Pulp composition

Abstract

To provide a new pulp composition capable of producing a pulp molding having improved strength.SOLUTION: A pulp composition comprises a polyol modified material, 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 polyol modified material is 0.2 pt.mass or over and 30 pts.mass or under relative to 100 pts.mass of the pulp substrate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a pulp composition.

Background Art

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

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Patent Document 1 does not describe or suggest anything about a paper strength agent, nor does it describe or suggest anything about the strength of pulp products.

[0005] An object of the present disclosure is to provide a novel pulp composition capable of producing a pulp molded article with improved strength.

Means for Solving the Problems

[0006] The present disclosure includes the following aspects: [Item 1] A pulp composition comprising a polyol-modified product, a pulp base material, 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 the amount of the polyol-modified product is 0.2 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the pulp base material. [Item 2] The pulp composition according to item 1, wherein the polyol-modified product is a compound obtained by modifying a polyol with a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group. [Item 3] The pulp composition according to item 1 or 2, wherein the polyol-modified product has an aliphatic hydrocarbon group having 6 to 40 carbon atoms which may have a substituent. [Item 4] The polyol-modified product is obtained by substituting one or more hydroxy groups of the polyol with a group represented by the following formula: The following formula: -Y O -Z O n [In the formula, 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, in each occurrence, independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).); Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 2 to 4 carbon atoms, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring; Z O is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group; n is an integer of 1 or more and 3 or less.] The pulp composition according to any one of items 1 to 3, which is a compound substituted with a group represented by the formula. [Item 5] Y Ois -O-Y O11 - or -O-Y O11 -Y O21 -Y O12 - [wherein each symbol is independently in 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; 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'-, -SO 2 -SO 2 NR'-, -C(OR')R'- or -C(OR')(-) 2 .], The pulp composition according to item 4, which is as described above. [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 monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and hydroxy group-containing compound polymers. [Item 7] The polyol is glucose, fructose, galactose, xylose; sucrose, cyclodextrin, 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, isomaltooligosaccharide, gellan gum, tamarind seed gum; Ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; Glucosamine; Ascorbic acid, inositol; Catechin, quercetin, anthocyanin; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; The pulp composition according to any one of items 1 to 6, which is at least one selected from the group consisting of polyglycerin, 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 contact angle of the polyol-modified product with hexadecane is 30° or more. [Item 9] The pulp composition according to any one of items 1 to 8, wherein the polyol-modified product is a polyglycerin-modified product. [Item 10] The pulp composition according to item 9, wherein the substitution rate of the hydroxy group of the polyglycerin-modified product is 40% or more. [Item 11] The pulp composition according to any one of items 1 to 10, wherein the amount of the paper strength agent is 2 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the polyol-modified product. [Item 12] A pulp molded product formed from the pulp composition according to any one of items 1 to 11. [Item 13] The pulp molded product according to item 12, which is formed by adhering a further polyol-modified product and a further paper strength agent to the surface. [Item 14] The pulp molded article according to item 12 or 13, which is for food contact. [Item 15] A method for producing a pulp composition according to any one of items 1 to 11, the method including a polyol modifier addition step of adding the polyol modifier to the pulp base material, and a paper strength agent addition step of adding the paper strength agent to the pulp base material. [Advantages of the Invention]

[0007] According to the present disclosure, a pulp molded article with improved strength can be produced. [Modes for Carrying Out the Invention]

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

[0009] [Definition of Terms] As used in this specification, the "n-valent group" means a group having n bonds, that is, a group forming n bonds. Further, the "n-valent organic group" means an n-valent group containing carbon. Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof. The derivative of the hydrocarbon group means a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen, etc. at the terminal or molecular chain of the hydrocarbon group.

[0010] As used in this specification, the "hydrocarbon group" means a group containing carbon and hydrogen, and is a group obtained by removing a hydrogen atom from a hydrocarbon. Such a hydrocarbon group is not particularly limited, but is C 1-20Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, etc. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. The hydrocarbon group may be substituted with one or more substituents.

[0011] In this specification, regardless of whether or not expressions such as "independently at each occurrence", "independently of each other", "independently respectively" or similar expressions are explicitly described, when a term (symbol) that can appear multiple times in a chemical structure is defined, the definition is applied independently for each occurrence, except when there is a description to the contrary.

[0012] The chemical structures described in this specification should be understood not to include chemical structures that are recognized by those skilled in the art as chemically impossible or extremely unstable.

[0013] <Release agent> The release agent in the present disclosure can adhere to a substrate (particularly a pulp substrate) and impart liquid repellency, such as water resistance, oil resistance, water repellency, oil repellency, and / or antifouling properties to the substrate, and can also function as a water repellent, an oil repellent, a water repellent, an oil repellent, and / or an antifouling agent.

[0014] The release agent of the present disclosure may contain a polyol-modified product as an active ingredient (the polyol-modified product will be described in detail separately in [Polyol-modified product]). The polyol-modified product itself may be used as a release agent, or may be used as a release agent in combination with other components as described below.

[0015] The repellent in the present disclosure may not have any selected from the group consisting of a compound having a fluoroalkyl group with 8 or more carbon atoms, a compound having a perfluoroalkyl group with 8 or more carbon atoms, a compound having a fluoroalkyl group with 4 or more carbon atoms, a compound having a perfluoroalkyl group with 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 in the present disclosure can impart liquid repellency to the substrate even without containing these fluorine compounds.

[0016] The volume occupancy ratio of particles of 100 μm or more measured by the laser diffraction scattering method 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 also 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, preferably 20% or less, particularly less than 10%. The method for setting the volume occupancy ratio of particles of 1 μm or more measured by the laser diffraction scattering method within the above range is not limited. For example, the particles in the raw material and / or the dispersion can be refined using a pulverizer, a homogenizer, or the like.

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

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

[0019] Measure the anion demand of a sample solution with a solid content of 0.1 g / L using a particle charge meter (MUTEK PCD-04 manufactured by BTG) with a 1 / 1000 normal potassium polyvinyl sulfonate solution, and calculate the ionic charge density (cation charge density) from the following formula (1). Alternatively, measure the cation demand in the same manner using a poly(diallyldimethylammonium chloride) solution instead of potassium polyvinyl sulfonate, and calculate the ionic charge density (anion charge density) from the following formula (1). Ionic charge density (μeq / g) = A / B (1) A: Cation demand or anion demand (μeq / L) B: Sample solution concentration (g / L)

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

[0021] [Properties, etc.] The properties, etc. that the polyol-modified product may have are shown below. Such properties, etc. may vary depending on the type of compound.

[0022] The HD (n-hexadecane) contact angle of the polyol-modified product may be 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, preferably 25° or more, more preferably 30° or more, and may also be 100° or less, 90° or less, or 75° or less. By the polyol-modified product having an HD contact angle of the above lower limit or more, good liquid repellency (particularly oil repellency) can be imparted to the substrate. The HD contact angle refers to the static contact angle of the spin-coated film of the polyol-modified product, and is obtained by dropping 2 μL of HD onto the spin-coated film and measuring the contact angle 1 second after droplet landing.

[0023] The water contact angle of the polyol-modified product may be 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and may also be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. By the polyol-modified product having a water contact angle of the above lower limit or more, good liquid repellency (particularly water repellency) can be imparted to the substrate. The water contact angle refers to the static contact angle of the spin-coated film of the polyol-modified product, and is obtained by dropping 2 μL of water onto the spin-coated film and measuring the contact angle 1 second after droplet landing.

[0024] The polyol-modified product is preferably a bio-based compound having carbon of bio-based origin. The bio-based content is measured in accordance with ASTM D6866. The bio-based content may be 20% or more, preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, still more preferably 70% or more, most preferably 80% or more or 90% or more, for example 100%. A high bio-based content means a small amount of use of fossil resource-based materials represented by petroleum and the like. From such a viewpoint, it can be said that the higher the bio-based content of the polyol-modified product, the more preferable.

[0025] The biodegradability of the polyol-modified product at the 180-day time point preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher such biodegradability, the more preferable. The biodegradability of the polyol-modified product at the 180-day time point may be, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 30% or more, more preferably 50% or more, still more preferably 70% or more, and most preferably 80% or more. The biodegradability of the polyol-modified product at the 60-day time point preferably has a biodegradability of 5% or more. Since the environmental load is reduced, the higher such biodegradability, the more preferable. The biodegradability of the polyol-modified product at the 60-day time point may be, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, preferably 10% or more, more preferably 30% or more. Such biodegradability may be the biodegradability defined in JIS K 6953-1 or ASTM D6400.

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

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

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

[0029] (A monovalent hydrocarbon group which may have a substituent) The polyol modifier may have a monovalent hydrocarbon group which may have a substituent.

[0030] The hydrocarbon group may be a monovalent hydrocarbon group having 1 to 40 carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and an aliphatic hydrocarbon group is preferred. For example, it may be an alkenyl group or an alkyl group having 1 to 3 double bonds. The hydrocarbon group may be branched, cyclic or linear, and more preferably linear.

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

[0032] The hydrocarbon group may have a substituent, but is preferably unsubstituted. Examples of the substituent include -OR’, -N(R’) 2, -COOR’, and halogen atoms, etc. (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) may be mentioned. The substituent may or may not have an 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 atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. For example, the hydrocarbon group may have 1 to 3 (for example, 1) -OR’ (especially -OH) as a substituent (for example, other than at the terminal).

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

[0034] The polysiloxane group has the following formula: -[-Si(R s ) 2 -O-] a - [wherein, R s is, independently at each occurrence, a hydrocarbon group having 1 to 40 carbon atoms or a reactive group, a is an integer of 5 or more and 10000 or less.] It may also be represented by

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

[0036] Examples of the hydrocarbon group 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.

[0037] Examples of hydrocarbon groups having 1 to 5 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, etc. (especially aliphatic hydrocarbon groups, especially alkyl groups, such as methyl group or ethyl group, especially methyl group).

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

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

[0040] a may be 3 or more, 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more, preferably 10 or more, and may also be 10000 or less, 7500 or less, 5000 or less, 3000 or less, 1500 or less, 1000 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less, preferably 500 or less.

[0041] In the polysiloxane group, R is a hydrocarbon group having 1 to 5 carbon atoms s The amount of s may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, preferably 50 mol% or more, based on the total of R s and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less. For example, 50 mol% or more of the total of R

[0042] In the polysiloxane group, R is a hydrocarbon group having 6 to 40 carbon atoms s The amount of s may be 3 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% or more, and may also be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, based on the total of R

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

[0044] The R s group may be introduced randomly or in blocks, but is preferably random.

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

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

[0047] Examples of the polysiloxane group 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、 -L s1 -[-Si(R s ) 2 -O-] a -R s [wherein, R s is, independently at each occurrence, a hydrocarbon group or a reactive group having 1 to 40 carbon atoms, and the terminal R s has one or more reactive groups, R s in the total of the R groups, 50 mol% or more is a methyl group, L s1 is a hydrocarbon group having 1 to 20 carbon atoms, a is 5 or more and 10,000 or less. ], JPEG2025083906000001.jpg2169[wherein, a represents an integer of 0 to 150, b represents an integer of 1 to 150, (a + b) is 5 to 200, and n is an integer of 0 to 36. ]

[0048] [Structure, etc. of the polyol-modified product] As an example of the polyol-modified product, a compound having a monovalent hydrocarbon group having 1 or more and 40 or less carbon atoms which may have a substituent or a monovalent polysiloxane group (for example, 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) can be mentioned. Examples and preferred ranges of the hydrocarbon group are as described above.

[0049] The polyol-modified product may contain an ester group, an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfonurea group, a sulfonurethane group, or a sulfonimide group (for example, an ester group, an amide group, a urethane group, a urea group, an imide group). For example, the polyol-modified product is -C(=O)-O-, -O-C(=O)-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO2 It may contain NR’- (wherein R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms)). The polyol modified product may be a compound in which a raw material compound and a modifying group (particularly a monovalent hydrocarbon group which may have the above-described substituent) are bonded via at least one of these groups. The polyol modified product may contain an amide structure. By the polyol modified product containing at least an amide structure, the liquid repellency can be improved. Here, the amide structure may be an amide structure in a broad sense, and may be selected from amide structures 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 sulfonamide group, a sulfourethane group, a sulfourea group, a sulfonimide group, etc. The amide structure may be - (C = O) N (-) 2 , - (C = S) N (-) 2 , and - S(=O) 2 N (-) 2 (wherein each group may be in a direction reversed left and right), and may be an amide structure selected from the group consisting of. Here, at least one of the bonds possessed by N of the amide structure may be bonded to a hydrogen atom. The amide structure is preferably - (C = O) N (-) 2 and may be an amide structure in a group selected from the group consisting of an amide group, a urethane group, a urea group, and an imide group.

[0050] The polyol modified product may be a compound obtained by chemically modifying a polyol so as to exhibit liquid repellency. The polyol modified product may be a polymer having a polymerization degree of 1 or more. From the viewpoint of improving liquid repellency, the polymerization degree of the polyol modified product may be 2 or more, may be 3 or more, may be 5 or more, may be 6 or more, preferably 7 or more, more preferably 8 or more, still more preferably 9 or more, and from the viewpoint of improving the handleability of the liquid repellent, it may be 100 or less, preferably 50 or less, more preferably 30 or less, still more preferably 15 or less. Here, the polymerization degree means the number of repeating monomer units constituting the polymer.

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

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

[0053] When the polyol-modified product in the present disclosure is a polysaccharide-modified product obtained by modifying a polysaccharide, the degree of polymerization of the polyol-modified product means the average degree of polymerization of the above polysaccharide. The analysis of the average degree of polymerization of the polysaccharide can be carried out as follows. Incidentally, the degree of polymerization is the number of monosaccharide units (fructose and glucose units) in the polysaccharide, and the average degree of polymerization is, for example, the top of the peaks of the respective analysis results obtained by ordinary analytical methods such as HPLC, GC, and HPAEC as follows. As the column, for example, ULTRON PS-80N (8 × 300 mm) manufactured by Shinwa Chemical Industries Co., Ltd. (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) or TSK-GEL G30000 PWXL (7.8 × 300 mm) manufactured by TOSOH Corporation (solvent: water, flow rate: 0.5 ml / min, temperature: 50°C) is used, and it can be measured by using a differential refractometer as a detector.

[0054] The polyol-modified product may be low molecular weight (for example, weight average molecular weight less than 1500, less than 1000, 500 or less) and / or high molecular weight. The weight average molecular weight of the polyol-modified product may be 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

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

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

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

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

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

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

[0061] (-Y O -Z O n ) In the polyol-modified product in the present disclosure, one or more hydroxy groups of the polyol are 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 direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O) 2 -, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-) 2, and -N(-) 2 (wherein, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and is a group composed of one or more selected from the group consisting of) Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences. Z O is an optionally substituted monovalent hydrocarbon group having 1 to 40 carbon atoms or a monovalent polysiloxane group. n is an integer of 1 or more and 3 or less.] may be substituted by a group represented by

[0062] (Y 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 direct bond, -O-, -C(=O)-, -C(=NR’)-, -S-, -S(=O) 2 -, -C(=S)-, -NR’-, -C(OR’)R’-, -C(OR’)(-) 2 , and -N(-) 2 (wherein, R’ is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms), and is a group composed of one or more selected from the group consisting of) Y O2 is a group composed of one or more selected from the group consisting of an optionally substituted aliphatic hydrocarbon group having 1 to 40 carbon atoms and 2 to 4 valences, an optionally substituted hydrocarbon aromatic ring, and an optionally substituted heterocyclic ring having 2 to 4 valences.

[0063] n is Z O bonded to Y Ois a number and can be an integer from 1 to 3. n can be 1 or more, 2 or more, or 3 or more, and can also be 3 or less, 2 or less, or 1 or less, for example, 2 or less.

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

[0065] Y O may contain at least an amide group, urethane group, urea group, imide group, thioamide group, thiourethane group, thiourea group, thioimide group, sulfonamide group, sulfourea group, sulfourethane group, or sulfonimide group. For example, Y O may contain -C(=O)-NR’-, -C(=S)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO 2 NR’-. By Y O containing these groups, the liquid repellency can be improved.

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

[0067] Y O1 is a direct bond or a polyvalent group. Y O1 The valence of may be 2 to 4, 2 to 3, or 2. Y O1 Preferably, it is not only a direct bond.

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

[0069] YO1 is composed of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -S(=O) 2 -, -NR’-, -C(OR’)R’-, and -C(OR’)(-) 2 (wherein, R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).). Y O1 Examples of Y 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’-, -SO 2 -, -SO 2 NR’-, -C(OR’)R’-, -C(OR’)(-) 2 etc (wherein, R’ is independently, in each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 4 carbon atoms).) are included.

[0070] Y O1 may contain at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfonamide group, a sulfourea group, a sulfourethane group, or a sulfonimide group. For example, Y O2 is -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO 2 NR’-. Y O1By containing these groups, the liquid repellency can be improved.

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

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

[0073] Y O2 Y is a group with a valence of two or more. O2 The valence of Y may be, for example, 2 to 4, 2 to 3, or 2.

[0074] Y O2 The carbon number of Y may be 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 may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0075] Y O2 Y is composed of one or more selected from the group consisting of a 2- to 4-valent aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a 2- to 4-valent hydrocarbon aromatic ring which may have a substituent, and a 2- to 4-valent heterocycle which may have a substituent.

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

[0077] The aliphatic hydrocarbon group may have a substituent. Examples of the substituent include -OR’, -N(R’) 2 , -COOR’, and a halogen atom, etc. (wherein, R’ is independently, in 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 an 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 atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0078] Examples of the hydrocarbon aromatic ring having a valence of 2 to 4 include groups obtained by removing 2 to 4 hydrogens 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, preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may also be 4 or less, 3 or less, or 2.

[0079] The hydrocarbon aromatic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’)2 , -COOR’, and halogen atoms, etc. (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) can be mentioned. The substituent may or may not have an 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 atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

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

[0081] The heterocyclic ring may have a substituent. Examples of the substituent include -R’, -OR’, -N(R’) 2, -COOR’, and halogen atoms, etc. (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) can be mentioned. The substituents 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 heterocycle having substituents, the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, for example 65 mol% or more, and may also be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

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

[0083] Y O2 Specific examples of -(CH 2 ) p -(p is 1 to 40, 1 to 20, or 1 to 10), A linear hydrocarbon group having unsaturated bonds with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, A hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH 2 ) q -Cy-(CH 2 ) 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) etc. are exemplified.

[0084] (Examples of Y O ) Examples of Y O are described. In the following, R’ is, in each occurrence, independently 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.

[0085] Examples of Y O when Y O is divalent 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 -, -Y O2 -Y O1 -Y O2 -Y O1 - etc. are exemplified.

[0086] Examples of Y O when Y O is trivalent 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 -YO1 -(Y O2 -Y O1 -) 2、 -Y O2 -(Y O1 -Y O2 -Y O1 -) 2 include the following.

[0087] Y O Examples of Y O when Y is tetravalent, -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 O2 -) 3、 -Y O1 -Y O2 -(Y O1 -Y O2 -) 3、 -Y O1 -(Y O2 -Y O1 -Y O2 -) 3 ; -Y O2 (-) 3 、-Y O2 -Y O1 (-) 3 、-Y O2 -(Y O1 -) 3 、-Y O2 -YO1 -Y O2 (-) 3 、-Y O2 -Y O1 (-Y O2 -) 3 、-Y O2 -(Y O1 -Y O2 -) 3 、-Y O2 -Y O1 -Y O2 -Y O1 (-) 3 、-Y O2 -Y O1 -Y O2 -(Y O1 -) 3、 -Y O2 -Y O1 -(Y O2 -Y O1 -) 3、 -Y O2 -(Y O1 -Y O2 -Y O1 -) 3 ; etc. can be mentioned.

[0088] Y O Preferred examples of -Y O1 -、-Y O1 -Y O2 -、-Y O1 -Y O2 -Y O1 -、-Y O1 -Y O2 (-) 2 、 -Y O2 -、-Y O2 -Y O1 -、-Y O2 -Y O1 -Y O2 -、-Y O2 -Y O1 (-) 2 、 etc. can be mentioned.

[0089] (Preferred Y O example) Preferably, Y O is -O-Y O11- or -O-Y O11 -Y O21 -Y O12 - [In the formula, each symbol is independent 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; 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'-, -SO 2 -, -SO 2 NR'-, -C(OR')R'- or -C(OR')(-) 2 .], may be.

[0090] Y O11 is a non-hydrocarbon linker, a direct bond or a polyvalent group.

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

[0092] Y O11 may be a direct bond, -C(=O)-, -C(=O)-NR'- or -C(=S)-NR'-;

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

[0094] Y O21The number of carbon atoms may be 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 may also be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

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

[0096] Y O21 Specific examples of -(CH 2 ) p -(where p is 1 to 40, 1 to 20, or 1 to 10), a linear hydrocarbon group having an unsaturated bond with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, a hydrocarbon group having a branched structure with 1 to 40, 1 to 20, or 1 to 10 carbon atoms, -(CH 2 ) q -Cy-(CH 2 ) r -(where 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) and the like can be mentioned.

[0097] 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’-, -SO 2 -, -SO 2 NR’-, -C(OR’)R’-, or -C(OR’)(-) 2 and may be so.

[0098] Y O12may contain at least an amide group, urethane group, urea group, imide group, thioamide group, thiourethane group, thiourea group, thioimide group, sulfonamide group, sulfourea group, sulfourethane group, or sulfonimide group. For example, Y O12 may be -C(=O)-NR’-, -O-C(=O)-NR’-, -NR’-C(=O)-, -NR’-C(=O)-NR’- or -SO 2 NR’-. Y C12 By containing these groups, the liquid repellency can be improved.

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

[0100] (Other modifying groups) The hydroxy group of the polyol may be substituted with a modifying group other than -Y O -Z O n Examples of the modifying group are an anionic group and / or a cationic group.

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

[0102] Examples of the salt of the anionic group include an alkali metal salt, an alkaline earth metal salt, or an ammonium salt, such as a methylammonium salt, an ethanolammonium salt, a triethanolammonium salt and the like.

[0103] Examples of the cationic group include an amino group, preferably a tertiary amino group and a quaternary amino group. In the tertiary amino group, two groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group) or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, such as a benzyl group (C6 H 5 -CH 2 -)) is preferably. In the quaternary amino group, the three groups bonded to the nitrogen atom are the same or different and are an aliphatic group having 1 to 5 carbon atoms (especially an alkyl group), an aromatic group having 6 to 20 carbon atoms (aryl group), or an araliphatic group having 7 to 25 carbon atoms (especially an aralkyl group, for example, a benzyl group (C 6 H 5 -CH 2 -)) is preferably. In the tertiary amino group and the quaternary amino group, the remaining one group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of a salt.

[0104] The cationic group which is a salt is a salt with an acid (organic acid or inorganic acid). Organic acids, for example, carboxylic acids having 1 to 20 carbon atoms (especially monocarboxylic acids such as acetic acid, propionic acid, butyric acid, stearic acid, etc.) are preferred.

[0105] [Method for producing polyol modified product] The polyol modified product may be produced by reacting a modifier having a modifying group (or a precursor structure of the modifying group) with the hydroxy group of the polyol.

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

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

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

[0109] The polyol may be a low molecular weight (for example, weight average molecular weight less than 1000, 500 or less) and / or a high molecular weight. The weight average molecular weight of the polyol may be 50 or more, 100 or more, 300 or more, 500 or more, 1000 or more, 3000 or more, 5000 or more, 10000 or more, 30000 or more, 100000 or more, 300000 or more, or 500000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 300000 or less, 100000 or less, 75000 or less, 50000 or less, 30000 or less, 10000 or less, 5000 or less, 3000 or less, 2000 or less, 1000 or less, or 500 or less.

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

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

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

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

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

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

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

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

[0118] Examples of amino acids include glucosamine, etc.

[0119] Examples of vitamins include ascorbic acid, inositol, etc.

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

[0121] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerin, trimethylolpropane, trimethylolethane, and the like. Hydroxyhydrocarbon is a hydrocarbon having a hydroxy group, which may be aromatic or aliphatic, but is preferably aliphatic. When referring to hydroxyhydrocarbon, it may mean hydroxyhydrocarbons other than compounds included in other groups such as polysaccharides (other hydroxyhydrocarbons).

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

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

[0124] Examples of polymer polyols are compounds obtained by polymerizing at least a part of the polyether polyol with an ethylenically unsaturated monomer in the polyether polyol. Examples of the ethylenically unsaturated monomer include acrylonitrile and styrene.

[0125] Examples of the polyester polyol may be compounds obtained by dehydrative condensation of a compound having a carboxyl group with two or more functional groups and a compound having a hydroxyl group with two or more functional groups. Examples of the compound having a carboxyl group with two or more functional groups include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, and acid anhydrides thereof. Examples of the compound having a hydroxyl group with two or more functional groups include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and polymers thereof.

[0126] (Modifier) The modifier is a compound having reactivity with the polyol, and is preferably a compound having a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a monovalent polysiloxane group as described above.

[0127] Examples of the modifier 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 Thiocyanate S=C=N-Z O Epoxy (CH 2 OCH)CH 2 O-Z O Halide G-Z O Amine H 2 N-Z O Hydroxy HO-Z O [In the formula, Z Ois as described above, and G is a halogen atom (for example, F, Cl, Br, or I).

[0128] Z in the structure of the above-mentioned modifier O may be replaced with any group constituting the modifying group. For example, Z O may be a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a group having a monovalent polysiloxane group. For example, Z O may be -Y O -Z O n and the like.

[0129] The polyol modifier may be synthesized by reacting a polyol with a modifier. For example, a modifier which is an acid halide compound, an acid anhydride, or a carboxylic acid is reacted with a hydroxy group of a polyol to form an ester bond, thereby synthesizing a polyol modifier. Further, a modifier which is a halide or an epoxy compound is reacted with a hydroxy group of a polyol to form an ether bond, thereby generating a polyol modifier. A person skilled in the art can appropriately design the reaction conditions between the polyol and the modifier, such as the use of a catalyst (for example, an acid catalyst or a base catalyst) and the use of a condensing agent, according to the target product.

[0130] [Amount of polyol modifier] The amount of the polyol modifier 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 in the repellent, and may also be 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. The polyol modifier alone may be used as the repellent.

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

[0132] The dispersant may use each of an organic dispersant and an inorganic dispersant, or may be a combination of an organic dispersant and an inorganic dispersant.

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

[0134] The dispersant may be non-fluorine.

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

[0136] The nonionic dispersant may be a low molecular weight type or a high molecular weight type. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0137] Examples of the nonionic dispersant include ether, ester, ester ether, alkanolamide, polyol, and amine oxide.

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

[0139] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols having 1 to 30 valences (particularly 2 to 10 valences) and 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0140] Examples of ester ethers are compounds obtained by adding an alkylene oxide (particularly ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols having 1 to 30 valences (particularly 2 to 10 valences) and 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0141] Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamine. Examples of 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 having 1 to 3 amino groups and 1 to 5 hydroxyl groups and 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0142] The polyol may be an alcohol having 2 to 5 valences and 10 to 30 carbon atoms. The amine oxide may be an oxide of an amine (secondary amine or preferably tertiary amine) (for example having 5 to 50 carbon atoms).

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

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

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

[0146] The nonionic dispersant has the formula: R 1 O-(CH 2 CH 2 O) p -(R 2 O) q -R 3 [wherein, R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group, R 2 each of which is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R 3is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, q is 0 or a number of 1 or more.] It may be a compound represented by

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

[0148] Specific examples of the nonionic dispersant include ethylene oxide and hexylphenol, isooctylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiol, sorbitan monofatty acid (C 7 -C 19 ) or alkyl (C 12 -C 18)Condensation products with amines, etc., sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters, lecithin derivatives, etc. are included. Examples of nonionic dispersants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxybutylene alkyl ethers, polyoxyethylene polyoxypropylene glycols, polyethyleneimine ethoxylates, etc.

[0149] 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 the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000. The nonionic dispersant may be a single kind or a mixture of two or more kinds. The nonionic dispersant may be a mixture of a compound having an HLB (hydrophilic-lipophilic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. Specifically, it is preferably selected from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene having an HLB of 1 to 18, and sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters having an HLB value of less than 7.

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

[0151] The cationic dispersant may be of low molecular weight (for example, with a molecular weight of 2000 or less, particularly 1000 or less), or may be of high molecular weight (for example, with a molecular weight of 2000 or more). The molecular weight of the cationic dispersant may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 1000000 or less, 750000 or less, 500000 or less, 250000 or less, 100000 or less, 50000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0152] The cationic dispersant may be aliphatic or aromatic, and examples include ammonium salts (such as quaternary ammonium salts). The cationic dispersant may be an oxyethylene-added type ammonium salt. Specifically, amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, benzethonium chloride, etc.; high molecular weight cationic dispersants such as polyquaternium-1 to 47, etc. Examples of the cationic dispersant include alkylamine salts, quaternary ammonium salts, etc.

[0153] The low molecular weight cationic dispersant is R 21 -N + (-R 22 )(-R 23 )(-R 24 )X - [In the formula, R 21 , R 22 , R 23 and R 24 are hydrogen, or a hydrocarbon group having 1 to 40 carbon atoms, X is an anionic group. ] It may be a compound represented by. R 21 , R 22 , R23 and -R 24 Specific examples of these include alkyl groups (e.g., methyl group, butyl group, stearyl group, palmitoyl group), aromatic groups (e.g., benzyl group, phenyl group), etc. Specific examples of X include halogen (e.g., chlorine), acids (e.g., hydrochloric acid, acetic acid). Examples of cationic dispersants include monoalkyltrimethylammonium salts (alkyl having 4 to 40 carbon atoms), benzalkonium chloride, and the like.

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

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

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

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

[0158] The anionic dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0159] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfonated fatty acid salts, N-acyl amino acid type dispersants, phosphoric acid mono- or diester type dispersants, and sulfosuccinic acid esters. As an example of an anionic dispersant, carboxylates (e.g., fatty acid salts) and the like can be mentioned.

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

[0161] The amphoteric dispersant may be of low molecular weight or high molecular weight. The molecular weight may be 100 or more, 500 or more, 1000 or more, 2000 or more, 4000 or more, or 6000 or more, and may also be 100000 or less, 10000 or less, 7500 or less, 5000 or less, 2500 or less, 1000 or less, 750 or less, or 250 or less.

[0162] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, betaine acetates, etc. Specifically, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetate betaine, fatty acid amide propyl dimethylaminoacetate betaine, etc. can be mentioned.

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

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

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

[0166] [Amount of dispersant] The amount of the dispersant may be 0.01 part by weight or more, 0.1 part 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, based on 100 parts by weight of the polyol-modified product, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

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

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

[0169] [Amount of liquid medium] The amount of the liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 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 1000 parts by weight or more with respect to 1 part by weight of the polyol-modified body, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

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

[0171] 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 1000 parts by weight or more with respect to 1 part by weight of the polyol-modified product, and may also be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0172] [Silicone] The water repellent agent in the present disclosure may contain silicone (polyorganosiloxane). By containing silicone, in addition to good water repellency, it can also have good texture and durability.

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

[0174] The weight average molecular weight of the silicone may be 1000 or more, 10000 or more, or 50000 or more, and may also be 500000 or less, 2500000 or less, 100000 or less, or 50000 or less.

[0175] [Amount of silicone] The amount of silicone may be 0.1 part 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 with respect to 100 parts by weight of the polyol modifier, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

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

[0177] [Amount of organic acid] The amount of organic acid may be 0.1 part 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 with respect to 100 parts by weight of the polyol modifier, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that the pH of the water repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. The water repellent may be acidic (pH 7 or less, for example 6 or less).

[0178] [Inorganic acid] The release agent of the present disclosure may contain an inorganic acid. Known inorganic acids can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid, and phosphoric acid. In the present disclosure, one kind of inorganic acid may be used, or two or more kinds may be used in combination. By adding an inorganic acid, the stability of the aqueous dispersion can be improved.

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

[0180] [Curing agent] The release agent of the present disclosure may contain a curing agent (active hydrogen-reactive compound or active hydrogen-containing compound).

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

[0182] The hardener 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 acts as a crosslinking agent. Examples of the polyisocyanate compound include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, it may be a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which the isocyanate group of the isocyanate compound is masked with a blocking agent to suppress the reaction.

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

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

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

[0186] Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of aromatic polyisocyanates are 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 and the like. These may be used alone or in combination of two or more.

[0187] Derivatives of polyisocyanates include, for example, various derivatives such as dimers, trimers, biurets, allophanates, carbodiimides, uretdiones, uretoimines, isocyanurates, iminooxadiazinediones, etc. of the above-mentioned polyisocyanate compounds. These may be used alone or in combination of two or more.

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

[0189] The blocking agent blocks the free isocyanate groups. The blocked polyisocyanate compound can regenerate the isocyanate groups and easily react with hydroxyl groups, for example, by heating to 100 °C or higher, for example, 130 °C or higher. Examples of the blocking agent are phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, etc. The polyisocyanate compound can be used alone or in combination of two or more.

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

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

[0192] [Amount of curing agent] The amount of the curing agent may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, 5 part by weight or more, 10 part by weight or more, 15 part by weight or more, or 20 part by weight or more, 50 part by weight or more, 75 part by weight or more, or 100 part by weight or more, based on 100 parts by weight of the polyol-modified product. Also, it may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0193] [Other components] The sizing agent may contain other components in addition to the above components. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield improvers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, fragrances, and the like. These may be used alone or in combination of two or more. In addition to the above components, as other components, other water and / or oil repellents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, anti-wrinkle agents, drying rate adjusters, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity adjusters, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage preventers, anti-wrinkle agents for washing, shape retainers, drape retainers, ironing property improvers, brightening agents, whitening agents, fabric softening clay, migration preventers such as polyvinylpyrrolidone, polymer dispersants, soil release agents, scum dispersants, fluorescent brightening agents such as 4,4-bis(2-sulfostyryl)biphenyl disodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, enzymes such as cellulase, amylase, protease, lipase, keratinase, etc. as fiber surface modifiers, defoaming agents, silk powders, surface-modified products thereof or emulsion dispersions (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (Kamo), Silkgen G Soluble S (Ichimaru Pharcos)) that can impart silk-like texture and functions such as moisture absorption and release, and anti-pollution agents (e.g., nonionic polymer compounds composed of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Gohou Chemical Industry Co., Ltd.), SRC-1 manufactured by Clariant Japan, etc.). These may be used alone or in combination of two or more.

[0194] [Amount of other components] The amount of each or the total amount of other components may be 0.1 part 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 with respect to 100 parts by weight of the polyol-modified product, and may also be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

[0195] <Pulp composition> The pulp composition in the present disclosure includes a polyol-modified product and a pulp base material. The pulp composition in the present disclosure can be excellent in oil resistance and / or water resistance, preferably both.

[0196] The pulp composition in the present disclosure is obtained by adding a polyol-modified product to a pulp base material. The pulp composition may be obtained by treating the pulp base material with a water-repellent agent containing a polyol-modified product, where the addition amount and composition of the water-repellent agent may be adjusted so that each component has a desired amount. Each component that can be included in the water-repellent agent may be added to the pulp composition as a separate additive.

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

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

[0199] 〔Pulp base material〕 The pulp composition contains a pulp base material. The pulp base material is composed of pulp, and the pulp may be wood pulp, non-wood pulp, wastepaper pulp, etc.

[0200] [Wood pulp] Examples of wood pulp include softwood kraft pulp obtained from Pinus, Larix, etc., and hardwood kraft pulp obtained from Acacia, Eucalyptus, Fagus, Populus (e.g., poplar), etc. Examples of softwood kraft pulp include, for example, unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), softwood sulfite pulp, etc. Also, examples of hardwood kraft pulp include, for example, unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), hardwood sulfite pulp, etc. Note that the pulp used is used alone or in combination. In addition to kraft pulp, in addition to softwood kraft pulp and hardwood kraft pulp, there are also mechanical pulps such as stone ground pulp (SGP), pressure ground pulp (PGW), refiner ground pulp (RGP), thermomechanical pulp (TGP), chemiground pulp (CGP), groundwood pulp (GP), thermomechanical pulp (TMP), etc. Furthermore, examples of wastepaper pulp include deinked wastepaper pulp, deinked and defibered wastepaper pulp, or deinked, defibered, and bleached wastepaper pulp produced from tea wastepaper, kraft envelope wastepaper, magazine wastepaper, newspaper wastepaper, flyer wastepaper, office wastepaper, cardboard wastepaper, high-quality wastepaper, Kent wastepaper, imitation wastepaper, deed wastepaper, etc.

[0201] Examples of non-wood pulp include pulp obtained from bagasse, kenaf, bamboo, linters, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, sisal hemp, jute, flax, ganpi, Mitsumata, kozo, etc.

[0202] The average fiber length of the pulp is preferably 0.1 mm or more, more preferably 0.3 mm or more, still more preferably 0.5 mm or more, from the viewpoint of improving oil resistance, and preferably 5.0 mm or less, more preferably 4.0 mm or less, still more 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 production.

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

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

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

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

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

[0208] [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 in the pulp composition, and may also be 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. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium is 50% by weight or more, particularly 90% by weight or more in the pulp composition, and when the pulp composition is prepared by external addition, the amount of the liquid medium is 30% by weight or less, particularly 10% by weight or less in the pulp composition.

[0209] [Polyol modifier] The pulp composition may contain a polyol modifier (particularly, the polyol modifier contained in the sizing agent). The sizing agent will be described in detail separately in <Sizing agent>.

[0210] [Amount of polyol modifier] The amount of the polyol-modified product may be 0.1 part by weight or more, 0.3 part by weight or more, 0.5 part by weight or more, 0.75 part 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, based on 100 parts by weight of the pulp base material. Also, it may be 20 parts by weight or less, 10 parts by weight or less, 7.5 parts by weight or less, 5.0 parts by weight or less, 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, 1.0 part by weight or less, 0.75 part by weight or less, or 0.5 part by weight or less, preferably 5.0 parts by weight or less, more preferably 3.0 parts by weight or less. The addition amount of the sizing agent added to the pulp base material may be adjusted so that the polyol-modified product reaches the desired amount.

[0211] In the external addition treatment, the amount of the polyol-modified product contained in the coating layer is 0.01 g / m 2 or more, 0.03 g / m 2 or more, 0.05 g / m 2 or more, 0.1 g / m 2 or more, 0.3 g / m 2 or more, 0.5 g / m 2 or more, or 1.0 g / m 2 or more, and may be 5.0 g / m 2 or less, 4.0 g / m 2 or less, 3.0 g / m 2 or less, 2.0 g / m 2 or less, 1.0 g / m 2 or less, 0.5 g / m 2 or less, 0.3 g / m 2 or less, or 0.1 g / m 2 or less.

[0212] 〔Paper strength agent〕 The pulp composition may contain a paper strength agent. Examples of the paper strength agent include Polyacrylamide-based paper strength agents such as cationic polyacrylamide, anionic polyacrylamide, and amphoteric polyacrylamide; Starch, enzyme-modified starch, thermo-chemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch, etc.), aldehyde-modified starch, cationized starch, starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, chitin nanofiber, cellulose nanofiber, and pullulan, polysaccharide sizing agents such as these modified polysaccharides (e.g., modified polysaccharides into which hydroxyl groups or cationic groups are introduced), etc.; Polyamide sizing agents such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epichlorohydrin resin, polyamide-polyamine-epichlorohydrin resin, polyamide-polyurea-formaldehyde resin, epoxidized polyamide resin, etc.; Urea / melamine sizing agents such as urea resin, melamine resin, urea-formaldehyde resin, melamine-formaldehyde resin, etc.; Polyvinyl alcohol sizing agents such as polyvinyl alcohol, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol, etc.; Styrene-butadiene copolymer, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylate ester, fatty acid diamide, polyethyleneimine resin, ketone aldehyde resin, etc. are mentioned. As the sizing agent in the present disclosure, polyacrylamide sizing agent, polysaccharide sizing agent, or polyamide sizing agent is preferable.

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

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

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

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

[0217] The amount of 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, preferably 2 parts by weight or more, based on 100 parts by weight of the polyol-modified product. Also, it may be 500 parts by weight or less, 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, or 50 parts by weight or less, preferably 200 parts by weight or less.

[0218] [Other Additives] In addition to the above, the pulp composition may contain additives used in the production of pulp products, such as fixing agents (such as aluminum sulfate), organic acids (such as formic acid and acetic acid), coagulants / flocculants, yield improvers, dyes, fluorescent dyes, slime control agents, and defoaming agents. The pulp composition contains components derived from the sizing agent, but each component that can be contained in the above-mentioned sizing agent may be separately added to the pulp composition as an additive. The pulp composition may not contain a coloring agent (for example, a dye).

[0219] [Amount of Other Additives] The amount of each other additive may be 0.1 part by weight or more, 1 part by weight or more, 3 part by weight or more, or 5 part by weight or more, based on 100 parts by weight of the pulp base material. Also, it may be 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less, based on the pulp base material.

[0220] The amount of each other additive may be 0.5 part by weight or more, 1 part by weight or more, 2 parts by weight or more, 3 parts by weight or more, 5 parts by weight or more, 7.5 parts by weight or more, 15 parts by weight or more, or 25 parts by weight or more, preferably 2 parts by weight or more, based on 100 parts by weight of the polyol-modified product. Also, it may be 500 parts by weight or less, 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, or 50 parts by weight or less, preferably 200 parts by weight or less.

[0221] <Method for Producing Pulp Product>

[0222] The pulp composition in the present disclosure can be obtained by treating a pulp substrate with a water-repellent agent containing a polyol-modified product.

[0223] If necessary, the obtained pulp composition can be subjected to treatment steps such as drying, heating, and shaping to obtain a pulp product.

[0224] The method for manufacturing a pulp product in the present disclosure may include a step of treating a pulp substrate with a water-repellent agent (a polyol-modified product addition step). The pulp substrate is treated with a water-repellent agent to obtain a pulp composition. A pulp composition may be manufactured by a polyol-modified product addition step of adding a polyol-modified product to the pulp substrate and a sizing agent addition step of adding a sizing agent to the pulp substrate. The polyol-modified product addition step and the sizing agent addition step may be performed separately or simultaneously. If necessary, the obtained pulp composition can be subjected to treatment steps such as drying, heating, and shaping to obtain a pulp product.

[0225] Regarding the type and composition of the pulp substrate and the water-repellent agent, the description of the above-mentioned "pulp composition" is incorporated by reference. The water-repellent agent of the present disclosure can be applied to the substrate by a conventionally known method as a treatment agent (especially a surface treatment agent). As a treatment method, the water-repellent agent in the present disclosure can be dispersed and diluted in an organic solvent or water if necessary, and attached to the inside and / or surface of the pulp substrate by a known method such as dip coating, spray coating, or foam coating, and then dried. After drying, a pulp product with the solid component in the water-repellent agent attached is obtained. Also, if necessary, it may be applied together with a suitable cross-linking agent and cured. The concentration of the water-repellent agent in the treatment agent in contact with the pulp substrate may be appropriately changed depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0226] The sizing agent in the present disclosure can be applied to a pulp substrate by a conventionally known method as a treating agent (especially a surface treating agent). As a treating method, the sizing agent in the present disclosure can be dispersed and diluted in an organic solvent or water if necessary, and then adhered to the inside and / or surface of the pulp substrate by a known method such as dip coating, spray coating, foam coating, etc., and dried. The dilution ratio may be appropriately changed depending on the concentration and use of the sizing agent, but may be 3 to 2000 times, for example, 10 to 100 times. After drying, a pulp product with the solid component of the sizing agent adhered thereto is obtained. Further, if necessary, it may be applied together with a suitable crosslinking agent and cured.

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

[0228] As a method for treating a pulp substrate, an internal addition treatment method in which a sizing agent is added to pulp before papermaking (for example, pulp slurry), or an external addition treatment method in which a sizing agent is applied to pulp after papermaking (for example, a pulp product) can be used. Examples of the internal addition treatment method include mixing, dipping, etc., and may include a step of adding a sizing agent to the pulp slurry and stirring and mixing. Examples of the external addition treatment method include spraying, coating, dipping treatment, foam coating, etc., and specifically include a pond type two-roll size press, a gate roll type, and a rod metering size press. The treatment may be an external addition treatment or an internal addition treatment. For example, when the pulp substrate is paper, it may be coated on the paper, or a solution may be adhered or sprayed on the paper, or it may be treated by mixing with the pulp slurry before papermaking. When the pulp substrate is a fiber material, examples of the treatment method include padding treatment, dipping treatment, spraying treatment, and coating treatment. Examples of the padding treatment include a method using a padding device described on pages 396 to 397 of the Fiber Dyeing Process Dictionary (published in 1963 by Nikkan Kogyo Shimbun Co., Ltd.) and pages 256 to 260 of Color Dyeing Chemistry III (published in 1975 by Jitsugyo Publishing Co., Ltd.). Examples of the coating treatment include a method using a coating machine described on pages 473 to 477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Sen’i Sha). Examples of the dipping treatment include a method using a batch dyeing machine described on pages 196 to 247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Sen’i Sha), and a liquid flow dyeing machine, an air flow dyeing machine, a drum dyeing machine, a winch dyeing machine, a washer dyeing machine, a cheese dyeing machine, etc. can be used. Examples of the spraying treatment include an air spray in which a treatment liquid is atomized with compressed air and sprayed, and a method using an air spray of a hydraulic atomization method.

[0229] The treatment method may be an internal addition treatment in which a sizing agent is added to the pulp slurry before papermaking. The method for manufacturing a pulp product including the internal addition treatment includes a step of adding a sizing agent to the pulp slurry and stirring and mixing it, and a step of subjecting the pulp composition prepared in this step to suction dewatering through a reticular body having a predetermined shape to deposit the pulp composition to form an intermediate pulp molded product, and a step of obtaining a pulp molded product by molding and drying the intermediate pulp molded product with a heated mold may include one or more of these steps. After the treatment, after simple drying at room temperature or high temperature, optionally, heat treatment may be performed depending on the properties of the pulp. The temperature of the heat treatment may be 150 °C or higher, 180 °C or higher, or 210 °C or higher, and may also be 300 °C or lower, 250 °C or lower, or 200 °C or lower, particularly 80 °C to 180 °C. By performing heat treatment within such a temperature range, excellent oil resistance, water resistance, etc. can be exhibited. An external addition treatment may be performed on the internally added pulp base material, treated with a sizing agent, and a further polyol modifier and / or a further paper strengthening agent may be adhered to the surface. Examples of the further polyol modifier and the further paper strengthening agent are as described above, but are not limited thereto.

[0230] The treatment method may be an external addition treatment in which a sizing agent is applied to the pulp base material after papermaking. The size press of the external addition treatment can also be classified as follows according to the coating method. One coating method is to supply a coating liquid (sizing liquid) to a nip portion formed by passing paper between two rubber rolls to create a coating liquid reservoir called a pond, and to apply the sizing liquid to both sides of the paper by passing the paper through this coating liquid reservoir. This is a so-called pond-type two-roll size press. The other coating methods are a gate roll type in which the sizing liquid is applied by a surface transfer type, and a rod metering size press. In the pond-type two-roll size press, the sizing liquid easily penetrates into the paper, and in the surface transfer type, the sizing liquid components tend to remain on the surface of the paper. The surface transfer type has a coating layer that tends to remain on the surface of the paper and has more coating layers formed on the surface than the pond-type two-roll size press. In the present disclosure, performance can be imparted to the paper even when the former pond-type two-roll size press is used. The paper treated in this way can show excellent oil resistance and water resistance, etc., by optionally undergoing a heat treatment in a temperature range of up to 300°C, for example up to 200°C, particularly 80°C to 180°C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

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

[0232] <Strength of Pulp Molded Product> 〔Dry Strength〕 The dry strength of the pulp molded product of the present disclosure is not particularly limited, but is evaluated by the specific tensile strength in the dry state measured according to JIS P 8113:2006. The specific dry tensile strength is the dry tensile strength divided by the density.

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

[0234] When a polyol-modified product is added to the pulp base material, the dry strength of the resulting pulp product decreases. Although not limited to the addition method, among the internal addition treatment method of adding the polyol-modified product to the pulp slurry before papermaking and the external addition treatment method of applying the polyol-modified product to the paper after papermaking, the internal addition treatment method results in a greater decrease in dry strength. In the present disclosure, it has been found that by adopting a specific composition, even when a polyol-modified product is used, a decrease in dry strength can be suppressed.

[0235] 〔Wet strength〕 The wet strength of the pulp molded product of the present disclosure is not particularly limited, but is evaluated by the specific wet tensile strength measured according to JIS P 8135:0998. The specific wet tensile strength is the wet tensile strength divided by the density.

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

[0237] When a polyol-modified product is added to a pulp base material, the wet strength of the resulting pulp product decreases. Although not limited to the addition method, in the internal addition treatment method of adding an oil-resistant agent to the pulp slurry before papermaking, and the external addition treatment method of applying an oil-resistant agent to the paper after papermaking, the internal addition treatment method results in a greater decrease in wet strength. In the present disclosure, it has been found that by adopting a specific composition, even when using a polyol-modified product, it is possible to suppress the decrease in wet strength.

Examples

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

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

[0240] [Preparation of Pulp Mold] Using an automatic mold forming machine, a pulp mold was prepared. A net-like body was placed on a metal pulp mold forming die provided with a large number of suction holes at the bottom, and a metal tank was placed at the top. The pulp slurry was placed in the upper metal tank. From the side opposite to the side where the net-like body of the pulp mold forming die was placed, the pulp-containing aqueous composition was suctioned and dehydrated at 0.1 to 1 MPa through the pulp mold forming die and the net-like body by a vacuum pump, and the solid content (such as pulp) contained in the pulp-containing aqueous composition was deposited on the net-like body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate was dried under a pressure of 0.1 to 1 MPa from above and below with a metal osmosis forming die heated to 60 to 200 °C. Thereby, a pulp mold formed in the shape of a container was manufactured.

[0241] [Practical Oil Resistance Test at 65 °C] The pulp mold was pretreated by storing it under the conditions of 23 °C and 50% humidity for 12 hours. 100 ml of corn oil at 65 °C was poured into the pulp mold, and after leaving it at room temperature for 45 minutes, the corn oil was taken out from the pulp mold, and the degree of oil stain on the pulp mold was evaluated. The evaluation values were set as follows according to the degree of penetration. 5: No penetration inside 4: Penetration inside. No penetration on the back side. 3: Penetration inside. Slight penetration on the back side. 2: Penetration inside. The penetration on the back side is less than 50% of the area. 1: Penetration inside. The penetration on the back side is 50% or more and less than 100% of the area. 0: Penetration throughout the back side.

[0242] [HD contact angle] A solution (or dispersion) with a solid content concentration of 1.0% of the liquid-repellent compound was spin-coated on a silicon wafer at 2500 rpm for 25 seconds to obtain a smooth spin-coated film. By heating this at 140 °C for 1 minute, a silicon wafer treated with the compound was produced. Chloroform was used as the solvent or dispersion medium. 2 μL of HD (hexadecane) was dropped onto the silicon wafer treated with the compound, and the static contact angle 1 second after droplet deposition was defined as the HD contact angle of the liquid-repellent compound.

[0243] [Tensile strength of pulp molded product] The tensile strength of the pulp mold is not particularly limited, but it was evaluated by the specific tensile strength in the dry state measured according to JIS P 8113:2006. Test pieces were cut out from the bottom surface of the pulp mold with a width of 15 mm, a length of 50 mm, and a thickness of 0.8 mm, and these were used. An autograph manufactured by Shimadzu Corporation was used as the apparatus, and the test was conducted under the conditions of a tensile interval of 30 mm and a tensile speed of 10 mm / min. The strength per unit area was calculated from the results of the tensile test. [Strength per unit area] = Breaking stress (N) / [Thickness (mm) * Test piece width (mm)] [Specific tensile strength] = Breaking stress (N) / [Test piece width (m) * Basis weight (g / m 2 )]

[0244] [Preparation Example 1: Preparation of decaglycerol decabehenate dispersion] As a polyol-modified product, 2 g of decaglycerol dodecabenzenesulfonate (degree of polymerization: 10, hydroxy group substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%), 0.2 g of polyethylene oxide trimethylnonyl ether (HLB: 13), and 17.8 g of water were mixed to obtain a precursor A of a water-dispersible release agent. After heating this precursor A of the water-dispersible release agent to 80°C, it was stirred at 7000 rpm for 20 minutes using a homogenizer to obtain a water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible release agent was 0%, and the median diameter D50 was 19.8 μm.

[0245] <Preparation Example 2: Preparation of Decaglycerol Heptabenzenesulfonate Dispersion> As a polyol-modified product, 2 g of decaglycerol heptabenzenesulfonate (degree of polymerization: 10, hydroxy group substitution rate: 7 / 12 * 100 [58%], bio-based ratio: 100%), 0.2 g of polyethylene oxide trimethylnonyl ether (HLB: 13), and 17.8 g of water were mixed to obtain a precursor A of a water-dispersible release agent. After heating this precursor A of the water-dispersible release agent to 80°C, it was stirred at 7000 rpm for 20 minutes using a homogenizer to obtain a water-dispersible release agent. The volume occupancy ratio of particles of 100 μm or more in the obtained water-dispersible release agent was 0%, and the median diameter D50 was 20.6 μm.

[0246] <Evaluation Example 1> Based on JIS K 6953-1:2011, a biodegradability test of decaglycerol dodecabenzenesulfonate (degree of polymerization: 10, hydroxy group substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%) was carried out. The biodegradability at the 30-day time point of the test period was 36%, and the biodegradability at the 60-day time point of the test period was 62%.

[0247] <Evaluation Example 2> Based on JIS K 6953-1:2011, a biodegradability test of decaglycerol heptabehenate (degree of polymerization 10, hydroxy group substitution rate: 7 / 12 * 100 [58%], bio-based ratio: 100%) was conducted. The biodegradability at the 30-day time point of the test period was 40%, and the biodegradability at the 60-day time point of the test period was 60%.

[0248] <Evaluation Example 3> Contact angle measurements of hexadecane were carried out for decaglycerol dodecabehenate (degree of polymerization 10, hydroxy group substitution rate: 12 / 12 * 100 [100%], bio-based ratio: 100%) and decaglycerol heptabehenate (degree of polymerization 10, hydroxy group substitution rate: 7 / 12 * 100 [58%], bio-based ratio: 100%).

[0249] TIFF2025083906000002.tif33155

[0250] <Example 1> The decaglycerol dodecabehenate dispersion of Preparation Example 1 was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio based on the pulp in terms of solid content was 5 wt%. After stirring for 30 seconds, a polyacrylamide-based paper strength agent was added at a ratio of 0.1% based on the pulp, and then stirred for 30 seconds to adjust a pulp-containing water-dispersed water-repellent agent. The pulp-containing water-dispersed water-repellent agent was put into an automatic mold forming machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m 2 It was. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0251] <Example 2> The decaglycerol deca behenyl ester dispersion of Preparation Example 1 was added to a pulp slurry with a concentration of 0.5 wt% so as to be in a ratio of 5 wt% based on the pulp in terms of solid content, stirred for 30 seconds, and then a polyacrylamide-based paper strengthening agent was added at a ratio of 0.5% based on the pulp and stirred for 30 seconds to prepare a pulp-containing water-dispersed water-repellent agent. The pulp-containing water-dispersed water-repellent agent was put into an automatic mold forming machine to prepare a pulp mold. The basis weight of the pulp mold was 500 g / m 2 2. An oil resistance test of the prepared pulp mold was carried out, and the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0252] <Example 3> The decaglycerol deca behenyl ester dispersion of Preparation Example 1 was added to a pulp slurry with a concentration of 0.5 wt% so as to be in a ratio of 5 wt% based on the pulp in terms of solid content, stirred for 30 seconds, and then a polyacrylamide-based paper strengthening agent was added at a ratio of 1.1% based on the pulp and stirred for 30 seconds to prepare a pulp-containing water-dispersed water-repellent agent. The pulp-containing water-dispersed water-repellent agent was put into an automatic mold forming machine to prepare a pulp mold. The basis weight of the pulp mold was 500 g / m 2 2. An oil resistance test of the prepared pulp mold was carried out, and the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0253] <Example 4> The decaglycerol deca behenyl ester dispersion of Preparation Example 1 was added to a pulp slurry with a concentration of 0.5 wt% so as to be in a ratio of 5 wt% based on the pulp in terms of solid content, stirred for 30 seconds, and then a polyamide-based paper strengthening agent was added at a ratio of 0.6% based on the pulp and stirred for 30 seconds to prepare a pulp-containing water-dispersed water-repellent agent. The pulp-containing water-dispersed water-repellent agent was put into an automatic mold forming machine to prepare a pulp mold. The basis weight of the pulp mold was 500 g / m2. An oil resistance test of the prepared pulp mold was carried out, and the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0254] <Example 5> The decaglycerol decabehenate dispersion of Preparation Example 1 was added to a pulp slurry with a concentration of 0.5 wt% so as to be in a ratio of 5 wt% with respect to the pulp in terms of solid content, stirred for 30 seconds, and then a polyamide sizing agent was added at a ratio of 0.9% based on the pulp, and stirred for 30 seconds to adjust a pulp-containing water-dispersed water repellent. The pulp-containing water-dispersed water repellent was put into an automatic mold forming machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m 2 It was. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0255] <Example 6> The decaglycerol heptabehenate dispersion of Preparation Example 2 was added to a pulp slurry with a concentration of 0.5 wt% so as to be in a ratio of 5 wt% with respect to the pulp in terms of solid content, stirred for 30 seconds, and then a polyacrylamide sizing agent was added at a ratio of 1.1% based on the pulp, and stirred for 30 seconds to adjust a pulp-containing water-dispersed water repellent. The pulp-containing water-dispersed water repellent was put into an automatic mold forming machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m 2 It was. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0256] <Example 7> The decaglycerol heptabehenate dispersion of Preparation Example 2 was added to a pulp slurry with a concentration of 0.5 wt% so as to be in a ratio of 5 wt% with respect to the pulp in terms of solid content, stirred for 30 seconds, and then a polyamide sizing agent was added at a ratio of 0.9% based on the pulp, and stirred for 30 seconds to adjust a pulp-containing water-dispersed water repellent. The pulp-containing water-dispersed water repellent was put into an automatic mold forming machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m 2 It was. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0257] <Example 8> The sugar fatty acid ester aqueous dispersion (polyd soybean oil fatty acid sucrose SEFOSE) was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio was 7 wt% based on the pulp in terms of solid content, stirred for 30 seconds, and then a polyacrylamide-based paper strength agent was added at a ratio of 1.1% based on the pulp and stirred for 30 seconds to prepare a pulp-containing water-dispersed water-repellent agent. The pulp-containing water-dispersed water-repellent agent was put into an automatic mold forming machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m 2 It was. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0258] <Comparative Example 1> Without adding a paper strength agent, the decaglycerol deca behenyl ester dispersion of Preparation Example 1 was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio was 5 wt% based on the pulp in terms of solid content, and stirred for 30 seconds to prepare a pulp-containing water-dispersed water-repellent agent. The pulp-containing water-dispersed water-repellent agent was put into an automatic mold forming machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m 2 It was. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

[0259] <Comparative Example 2> Without adding a paper strength agent, the decaglycerol hepta behenyl ester dispersion of Preparation Example 2 was added to a pulp slurry with a concentration of 0.5 wt% so that the ratio was 5 wt% based on the pulp in terms of solid content, and stirred for 30 seconds to prepare a pulp-containing water-dispersed water-repellent agent. The pulp-containing water-dispersed water-repellent agent was put into an automatic mold forming machine to produce a pulp mold. The basis weight of the pulp mold was 500 g / m 2 It was. When the oil resistance test of the produced pulp mold was carried out, the oil resistance performance was 4 points. The results of the tensile test are shown in Table 1.

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

[0261] [Table 1. Evaluation results of the tensile test of the pulp mold] TIFF2025083906000003.tif140155

Claims

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

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

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

4. The polyol-modified product is obtained by substituting one or more hydroxy groups of the polyol with a group represented by the following formula: The following formula: -Y Ｏ -Z Ｏ ｎ [In the formula, Y Ｏ is a 1 + n-valent group composed of one or more selected from the group consisting of Y Ｏ１ and Y Ｏ２ and is a 1 + n-valent group composed of one or more selected from the group consisting of Y Ｏ１ is a group consisting of one or more selected from the group consisting of direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O) ２ -, -C(=S)-, -NR'-, -C(OR')R'-, -C(OR')(-) ２ , and -N(-) ２ (wherein, R' is, independently at each occurrence, a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms (for example, 1 to 20, 1 to 10, or 1 to 4 carbon atoms).), and is a group composed of one or more selected from the group consisting of 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 which may have a substituent, a divalent to tetravalent hydrocarbon aromatic ring which may have a substituent, and a divalent to tetravalent heterocyclic ring which may have a substituent, Z Ｏ is a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a monovalent polysiloxane group, n is an integer of 1 or more and 3 or less.] The pulp composition according to claim 1 or 2.

5. Y Ｏ is -O-Y Ｏ１１ - or -O-Y Ｏ１１ -Y Ｏ２１ -Y Ｏ１２ - [In the formula, each symbol is independently in each occurrence, Y Ｏ１１ is a direct bond, -C(=O)-, -C(=O)-NR'-, or -C(=S)-NR'- and Y Ｏ２１ is a hydrocarbon group having 1 to 40 carbon atoms, 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'-, -SO ２ -, -SO ２ NR'-, -C(OR')R'-, or -C(OR')(-) ２ is.], The pulp composition according to claim 4.

6. The pulp composition according to claim 1 or 2, wherein the polyol is at least one selected from the group consisting of monosaccharides, oligosaccharides, polysaccharides, sugar alcohols (reducing sugars), hydroxy acids, amino acids, vitamins, flavonols, hydroxy hydrocarbons, and hydroxy group-containing compound polymers.

7. The polyol is 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, isomalto-dextrin, gellan gum, tamarind seed gum; ascorbic acid, kojic acid, quinic acid, chlorogenic acid, gluconic acid; glucosamine; ascorbic acid, inositol; catechin, quercetin, anthocyanin; Glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, trimethylolpropane, trimethylolethane; The pulp composition according to claim 1 or 2, which is at least one selected from the group consisting of polyglycerin, polyvinyl alcohol, hydroxyethyl (meth) acrylate polymer, hydroxypropyl (meth) acrylate polymer, and hydroxybutyl (meth) acrylate polymer.

8. The pulp composition according to claim 1 or 2, wherein the hexadecane contact angle of the polyol-modified body is 30° or more.

9. The pulp composition according to claim 1 or 2, wherein the polyol-modified body is a polyglycerin-modified body.

10. The pulp composition according to claim 9, wherein the hydroxy group substitution rate of the polyglycerin-modified body is 40% or more.

11. The pulp composition according to claim 1, wherein the amount of the paper strengthening agent is 2 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the polyol-modified body.

12. A pulp molded article formed from the pulp composition according to claim 1 or 2.

13. The pulp molded article according to claim 12, which is formed by adhering a further polyol-modified body and a further paper strengthening agent to the surface.

14. The pulp molded article according to claim 12, which is for food contact.

15. A method for producing the pulp composition according to claim 1 or 2, comprising a polyol-modified body adding step of adding the polyol-modified body to the pulp base material, and a paper strengthening agent adding step of adding the paper strengthening agent to the pulp base material.

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