 100 ml of corn oil at 65°C into the pulp mold and allowing it to stand at room temperature for 45 minutes, the corn oil was removed from the mold, and the degree of oil staining in the pulp mold was evaluated. The evaluation scores were set as follows according to the degree of staining.

5: No stains inside the pulp mold.
4: Stains inside the pulp mold. No stains on the backside.
3: Stains inside the pulp mold. Slight stain bleed out on the backside.
2: Stains inside the pulp mold. The area of stain bleed out to the backside is less than 50% of the total area.
1: Stains inside the pulp mold. The area of stain bleed out to the backside is 50% or more and less than 100% of the total area.
0: Stains over the backside.

[HD contact angle]

A smooth spin-coated film was prepared by spin-coating a solution (or a dispersion) of the liquid-repellent compound with a solid concentration of 1.0% on a silicon wafer under conditions of 2,500 rpm and 25 seconds. This was heated at 140°C for 1 minute to give a silicon wafer treated with the compound. Chloroform was used as the solvent or the dispersion medium. 2 µL of HD (hexadecane) was dropped on the silicon wafer treated with the compound, and the static contact angle one second after the droplet reached the film was determined as the HD contact angle of the liquid-repellent compound.

[Tensile strength of pulp mold product]

The tensile strength of the pulp mold is not limited, and was evaluated based on the specific tensile strength in the dry condition which is measured according to JIS P 8113:2006. A test piece with a width of 15 mm, a length of 50 mm and a thickness of 0.8 mm, which was cut from the bottom of the pulp mold, was used. The test was performed by Autograph manufactured by Shimadzu Corporation under conditions of a tensile length of 30 mm and a tensile speed of 10 mm/ minute.
The strength per unit area was calculated from the results of the tensile test. [Strength per unit area] = stress at break (N)/ [thickness (mm) * width of test piece (mm)] [Specific tensile strength] = stress at break (N)/ [width of test piece (m) * basis weight (g/m²)]

2 g of decaglycerol dodecabehenyl ester (degree of polymerization: 10, hydroxy group substitution ratio: 12/12*100 [100%], biobased ratio: 100%), which was a modified body of polyol, 0.2 g of polyethylene oxide trimethylnonyl ether (HLB: 13) and 17.8 g of water were mixed to give a precursor of water-dispersible repellent A. The precursor of water-dispersible repellent A was heated to 80°C and then stirred by a homogenizer at 7,000 rpm for 20 minutes to give a water-dispersible repellent. The resulting water-dispersible repellent had a volume abundance ratio of particles with a size of 100 µm or larger of 0% and a median diameter D50 of 19.8 µm.

2 g of decaglycerol heptabehenyl ester (degree of polymerization: 10, hydroxy group substitution ratio: 7/12*100 [58%], biobased ratio: 100%, which was a modified body of polyol, 0.2 g of polyethylene oxide trimethylnonyl ether (HLB: 13) and 17.8 g of water were mixed to give a precursor of water-dispersible repellent A. The precursor of water-dispersible repellent A was heated to 80°C and then stirred by a homogenizer at 7,000 rpm for 20 minutes to give a water-dispersible repellent. The resulting water-dispersible repellent had a volume abundance ratio of particles with a size of 100 µm or larger of 0% and a median diameter D50 of 20.6 µm.

A biodegradation test of decaglycerol dodecabehenyl ester (degree of polymerization: 10, hydroxy group substitution ratio: 12/12*100 [100%], biobased ratio: 100%) was performed according to JIS K 6953-1:2011. The biodegradation as of the 30th day of the test was 36% and the biodegradation as of the 60th day of the test was 62%.

A biodegradation test of decaglycerol heptabehenyl ester (degree of polymerization: 10, hydroxy group substitution ratio: 7/12*100 [58%], biobased ratio: 100%) was performed according to JIS K 6953-1:2011. The biodegradation as of the 30th day of the test was 40% and the biodegradation as of the 60th day of the test was 60%.

The hexadecane contact angle of decaglycerol dodecabehenyl ester (degree of polymerization: 10, hydroxy group substitution ratio: 12/12*100 [100%], biobased ratio: 100%) and decaglycerol heptabehenyl ester (degree of polymerization: 10, hydroxy group substitution ratio: 7/12*100 [58%], biobased ratio: 100%) was measured.

Name of liquid-repellent compound HD contact angle (n-hexadecane) static contact angle/°

Decaglycerol heptabehenyl ester 42.0

Decaglycerol heptabehenyl ester 40.5

The decaglycerol dodecabenenyl ester dispersion of Preparation Example 1 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, and the mixture was stirred for 30 seconds. Then a polyacrylamide-based paper strength agent was added thereto at a ratio of 0.1% relative to the pulp, and the mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

The decaglycerol dodecabenenyl ester dispersion of Preparation Example 1 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, and the mixture was stirred for 30 seconds. Then a polyacrylamide-based paper strength agent was added thereto at a ratio of 0.5% relative to the pulp, and the mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

The decaglycerol dodecabenenyl ester dispersion of Preparation Example 1 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, and the mixture was stirred for 30 seconds. Then a polyacrylamide-based paper strength agent was added thereto at a ratio of 1.1% relative to the pulp, and the mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

The decaglycerol dodecabenenyl ester dispersion of Preparation Example 1 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, and the mixture was stirred for 30 seconds. Then a polyamide-based paper strength agent was added thereto at a ratio of 0.6% relative to the pulp, and the mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

The decaglycerol dodecabenenyl ester dispersion of Preparation Example 1 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, and the mixture was stirred for 30 seconds. Then a polyamide-based paper strength agent was added thereto at a ratio of 0.9% relative to the pulp, and the mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

The decaglycerol heptabenenyl ester dispersion of Preparation Example 2 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, and the mixture was stirred for 30 seconds. Then a polyacrylamide-based paper strength agent was added thereto at a ratio of 1.1% relative to the pulp, and the mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

The decaglycerol heptabenenyl ester dispersion of Preparation Example 2 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, and the mixture was stirred for 30 seconds. Then a polyamide-based paper strength agent was added thereto at a ratio of 0.9% relative to the pulp, and the mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

A sugar fatty acid ester water dispersion (sucrose polysoyate, SEFOSE) was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 7% by weight in terms of solid content, relative to pulp, and the mixture was stirred for 30 seconds. Then a polyacrylamide-based paper strength agent was added thereto at a ratio of 1.1% relative to the pulp, and the mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

The decaglycerol dodecabenenyl ester dispersion of Preparation Example 1 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, without adding the paper strength agent. The mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

The decaglycerol heptabenenyl ester dispersion of Preparation Example 2 was added to pulp slurry with a concentration of 0.5% by weight so that the ratio of the dispersion was 5% by weight in terms of solid content, relative to pulp, without adding the paper strength agent. The mixture was stirred for 30 seconds to give a pulp-containing water-dispersible repellent. The pulp-containing water-dispersible repellent was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results of the tensile test are shown in Table 1.

A pulp mold was prepared without adding the modified body of polyol or the paper strength agent. A pulp slurry with a concentration of 0.5% by weight was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold had a basis weight of 500 g/m². The pulp mold prepared was subjected to the oil-resistance test, which scored 0 points. The results of the tensile test are shown in Table 1.

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

Evaluation Example	Name of liquid-repellent compound	Amount of liquid-repellent compound added (relative to pulp)	Paper strength agent	Amount of paper strength agent added (relative to pulp)	Tensile strength
Evaluation Example	Name of liquid-repellent compound		Paper strength agent	Amount of paper strength agent added (relative to pulp)	Strength per unit area (N/[mm]²)	Specific tensile strength (N/[g/m])
Example 1	Decaglycerol dodecabehenyl ester	5wt%	Polyacrylamide-based paper strength agent	0.1wt%	14.16	22.7
Example 2	Decaglycerol dodecabehenyl ester	5wt%	Polyacrylamide-based paper strength agent	0.5wt%	21.34	34.1
Example 3	Decaglycerol dodecabehenyl ester	5wt%	Polyacrylamide-based paper strength agent	1.1wt%	24.42	39.1
Example 4	Decaglycerol dodecabehenyl ester	5wt%	Polyamide-based paper strength agent	0.6wt%	21.85	35.0
Example 5	Decaglycerol dodecabehenyl ester	5wt%	Polyamide-based paper strength agent	0.9wt%	21.61	34.6
Example 6	Decaglycerol heptabehenyl ester	5wt%	Polyacrylamide-based paper strength agent	1.1wt%	22.48	36.0
Example 7	Decaglycerol heptabehenyl ester	5wt%	Polyamide-based paper strength agent	0.9wt%	21.03	33.6
Example 8	Sucrose polysoyate	7wt%	Polyacrylamide-based paper strength agent	1.1wt%	21.98	35.1
Comparative Example 1	Decaglycerol dodecabehenyl ester	5wt%	-	-	10.12	16.2
Comparative Example 2	Decaglycerol heptabehenyl ester	5wt%	-	-	10.92	17.5
Comparative Example 3	-	-	-	-	17.5	28.0

Claims

A pulp composition comprising a modified body of polyol, a pulp substrate and a paper strength agent, wherein
the paper strength agent is at least one selected from the group consisting of a polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent and a polyamide-based paper strength agent, and

an amount of the modified body of polyol is 0.2 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the pulp substrate.
The pulp composition according to claim 1, wherein the modified body of polyol is a compound formed by modifying polyol with a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or with a monovalent polysiloxane group.
The pulp composition according to claim 1 or 2, wherein the modified body of polyol has an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.
The pulp composition according to any one of claims 1 to 3, wherein the modified body of polyol is a compound formed by replacing one or more hydroxy groups of polyol with a group represented by the following formula:

-Y^O-Z^O _n

wherein Y^O is a 1+n valent group composed of one or more selected from the group consisting of Y^O1 and Y^O2,

Y^O1 is a group composed of one or more selected from the group consisting of 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, for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms,

Y^O2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent,

Z^O is a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms and optionally having a substituent or a monovalent polysiloxane group, and

n is an integer of 1 or more and 3 or less.
The pulp composition according to claim 4, wherein
Y^O is

-O-Y^O11- or

-O-Y^O11-Y^O21-Y⁰¹².

wherein, 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-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO₂-, - SO₂NR'-, -C(OR')R'-, or -C(OR')(-)₂.
The pulp composition according to any one of claims 1 to 5, wherein the polyol is at least one selected from the group consisting of a monosaccharide, an oligosaccharide, a polysaccharide, a sugar alcohol (reducing sugar), a hydroxy acid, an amino acid, vitamin, flavonol, hydroxyhydrocarbon and a polymer of a hydroxy group-containing compound.
The pulp composition according to any one of claims 1 to 6, wherein the polyol is at least one 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;

glycerol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane;

polyglycerol, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer and hydroxybutyl (meth)acrylate polymer.
The pulp composition according to any one of claims 1 to 7, wherein the modified body of polyol has a hexadecane contact angle of 30° or more.
The pulp composition according to any one of claims 1 to 8, wherein the modified body of polyol is a modified body of polygrycerol.
The pulp composition according to claim 9, wherein the modified body of polyglycerol has a hydroxy group substitution ratio of 40% or more.
The pulp composition according to any one of claims 1 to 10, wherein an amount of the paper strength agent is 2 parts by weight or more and 200 parts by weight or less based on 100 parts by weight of the modified body of polyol.
The pulp composition according to any one of claims 1 to 11, wherein
the modified body of polyol is a compound formed by replacing a hydroxy group of monosaccharide or polyglycerol with a group represented by the following formula:

-O-C(=O)-Z^O

wherein Z^O is an aliphatic hydrocarbon group having 14 or more and 24 or less carbon atoms, and

the modified body of polyol has a hydroxy group substitution ratio of 40% or more.
A pulp formed article formed from the pulp composition according to any one of claims 1 to 12.
The pulp formed article according to claim 13, comprising a further modified body of polyol and a further paper strength agent adhered to the surface.
The pulp formed article according to claim 13 or 14, which is for food contact.
A method for producing the pulp composition according to any one of claims 1 to 12, comprising a modified body of polyol -addition of adding the modified body of polyol to the pulp substrate, and a paper strength agent-addition of adding the paper strength agent to the pulp substrate.