Surface modifier

Abstract

The present invention provides a hydrocarbon-based surface modifier capable of imparting higher water repellency due to being a surface modifier containing an isoprenoid compound.

Description

Surface modifier

[0001] This disclosure relates to surface modifiers and products modified by said surface modifiers.

[0002] In recent years, progress has been made in developing hydrocarbon-based surface modifiers that can impart water repellency to various substrates.

[0003] Japanese Patent Publication No. 2021-155492

[0004] The purpose of this disclosure is to provide a hydrocarbon-based surface modifier that can impart higher water repellency.

[0005] The disclosure includes the following embodiments: [Clause 1] A surface modifier comprising an isoprenoid compound. [Clause 2] The surface modifier according to Claim 1, wherein the isoprenoid compound is a terpene or a terpenoid. [Clause 3] The surface modifier according to Claim 2, wherein the terpene is a compound selected from the group consisting of monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, sesquaterpenes, tetraterpenes, and pentaterpenes, and the terpenoid is a compound selected from the group consisting of monoterpenoids, sesquiterpenoids, diterpenoids, sesterterpenoids, triterpenoids, sesquaterpenoids, tetraterpenoids, and pentaterpenoids. [Clause 4] The surface modifier according to any one of Claims 1 to 3, wherein the isoprenoid compound is a steroid compound. [Clause 5] The surface modifier according to Claim 4, wherein the steroid compound is a sterol compound. [Clause 6] The surface modifier according to any one of Claims 1 to 3, wherein the isoprenoid compound is vitamin D. [Item 7] The isoprenoid compound is a surface modifier according to any one of items 1 to 6, wherein the isoprenoid compound has 15 to 70 carbon atoms. [Item 8] The isoprenoid compound is of the following formula: R １４ - (-CR １１ =CR １２ -R １３ -) ｎ -R １４ (I) [wherein, R １１ and R １２is, in each occurrence, independently, a hydrogen atom or a C １－１２ alkyl group, and R １３ is, in each occurrence, independently, a single bond or a C １－１２ alkylene group, and R １４ is, independently, a C １－４０ hydrocarbon group, and n is an integer from 1 to 100. The surface modifier according to any one of items 1 to 3, which is a compound represented by ]. [Item 9] The surface modifier according to item 8, wherein n is 4 or more. [Item 10] The surface modifier according to any one of items 1 to 9, wherein the isoprenoid compound has a ring structure. [Item 11] The surface modifier according to item 10, wherein the ring structure has a 4- to 10-membered ring. [Item 12] The surface modifier according to item 10 or 11, wherein the ring structure contains an unsaturated structure. [Item irteen] The surface modifier according to any one of items 10 to 12, wherein the ring structure is a condensed polycyclic structure containing 4 or more rings. [Item 14] The ring structure is represented by the following formula: A surface modifier according to any one of claims 10 to 13, comprising a structure (II) which may contain an unsaturated bond between adjacent ring member carbons, represented by. [Item 15] The surface modifier according to item 14, wherein the structure (II) has at least one methyl group at the C10 and C13 positions and contains a double bond between the C7 carbon and the C8 carbon. [Item sixteen] The surface modifier according to item 15, wherein the structure (II) further has an -OH group at the C3 position. [Item 17] The structure (II) further has a group represented by -O-C(=O)R ２ 、 -C(=O)-OR ２ or -O-C(=O)OR ２ [wherein, R ２ is a C １－４０ hydrocarbon group.]. The surface modifier according to item 15, having a group represented by. [Item 18] The surface modifier according to item 17, wherein R ２ is a C ３－２０ alkyl group. [Item 19] The ring structure is represented by the following formula: A surface modifier according to any one of claims 10 to 13, comprising a structure (III) which may contain unsaturated bonds between adjacent ring member carbons. [Clause 20] The surface modifier according to claim 19, wherein the structure (III) has two methyl groups at the C4 position, at least one methyl group at the C8, C10, and C20 positions, and contains a double bond between the C12 and C13 carbons. [Clause 21] The surface modifier according to claim 20, further comprising a -COOH group at the C17 position. [Clause 22] The surface modifier according to claim 20 or 21, further comprising a monovalent hydrocarbon group at the C20 position. [Clause 23] The surface modifier according to any one of claims 1 to 22, wherein the isoprenoid compound is derived from a natural product. [Item 24] The surface modifier according to Item 1, wherein the isoprenoid compound is selected from the group consisting of β-carotene, squalene, β-caryophyllene, oleanolic acid, stearyl glycyrrhetinate, brassicasterol, stigmasterol, cholesterol, cholecalciferol, β-sitosterol, ergosterol, cholesteryl oleate, cholesteryl myristart, cholesteryl stearate, cholesterol butyrate, cholesteryl linoleate, cholesterol benzoate, cholesteryl decanoate, cholesterol-5-en-3-ol, and cholesteryl oleyl carbonate. [Clause 25] The surface modifier according to Claim 1, wherein the isoprenoid compound is selected from the group consisting of β-carotene, oleanolic acid, brassicasterol, stigmasterol, cholesterol, cholecalciferol, β-sitosterol, ergosterol, cholesteryl oleate, cholesteryl myristart, cholesteryl stearate, cholesterol butyrate, cholesteryl linoleate, cholesterol benzoate, and cholesteryl decanoate. [Clause 26] The surface modifier according to any one of Claims 1 to 25, which is an aqueous dispersion composition. [Clause 27] The surface modifier according to any one of Claims 1 to 26, which comprises one or more selected from the group consisting of surfactants, silicones, waxes, organic acids, and curing agents. [Clause 28] The surface modifier according to any one of Claims 1 to 27, which is for textile products or paper products. [Clause 29] A product modified with the surface modifier according to any one of Claims 1 to 28.[Clause 30] The product according to Claim 29, which is a textile product or a paper product. [Clause 31] A method for producing a modified product, comprising the step of modifying a substrate with a surface modifier according to any one of Claims 1 to 28. [Clause 32] The method for producing a product according to Claim 31, wherein the modification is an internal modification.

[0006] According to this disclosure, a hydrocarbon-based surface modifier that can impart higher water repellency can be provided.

[0007] <Definition of Terms> As used herein, "n-valent group" means a group having n bonds, that is, a group that forms n bonds with other groups (or atoms). Also, "n-valent organic group" means an n-valent group containing carbon. Such organic groups are not particularly limited, but may be hydrocarbon groups or derivatives thereof. A derivative of a 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 a hydrocarbon group.

[0008] As used herein, "hydrocarbon group" means a group containing carbon and hydrogen, obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include C １－４０ Examples of hydrocarbon groups include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. If explicitly stated, the hydrocarbon group may be substituted with one or more substituents.

[0009] In this specification, unless otherwise stated, whether or not the phrases "independently in each occurrence," "independently of each other," "independently of each other," or similar expressions are explicitly stated, when a term (symbol) that may appear multiple times in a chemical structure is defined, the definition shall apply independently to each occurrence.

[0010] In this specification, unless otherwise specified, if a molecule may have multiple stereoisomers (geometric and optical isomers), it shall encompass all possible stereoisomers. For example, in this specification, "limonene" refers to either "d-limonene" or "l-limonene" unless otherwise specified.

[0011] In this specification, unless otherwise specified, if a compound may have one or more hydrates, it shall include the anhydride and all hydrates that the compound may take. For example, in this specification, "oxalic acid" refers to either "oxalic acid anhydride" or "oxalic acid dihydrate" unless otherwise specified.

[0012] The chemical structures described herein should be understood to exclude any chemical structures that would be considered chemically impossible or extremely unstable by those skilled in the art.

[0013] <Surface Modifier> The surface modifiers disclosed herein include isoprenoid compounds.

[0014] <Isoprenoid Compounds> As used herein, "isoprenoid" means an isoprene unit having 5 carbon atoms (C ５ H ８ This term refers to compounds that have one or more basic structures, and compounds that can be derived from such compounds. This group of compounds includes isoprene, hemiterpenoids, terpenes, and terpenoids derived from terpenes. Isoprene compounds may include those produced by biosynthesis and those produced by industrial methods.

[0015] As used herein, "hemiterpenoid" refers to a compound that can be derived from one molecule of isoprene, and may include, for example, compounds obtained by hydration of isoprene followed by oxidation, oxygenation (epoxidation), etc. Specific examples of hemiterpenoids include, but are not limited to, prenol, 3-methyl-3-buten-2-ol, tigric acid, angelic acid, senecioic acid, and isovaleric acid.

[0016] As used herein, "terpene" refers to a compound that can be produced by the addition reaction of two or more isoprene molecules, and a hydrocarbon compound obtained by one or more steps of cyclization, ring opening, rearrangement, addition, condensation, substitution, etc. of said compound. Typically, these compounds may be a compound formed by the condensation of at least one molecule of isopentenyl diphosphate (IPP) and at least one molecule of dimethylallyl diphosphate (DMAPP), and a hydrocarbon compound obtained by one or more steps of cyclization, ring opening, rearrangement, addition, condensation, substitution, hydrogenation, etc. of said compound. Terpenes are (C ５ H ８ ) ｎ Terpenes can be represented as (where n is an integer greater than or equal to 2), and include not only linear compounds in which two or more isoprene atoms are linked in a chain, but also cyclic compounds that can be produced by intramolecular cyclization reactions of such linear compounds. Examples of terpenes include monoterpenes (n=2), sesquiterpenes (n=3), diterpenes (n=4), sesterterpenes (n=5), triterpenes (n=6), sesquaterpenes (n=7), tetraterpenes (n=8), pentaterpenes (n=9), and polyterpenes (n=10 or more). Furthermore, since terpenes can be formed via one or more induction reactions as described above, the number of carbon atoms in terpenes may increase or decrease from a multiple of 5. For similar reasons, the number of hydrogen atoms in terpenes may increase or decrease from a multiple of 8. For example, squalene is a triterpene, but it has 50 hydrogen atoms.

[0017] As used herein, "terpenoid" refers to a compound having one or more oxygen atoms that can be derived from the terpenes described above. "Can be derived from terpenes" is not limited to compounds that can be directly derived from terpenes through a single reaction, but may also refer to compounds that can be derived through two or more reactions. For example, a compound having one or more oxygen atoms obtained from terpenes through one or more reactions such as cyclization, ring opening, rearrangement, addition, condensation, substitution, or hydrogenation is a terpenoid, and examples include alcohols, aldehydes, ketones, oxides, esters, amides, and amines. Examples of terpenoids include monoterpenoids derived from monoterpenes, sesquiterpenoids derived from sesquiterpenes, diterpenoids derived from diterpenes, sesterterpenoids derived from sesterterpenes, triterpenoids derived from triterpenes, sesquaterpenoids derived from sesquaterpenes, tetraterpenoids derived from tetraterpenes, pentaterpenoids derived from pentaterpenes, and polyterpenoids derived from polyterpenes. Furthermore, since terpenoids can be derived from other compounds via one or more induction reactions as described above, the number of carbon atoms in terpenoids may increase or decrease from a multiple of 5. For similar reasons, the number of hydrogen atoms in terpenoids may increase or decrease from a multiple of 8. For example, quasine is a triterpenoid, but it has 22 carbon atoms.

[0018] In this specification, isoprenoids are classified as "terpenes" if they do not contain an oxygen atom in their molecule, and as "terpenoids" if they contain one or more oxygen atoms.

[0019] Furthermore, isoprenoids, hemiterpenoids, terpenes, and terpenoids may also contain atoms other than carbon atoms, hydrogen atoms, and oxygen atoms, such as nitrogen atoms, sulfur atoms, halogen atoms, phosphorus atoms, etc.

[0020] <Terpenes> In one embodiment, the isoprenoid compound is a terpene. Preferred terpenes included in the surface modifier of this disclosure are monoterpenes (n=2), sesquiterpenes (n=3), diterpenes (n=4), sesterterpenes (n=5), triterpenes (n=6), sesquaterpenes (n=7), tetraterpenes (n=8), or pentaterpenes (n=9).

[0021] Monoterpenes can be compounds produced by the addition reaction (e.g., radical addition reaction) of two isoprene molecules, or compounds formed by the removal of a phosphate group from geranyl diphosphate (GPP) formed by the condensation of one IPP molecule and one DMAP molecule, or compounds obtained by hydrogenation thereof. Examples of such compounds include α-ocimene, β-ocimene, α-myrcene, and β-myrcene. Monoterpenes can also be compounds formed from GPP via a single cyclization reaction, or compounds obtained by hydrogenation thereof. Examples of such compounds include limonene, α-terpinene, β-terpinene, γ-terpinene, δ-terpinene, α-phellandrene, β-phellandrene, p-cymene, α-pinene, β-pinene, and p-menthane. Monoterpenes can also be compounds formed from GPP via two or more cyclization reactions, or compounds obtained by hydrogenation thereof. Examples of such compounds include carene, sabinene, camphene, α-thugen, and β-thugen. Monoterpenes also include halomones containing halogen atoms.

[0022] Sesquiterpenes may be compounds produced by the addition reaction of three isoprene molecules (e.g., radical addition reaction), or compounds formed by the removal of a phosphate group from farnesyl diphosphate (FPP), which is formed by the condensation of GPP and IPP, or compounds obtained by hydrogenating such compounds. Examples of such compounds include α-farnesene, β-farnesene, α-caryophyllene, and β-caryophyllene. Furthermore, sesquiterpenes may be compounds formed from FPP through a single cyclization reaction, or compounds obtained by hydrogenating such compounds. Examples of such compounds include α-santarene, β-santarene, α-elemene, β-elemene, γ-elemene, δ-elemene, germacrene, zingiberene, α-bisabolene, β-bisabolene, and γ-bisabolene. Furthermore, sesquiterpenes may be compounds formed from FPP through two or more cyclization reactions, or compounds obtained by hydrogenating such compounds. Examples of such compounds include driman, valensene, thujopsene, α-selinene, β-selinene, γ-selinene, δ-selinene, amorphous-4,11-diene, isocomene, α-cadinene, β-cadinene, γ-cadinene, δ-cadinene, cadalene, guaiazulene, α-guayene, β-guayene, γ-guayene, δ-guayene, copaene, α-cedrene, β-cedrene, vetivebazulene, and longifolene.

[0023] Diterpenes can be compounds produced by the addition reaction of four isoprene molecules (e.g., radical addition reaction), or compounds formed by the removal of a phosphate group from geranylgeranyl diphosphate (GGPP), which is formed by the condensation of FPP and IPP, or compounds obtained by hydrogenating it. Examples of such compounds include phytane. Diterpenes can also be compounds formed from GGPP via a single cyclization reaction, or compounds obtained by hydrogenating it. Examples of such compounds include prenylbisavorane and cembran. Diterpenes can also be compounds formed from GGPP via two or more cyclization reactions, or compounds obtained by hydrogenating them. Examples of such compounds include stemarene, labdan, haliman, gunaphalan, colensane, clerodan, abietan, traquiloban, basman, euniceran, casban, dafnan, ingenan, taxane, sucralene, 18-norabiethane, and pristane.

[0024] Sesterterpenes may be compounds produced by the addition reaction of five isoprene molecules (e.g., radical addition reaction), or compounds formed by the removal of a phosphate group from geranylfarnesyl diphosphate formed by the condensation of GGPP and IPP, or compounds obtained by hydrogenation or cyclization thereof.

[0025] Triterpenes may be compounds produced by the addition reaction (e.g., radical addition) of six isoprene molecules, or compounds that can be formed from two FPP molecules by farnesyl diphosphate farnesyltransferase, or compounds obtained by hydrogenation, one or more cyclizations, etc. Examples of such compounds include cucurbitan, squalene, squalane, oleanane, hopane, dipropten, cholestane, corane, 5α-pregnane, 5β-pregnane, androstan, and estran.

[0026] Sesquaterpenes may be compounds produced by the addition reaction of seven isoprene molecules (e.g., radical addition reaction), or compounds formed by the removal of a phosphate group from a compound formed by the condensation of GGPP and FPP, or compounds obtained by hydrogenation, cyclization, etc.

[0027] Tetraterpenes may be compounds produced by the addition reaction of eight isoprene molecules (e.g., radical addition reaction), compounds formed by the condensation of two GGPPs, or compounds obtained by hydrogenation, cyclization, etc. Examples of such compounds include phytoene, phytofluene, α-carotene, β-carotene, γ-carotene, δ-carotene, lycopene, ε-carotene, ζ-carotene, and neurospolene.

[0028] Pentaterpenes may be compounds produced by the addition reaction (e.g., radical addition) of nine isoprene molecules, or compounds obtained by hydrogenation, cyclization, etc.

[0029] The surface modifier disclosed herein may contain only one of the terpenes described above, or it may contain two or more.

[0030] In one embodiment, the surface modifier of the present disclosure comprises only one of the terpenes described above.

[0031] In one embodiment, the surface modifier of the present disclosure comprises two or more of the terpenes described above.

[0032] In one embodiment, the surface modifier of the present disclosure comprises β-caryophyllene.

[0033] In one embodiment, the surface modifier of the present disclosure comprises squalene.

[0034] In one embodiment, the surface modifier of the present disclosure comprises a β-carotenoid.

[0035] <Terpenoids> In one aspect, isoprenoid compounds are terpenoids.

[0036] The terpenoids included in the surface modifier of this disclosure are preferably monoterpenoids, sesquiterpenoids, diterpenoids, sesterterpenoids, triterpenoids, sesquaterpenoids, tetraterpenoids, or pentaterpenoids.

[0037] Monoterpenoids may be derivatives of compounds produced by the addition reaction (e.g., radical addition) of two isoprene molecules, or compounds obtained by using geranyl diphosphate (GPP), which is formed by the condensation of one IPP molecule and one DMAP molecule, as a precursor, and then undergoing rearrangement, substitution, addition, elimination, oxidation, cyclization, hydrolysis, hydrogenation, etc. of GPP. Examples of monoterpenoids include geranyl diphosphate, geraniol, α-terpineol, β-terpineol, γ-terpineol, δ-terpineol, geranial, neral, nerol, citronellal, linalool, menthol, thymol, carvacrol, camphor, borneol, cineole, ascaridol, p-menthane-3,8-diol, hydroxycitronellal, carveol, α-methylene-4-methyl-5-oxo-3-cyclohexene-1-acetic acid, cantharidin, geranyl acetate, linalyl acetate, safranal, rodinol, hinokitiol, thujapridine, cuminaldehyde, dihydrocarveol, and others.

[0038] Sesquiterpenoids are derivatives of compounds produced by the addition reaction (e.g., radical addition) of three isoprene molecules, or compounds obtained by using farnesyl diphosphate (FPP), formed by the condensation of one GPP molecule and one IPP molecule, as a precursor, and then undergoing rearrangement, substitution, addition, elimination, oxidation, cyclization, hydrolysis, hydrogenation, etc. of FPP. Examples of sesquiterpenoids include farnesyl diphosphate, farnesol, bisabolol, costol, santonin, nookatone, artemisiaic acid, cedrol, isoverelal, merlidial, acolan, hirsutamic acid, gilinal, abscisic acid, guaiol, santalol, santanic acid, deoxynivalenol, trichothecene, nardocinone, nivalenol, nerolidol, bisacron, and the like.

[0039] Diterpenoids may be derivatives of compounds produced by the addition reaction (e.g., radical addition reaction) of four isoprene molecules, or compounds obtained by using geranylgeranyl diphosphate (GGPP), formed by the condensation of one FPP molecule and one IPP molecule, as a precursor, and then undergoing rearrangement, substitution, addition, elimination, oxidation, cyclization, hydrolysis, hydrogenation, etc. of GGPP. Examples of diterpenoids include geranylgeranyl diphosphate, isophytol, cafestol, carnosic acid, ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J, ginkgolide M, grayanotoxin I, grayanotoxin II, grayanotoxin III, geranylgeraniol, salvinolin, gibberellin, gibberellic acid, sclareol, steviol, daphnetoxin, thiamrin, tidilanol tigrete, tryptonide, tryptride, phytanic acid, ferginol, forskolin, fusicococcin A, prostratin, phorbol, mucilin, momilactone B, lagokirin, and others.

[0040] Sesterterpenoids may be derivatives of compounds produced by the addition reaction (e.g., radical addition) of five isoprene molecules, or compounds obtained by using geranylfarnesyl diphosphate (GFPP), formed by the condensation of one molecule of GGPP and one molecule of IPP, as a precursor, and then undergoing rearrangement, substitution, addition, elimination, oxidation, cyclization, hydrolysis, hydrogenation, etc. of GFPP. Examples of sesterterpenoids include geranylfarnesol, scalarin, and ophiovorin.

[0041] Triterpenoids may be derivatives of compounds produced by the addition reaction (e.g., radical addition) of six isoprene molecules, or compounds that can be formed by farnesyl diphosphate farnesyltransferase, which is formed by the condensation of two FPP molecules, as precursors, and may be compounds obtained by transposition, substitution, addition, elimination, oxidation, cyclization, hydrolysis, hydrogenation, etc. of said compounds. Examples of triterpenoids include α-amyrin, β-amyrin, ursolic acid, ambrain, quasin, cucurbitacin, sapogenin, ziziphine, ginsenoside, soy saponin, nimbine, hodulcin, holoturin A, holoturin B, etc.

[0042] Sesquaterpenoids may be derivatives of compounds produced by the addition reaction (e.g., radical addition reaction) of seven isoprene molecules, or compounds obtained through the rearrangement, substitution, addition, elimination, oxidation, cyclization, hydrolysis, hydrogenation, etc., of compounds formed by the condensation of GGPP and FPP, etc.

[0043] Tetraterpenoids can be compounds produced by the addition reaction of eight isoprene molecules (e.g., radical addition reaction), or compounds formed by the condensation of two GGPP molecules, etc., followed by the removal of a phosphate group from such a compound, and then obtained through rearrangement, substitution, addition, elimination, oxidation, cyclization, hydrolysis, hydrogenation, etc. Examples of tetraterpenoids include lutein, zeaxanthin, canthaxanthin, fucoxanthin, astaxanthin, antheraxanthin, violaxanthin, α-cryptoxanthin, β-cryptoxanthin, echinenone, 3-hydroxyechinenone, 3'-hydroxyechinenone, adonizanthin, phenicoxanthin, and the like.

[0044] <Steroid Compounds> In one aspect, isoprenoid compounds are steroid compounds.

[0045] In this specification, "steroid compound" (sometimes simply referred to as "steroid") is an isoprenoid compound having a basic skeleton represented by the chemical formula shown in the following formula (II) (hereinafter also referred to as the steroid skeleton).

[0046] Steroid compounds typically have methyl groups at the C10 and C13 positions of their steroid skeleton, and often an alkyl group at the C17 position. However, this specification is not limited to such compounds; any isoprenoid compound having a steroid skeleton is referred to as a steroid. Steroids may be terpenes or terpenoids.

[0047] Steroid compounds can be broadly classified into five types based on differences in the structure of their steroid skeleton: cholestane, coran, pregnane, androstan, and estran. Examples of cholestane-type steroids include cholestane, cholestane, sterol, cholesteryl oleate, cholesteryl myristart, cholesteryl stearate, cholesterol butyrate, cholesteryl linoleate, cholesterol benzoate, cholesteryl decanoate, cholest-5-en-3-ol, and cholesteryl oleyl carbonate. Cholestane is a compound that has one or more double bonds at any position in its steroid skeleton; for example, the bond between the C4 and C5 positions may be a double bond. Sterol is a general term for compounds that have a hydroxyl group at the C3 position. Examples of coran-type steroids include coran and cholic acid. Examples of pregnane-type steroids include 5α-pregnane, 5β-pregnane, cortisone, hydrocortisone, progesterone, cyproterone acetate, danazol, and fluocinonide. Examples of androstan-type steroids include 5α-androstan, 5β-androstan, testosterone, and dihydrotestosterone. Examples of estran-type steroids include 5α-estran, 5β-estran, estren, nandrolone, estratriene, and estratriene-17β-ol. Cholestane-type steroid compounds are more preferred among the steroid compounds disclosed herein.

[0048] Aside from that, steroid compounds can be broadly classified into glucocorticoids and mineralocorticoids. Examples of glucocorticoids include cortisol, corticosterone, and cortisone. Examples of mineralocorticoids include aldosterone, deoxycorticosterone, and fludrocortisone.

[0049] In one embodiment, the isoprenoid compound is a sterol compound.

[0050] In this specification, "sterol compound" (sometimes simply referred to as "sterol") is a cholestane-type steroid having a basic skeleton in which an OH group is bonded to the C3 position of formula (II) above.

[0051] Examples of sterols include cholesterol, ergosterol, dehydroepiandrosterone, estradiol, 3-hydroxyestratriene, β-sitosterol, campesterol, stigmasterol, brassicasterol, and brazicasterol.

[0052] In one embodiment, the isoprenoid compound is vitamin D.

[0053] As for vitamin D, ergocalciferol (vitamin D ２ ) and cholecalciferol (vitamin D ３ Examples include the following. Cholecalciferol is more preferred as the isoprenoid compound of this disclosure.

[0054] The carbon number of the isoprenoid compounds of this disclosure may be 5 or more, 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 40 or more, or 50 or more. Alternatively, the carbon number of the isoprenoid compounds of this disclosure may be 180 or less, 150 or less, 120 or less, 100 or less, 90 or less, 80 or less, or 70 or less. For example, the carbon number of the isoprenoid compounds of this disclosure may be 5 to 180, preferably 15 to 70, and more preferably 20 to 50.

[0055] In one embodiment, the isoprenoid compound of the present disclosure is given by the following formula: R １４ - (-CR １１ =CR １２ -R １３ -) ｎ -R １４ (I) [wherein, R １１ and R １２ In each appearance, independently, a hydrogen atom or C １－１２ It is an alkyl group, R １３ Each occurrence is independently of a single bond or C １－１２ It is an alkylene group, R １４ Each of these is independently a hydrogen atom or C １－４０ It is a hydrocarbon group, and n is an integer from 1 to 100. It is a compound represented by [ ].

[0056] R １１ and R １２ In each appearance, independently, a hydrogen atom or C １－１２ It is an alkyl group.

[0057] R １１ and R １２ C in １－１２ The alkyl group has preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and tert-butyl groups, but methyl is particularly preferred.

[0058] R １１ C １－１２ If it is an alkyl group, R １２ It is preferable that it is a hydrogen atom.

[0059] R １２ C １－１２ If it is an alkyl group, R １１ It is preferable that it is a hydrogen atom.

[0060] In one embodiment, R １１ and R １２ This is a hydrogen atom.

[0061] In one embodiment, R １１ R is a methyl group, １２ It is a hydrogen atom.

[0062] In one embodiment, R １１ R is a hydrogen atom, １２ It is a methyl group.

[0063] R １３ Each occurrence is independently of a single bond or C １－１２ It is an alkylene group.

[0064] R １３ C in １－１２ The alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 6. Examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, isopropylene, and tert-butylene groups, but methylene or ethylene groups are particularly preferred.

[0065] In one embodiment, R １３ It is a single bond.

[0066] In one embodiment, R １３ This is an ethylene group.

[0067] R １４ Each of these is independently a hydrogen atom or C １－４０ It is a hydrocarbon group.

[0068] R １４ The hydrocarbon group in may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group (e.g., an alkyl group), or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear. If the hydrocarbon group is substituted, it is preferably substituted with an alkyl group (e.g., a methyl group or an ethyl group), and preferably not substituted with substituents other than alkyl groups. The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, 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. １４ The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 3 to 10.

[0069] In one embodiment, R １４ This is a hydrogen atom.

[0070] In one embodiment, R １４ This is a methyl group.

[0071] n is an integer between 1 and 100.

[0072] n is 1 or greater, and may be 2 or greater, 3 or greater, 4 or greater, 6 or greater, 10 or greater, 12 or greater, 15 or greater, 20 or greater, or 30 or greater. Also, n is 100 or less, and may be 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 15 or less, or 10 or less. n is preferably 4 or greater, more preferably 7 or greater. Also, n is preferably 20 or less, more preferably 12 or less. Also, n is preferably 4 to 20, more preferably 7 to 12.

[0073] In one preferred embodiment, the isoprenoid compound includes a ring structure. The type of ring structure is not particularly limited and may be any ring with three or more members. For example, the ring structure may be an aliphatic ring or an aromatic ring. The ring structure may also contain double and / or triple bonds. The ring structure may also be a heterocycle in which some of the atoms forming the ring are atoms other than carbon atoms (e.g., boron, oxygen, nitrogen, sulfur, silicon, etc.). The ring structure may also be a fused ring in which two or more atoms constituting one ring are simultaneously constituent atoms of another ring. The ring structure may also be a spirocycle in which two rings share only one of the same atoms. Specific examples of such ring structures include propane ring, butane ring, cyclopentane ring, cyclopentene ring, cyclohexane ring, cyclohexene ring, cyclohexine ring, cyclooctane ring, 1,3-cyclohexadiene ring, adamantane ring, decalin ring, norbornane ring, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, azulene ring, chrysene ring, benzofluoracene ring, pyrene ring, coronene ring, keklen ring, 3,4-benzopyrene ring, pyridine ring, pyridinium ring, thiophene ring, phosphole ring, imidazole ring, pyrazole ring, borol ring, Examples include thiazole rings, oxetane rings, 1,3-dioxetane rings, pyrrole rings, pyran rings, azepine rings, silole rings, piperidine rings, tetrahydrofuran rings, tetrahydropyran rings, phospholine rings, morpholine rings, 1,4-dioxane rings, furan rings, oxirane rings, indole rings, benzimidazole rings, purine rings, quinoline rings, isoquinoline rings, thiaidine rings, quinazoline rings, pteridine rings, chromene rings, isochromene rings, carbazole rings, choline rings, porphyrin rings, spiropentadiene rings, sterane skeletons, steroid skeletons, sterol skeletons, and the like. Furthermore, isoprenoid compounds may have multiple ring structures in their molecules. In addition, it is preferable that at least one of the hydrogen atoms on these rings is substituted with a monovalent organic group.

[0074] In this specification, if one ring shares one or more atoms with another ring (structure), the two rings (structures) shall be considered to form a single ring structure. Conversely, if one ring does not share any atoms with another ring (structure), the two rings (structures) shall be considered to form separate ring structures. For example, in cyclohexylbenzene, the cyclohexane ring and the benzene ring form different ring structures. Therefore, cyclohexylbenzene is considered a molecule having two ring structures.

[0075] It is more preferable that at least one of the ring structures has 4 to 10 members. The surface modifier of the present disclosure can exhibit better water repellency if the isoprenoid compound has 4 to 10 members. If the isoprenoid compound contains multiple ring structures, it is sufficient that at least one of them has 4 to 10 members. Also, if the ring structure is a fused ring, it is sufficient that at least one of the rings forming the fused ring has 4 to 10 members. The ring structure is more preferably a 4 to 6 member ring, and even more preferably a 5 to 6 member ring.

[0076] It is more preferable that at least one of the ring structures includes an unsaturated structure. As used herein, "unsaturated structure" refers to a chemical bond between adjacent atoms that is valence 2 or higher, and is typically formed from one σ bond and one or two π bonds. The number of unsaturated structures in a single ring structure may be one or more. The unsaturated structure may be a triple bond, but is preferably a double bond. The unsaturated structure may be a double bond between carbon and nitrogen, carbon and oxygen, carbon and sulfur, nitrogen and nitrogen, sulfur and sulfur, etc., but is more preferably a carbon-carbon double bond. Furthermore, it is even more preferable that the unsaturated structure is located between carbon atoms forming a 4- to 10-membered ring in the ring structure.

[0077] It is more preferable that at least one of the ring structures is a condensed polycyclic structure containing four or more rings. At least one of the rings forming the condensed polycyclic structure is preferably a 4- to 10-membered ring, and more preferably a 4- to 6-membered ring. Furthermore, it is preferable that the condensed polycyclic structure includes an unsaturated structure. Examples of such polycyclic structures include the steroid skeleton described above, as well as the lupin skeleton, oleanane skeleton, ursan skeleton, and the like.

[0078] In a more preferred embodiment, the isoprenoid compound of the present disclosure is of the following formula: This is a compound containing structure (II), which may include unsaturated bonds between adjacent ring member carbons, as represented by .

[0079] In a more preferred embodiment, structure (II) has methyl groups at the C10 and C13 positions and contains a double bond between the C7 and C8 carbon atoms, as represented by the following formula (II-2).

[0080] Furthermore, hydrogen atoms on the steroid skeleton in structure (II-2) may be substituted with substituents (i.e., monovalent groups). In particular, it is preferable that the hydrogen atoms at positions C3 and C17 be substituted with substituents. It is preferable that the hydrogen atoms on other carbons not be substituted with substituents. Also, in structure (II-2), one hydrogen atom bonded to adjacent carbon atoms may be eliminated from each to form a carbon-carbon double bond. For example, in structure (II-2), one hydrogen atom bonded to positions C7 and C8 may be eliminated from each to form a double bond between the carbon at position C7 and the carbon at position C8.

[0081] Examples of substituents at the C3 position include -R ２ , -OR ２ , -NR ２ ２ , -OC(=O)-R ２ , -C(=NR ２ ) R ２ , -C(=O)-OR ２ , -OC(=O)-OR ２ , -C(=O)-NR ２ ２ , -SO ２ (NR ２ )２ may be (R ２ is, independently of each other, a hydrogen atom, a halogen atom or a C １－４０ hydrocarbon group). The halogen atom may be any of fluorine, bromine, chlorine or iodine. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, may be a saturated aliphatic hydrocarbon group (for example, an alkyl group), or may also be an unsaturated aliphatic hydrocarbon group (for example, an alkenyl group). The hydrocarbon group is branched or linear, for example, linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group may be a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms of the hydrocarbon group may be 1 or more, 2 or more, 4 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, 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.

[0082] In a preferred embodiment, the substituent at the C3 position is -OR ２１ (wherein R ２１ is a hydrogen atom, a halogen atom or a C １－４０ hydrocarbon group). The halogen atom and the hydrocarbon group may be the same as the above R ２ . R ２１ being a hydrogen atom (that is, the substituent at the C3 position being -OH) is particularly preferred. In this case, the compound of structure (II-2) is classified as a sterol compound.

[0083] In another preferred embodiment, the substituent at the C3 position is -O-C(=O)-R ２２ 、 -C(=O)-OR ２２ or -O-C(=O)-OR ２２ (wherein R ２２ is a hydrogen atom, a halogen atom or a C １－４０ hydrocarbon group). Among them, -O-C(=O)-R ２２ is particularly preferred. The halogen atom may be the same as the above R ２ . R ２２ is C １－４０It is particularly preferable that the hydrocarbon group is a hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group (e.g., an alkyl group), or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear. If the hydrocarbon group is substituted, it is preferable that it is substituted with an alkyl group (e.g., a methyl group or an ethyl group), and preferably not substituted with substituents other than alkyl groups. The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, 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. ２２ The number of carbon atoms in the hydrocarbon group is preferably 2 to 30, more preferably 3 to 20, and even more preferably 6 to 18.

[0084] R ２２ Specific examples of hydrocarbon groups in this context include: -Ph (phenyl group) -CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH=CHCH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH<000​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​１７ ２ , -OC(=O)-R １７ , -C(=NR １７ ) R １７ , -C(=O)-OR １７ , -OC(=O)-OR １７ , -C(=O)-NR １７ ２ , -SO ２ (NR １７ ) ２ It is acceptable (R １７ Each of these is independently a hydrogen atom, a halogen atom, or C １－４０ (Hydroxide group). As for halogen atoms, the above R ２ It may be similar to the above. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group (e.g., an alkyl group), or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear. If the hydrocarbon group is substituted, it is preferably substituted with an alkyl group (e.g., a methyl group or an ethyl group), and preferably not substituted with substituents other than alkyl groups. The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, 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. R １７ The number of carbon atoms in the hydrocarbon group is preferably 2 to 30, more preferably 4 to 20, and even more preferably 6 to 18.

[0086] In a preferred embodiment, the substituent at the C17 position is -R １７１ (In the formula, In the formula, R １７１ is a hydrogen atom, halogen atom or C １－４０ (It is a hydrocarbon group). As for halogen atoms, the above R ２ It may be the same as R. １７１ C １－４０It is particularly preferable that the hydrocarbon group is an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but it is preferable that it is an aliphatic hydrocarbon group. It may be a saturated aliphatic hydrocarbon group (e.g., an alkyl group) or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear. If the hydrocarbon group is substituted, it is preferable that it is substituted with an alkyl group (e.g., a methyl group or an ethyl group), and it is preferable that it is not substituted with substituents other than alkyl groups. The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, 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. １７１ The number of carbon atoms in the hydrocarbon group is preferably 2 to 30, more preferably 3 to 20, and even more preferably 6 to 18.

[0087] R １７１ Specific examples of hydrocarbon groups in this context include the following: -CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH = CHCH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH(CH ３ )CH ２ CH ２ CH ２ CH (CH ３ ) ２ -CH(CH ３ )CH=CHCH(CH ３ )CH(CH ３ ) ２

[0088] In other preferred embodiments, the isoprenoid compound of the present disclosure is of the following formula (III): This is a compound containing a structure (hereinafter also referred to as structure (III)) which may include unsaturated bonds between adjacent ring member carbons, represented by .

[0089] In the above structure (III), each carbon atom constituting the ring is referred to by the number shown in the following formula.

[0090] In a more preferred embodiment, structure (III) has two methyl groups at the C4 position, at least one methyl group at the C8, C10, and C20 positions, and contains a double bond between the C12 and C13 carbon atoms, as represented by the following formula (III-2).

[0091] Furthermore, hydrogen atoms in structure (III-2) may be substituted with substituents (i.e., monovalent groups). In particular, it is preferable that one of the two hydrogen atoms on the C3 position, one of the two hydrogen atoms on the C17 position, and the hydrogen atom on the C20 position are substituted with substituents. It is preferable that the hydrogen atoms on the other carbons are not substituted with substituents. In addition, in structure (III-2), a carbon-carbon double bond may be formed between carbon atoms other than those between the C12 and C13 positions by the elimination of one hydrogen atom from each of two adjacent carbon atoms, but it is preferable that structure (III-2) does not contain double bonds other than those between the C12 and C13 positions.

[0092] Examples of substituents at the C3 position include -R ２ -OH, -OR ２ , -NR ２ ２ , -OC(=O)-R ２ , -C(=NR ２ ) R ２ , -COOH, -C(=O)-OR ２ , -OC(=O)-OR ２ , -C(=O)-NR ２ ２ , -SO ２ (NR ２ ) ２ It is acceptable (R ２ Each of these is independently a hydrogen atom, a halogen atom, or C １－４０(Hydrogen group). The halogen atom may be fluorine, bromine, chlorine, or iodine. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be a saturated aliphatic hydrocarbon group (e.g., an alkyl group), or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear, for example, linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group may be a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less.

[0093] In a preferred embodiment, the substituent at the C3 position is -OH.

[0094] Examples of substituents at the C17 position include -R ２ -OH, -OR ２ , -NR ２ ２ , -OC(=O)-R ２ , -COOH, -C(=NR ２ ) R ２ , -C(=O)-OR ２ , -OC(=O)-OR ２ , -C(=O)-NR ２ ２ , -SO ２ (NR ２ ) ２ It is acceptable (R ２ Each of these is independently a hydrogen atom, a halogen atom, or C １－４０(Hydrogen group). The halogen atom may be fluorine, bromine, chlorine, or iodine. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be a saturated aliphatic hydrocarbon group (e.g., an alkyl group), or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear, for example, linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group may be a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less.

[0095] In a preferred embodiment, the substituent at the C17 position is -COOH.

[0096] Examples of substituents at the C20 position include -R ２ , -OR ２ , -NR ２ ２ , -COOH, -OC(=O)-R ２ , -C(=NR ２ ) R ２ , -C(=O)-OR ２ , -OC(=O)-OR ２ , -C(=O)-NR ２ ２ , -SO ２ (NR ２ ) ２ It is acceptable (R ２ Each of these is independently a hydrogen atom, a halogen atom, or C １－４０(Hydrogen group). The halogen atom may be fluorine, bromine, chlorine, or iodine. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may be a saturated aliphatic hydrocarbon group (e.g., an alkyl group), or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear, for example, linear. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group may be a saturated aliphatic hydrocarbon group (alkyl group). The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, and may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less.

[0097] In one preferred embodiment, the substituent at the C20 position is -R ２１ (In the formula, R ２１ is a hydrogen atom, halogen atom or C １－４０ (The hydrocarbon group is) The halogen atom and hydrocarbon group are as follows: ２ It may be the same as R. ２１ C is a hydrogen atom. １－４０ It is more preferable that the hydrocarbon group is a hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group (e.g., an alkyl group), or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear. If the hydrocarbon group is substituted, it is preferable that it is substituted with an alkyl group (e.g., a methyl group or an ethyl group), and it is preferable that it is not substituted with substituents other than alkyl groups. The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, 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. ２１ The number of carbon atoms in the hydrocarbon group is preferably 1 to 30, more preferably 1 to 10, and even more preferably 1 to 5, with a methyl group being particularly preferred.

[0098] In another preferred embodiment, the substituent at the C20 position is -C(=O)-OR ２１ (In the formula, R ２１ is a hydrogen atom, halogen atom or C １－４０ (The hydrocarbon group is) The halogen atom and hydrocarbon group are as follows: ２ It may be the same as R. ２１ C １－４０ It is more preferable that the hydrocarbon group is a hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group (e.g., an alkyl group), or an unsaturated aliphatic hydrocarbon group (e.g., an alkenyl group). The hydrocarbon group may be branched or linear. If the hydrocarbon group is substituted, it is preferable that it is substituted with an alkyl group (e.g., a methyl group or an ethyl group), and it is preferable that it is not substituted with substituents other than alkyl groups. The number of carbon atoms in the hydrocarbon group may be 1 or more, 2 or more, 4 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, 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. ２２ The number of carbon atoms in the hydrocarbon group is preferably 2 to 30, more preferably 3 to 25, and even more preferably 6 to 20.

[0099] R ２１ Specific examples of hydrocarbon groups in this context include the following: -CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH=CHCH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ CH ３ -CH(CH ３ )CH ２ CH ２ CH ２ CH(CH ３ )２ -CH(CH ３ )CH=CHCH(CH ３ )CH(CH ３ ) ２

[0100] Specific examples of isoprenoid compounds included in the surface modifiers of this disclosure include β-carotene, squalene, β-caryophyllene, oleanolic acid, stearyl glycyrrhetinate, brassicasterol, stigmasterol, cholesterol, cholecalciferol, β-sitosterol, ergosterol, cholesteryl oleate, cholesteryl myristart, cholesteryl stearate, cholesterol butyrate, cholesteryl linoleate, cholesterol benzoate, cholesteryl decanoate, cholesterol-5-en-3-ol, and cholesteryl oleyl carbonate.

[0101] Preferred specific examples of isoprenoid compounds included in the surface modifiers of this disclosure include β-carotene, oleanolic acid, brassicasterol, stigmasterol, cholesterol, cholecalciferol, β-sitosterol, ergosterol, cholesteryl oleate, cholesteryl myristart, cholesteryl stearate, cholesterol butyrate, cholesteryl linoleate, cholesterol benzoate, and cholesteryl decanoate.

[0102] The isoprenoid compounds contained in the surface modifiers of this disclosure are preferably derived from natural products, and are preferably compounds biosynthesized in plants, animals, or fungi. The isoprenoid compounds can be isolated, for example, by subjecting an extract of a specific plant to processes such as centrifugation, distillation, recrystallization, or chromatography. Alternatively, the isoprenoid compounds may be commercially available products.

[0103] [Composition of the Isoprenoid Compound] The isoprenoid compound contained in the surface modifier of this disclosure may be one type only, or two or more types may be used in combination. The amount of the isoprenoid compound may be 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, or 90% by weight or more, based on the total weight of the surface modifier, or 95% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, 55% by weight or less, 45% by weight or less, 35% by weight or less, 25% by weight or less, 15% by weight or less, or 5% by weight or less.

[0104] [Dispersant] The surface modifier of the present disclosure preferably contains a dispersant (for example, a cationic dispersant).

[0105] The dispersant may be at least one selected from organic dispersants and inorganic dispersants. The dispersant may be at least one selected from anionic dispersants, nonionic dispersants, cationic dispersants, amphoteric dispersants, and inorganic dispersants.

[0106] The dispersant preferably contains a cationic dispersant. The dispersant may be a cationic dispersant alone, or it may be used in combination with other dispersants. Examples of dispersant combinations include a combination of a cationic dispersant and a nonionic dispersant, a combination of a cationic dispersant and an anionic dispersant, a combination of a cationic dispersant and an amphoteric dispersant, a combination of a cationic dispersant and an inorganic dispersant, and so on, with a preferred combination being a cationic dispersant and a nonionic dispersant. The surface modifier does not have to contain dispersants other than cationic dispersants, such as anionic dispersants and / or nonionic dispersants (e.g., anionic dispersants). The dispersant may contain dispersants other than fatty acid esters having an HLB value of 7 or higher. For example, the dispersant may contain a fatty acid ester-based dispersant having an HLB value of less than 7, or it may contain dispersants other than fatty acid esters.

[0107] The dispersant may be either an organic dispersant or an inorganic dispersant, or a combination of both.

[0108] Organic dispersants may be used as dispersants. Organic dispersants can be classified into nonionic dispersants, anionic dispersants, cationic dispersants, and amphoteric dispersants, and the term "organic dispersant" may refer to surfactants.

[0109] The dispersant may be hydrocarbon-based.

[0110] [Nonionic Dispersant] The dispersant may contain a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0111] The nonionic 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, 750 or less, or 250 or less.

[0112] Examples of nonionic dispersants include ethers, esters, ester ethers, alkanolamides, polyols, and amine oxides.

[0113] Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

[0114] Examples of esters are esters of alcohols and fatty acids. Examples of alcohols are alcohols with 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) with 1 to 30 valencies (especially 2 to 10 valencies) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0115] Examples of ester ethers are compounds obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols with 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) with a novalence of 1 to 30 (especially 2 to 10) (e.g., aliphatic alcohols). Examples of fatty acids are saturated or unsaturated fatty acids with 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.

[0116] Examples of alkanolamides are formed from fatty acids and alkanolamines. Alkanolamides may be monoalkanolamides or dialkanolaminos. Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. Alkanolamines may be alkanols having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

[0117] The polyol may be a divalent to pentavalent alcohol having 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).

[0118] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The number of carbon atoms in the alkylene group of the oxyalkylene group is preferably 2 to 10. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0119] 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.

[0120] The nonionic dispersant may be an alkylene oxide adduct of linear and / or branched aliphatic (saturated and / or unsaturated) groups, a polyalkylene glycol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sorbitan ester of linear and / or branched fatty acids (saturated and / or unsaturated), a glycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyglycerol ester of linear and / or branched fatty acids (saturated and / or unsaturated), a sucrose ester of linear and / or branched fatty acids (saturated and / or unsaturated), a polyoxyethylene (POE) / polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, and the like. Among these, those in which the alkylene oxide addition portion and the polyalkylene glycol portion are structured as polyoxyethylene (POE), polyoxypropylene (POP), or a POE / POP copolymer (which may be a random copolymer or a block copolymer) are preferred. Furthermore, the nonionic dispersant does not need to contain aromatic groups.

[0121] Nonionic dispersants are given by formula: R １ O-(CH ２ CH ２ O) ｐ - (R ２ O) ｑ -R ３ [In the formula, R １ R is an alkyl group having 1 to 22 carbon atoms, or an alkenyl group or acyl group having 2 to 22 carbon atoms. ２ Each of them is independently identical or distinct, an alkylene group having 3 or more carbon atoms (for example, 3 to 10), R ３ The compound may be represented by [where p is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms, p is a number of 2 or more, and q is a number of 0 or 1 or more].

[0122] R １ The carbon atoms have 8 to 20 carbon atoms, and are more preferably 10 to 18 carbon atoms. １Preferred specific examples include the octyl group, nonyl group, trimethylnonyl group, lauryl group, tridecyl group, oleyl group, and stearyl group. ２ Examples include propylene groups and butylene groups. In nonionic dispersants, p may be a number of 3 or more (e.g., 5 to 200). q may be a number of 2 or more (e.g., 5 to 200). That is, -(R ２ O) ｑ - may form a polyoxyalkylene chain. The nonionic dispersant may be a polyoxyethylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. Examples of hydrophobic oxyalkylene chains include oxypropylene chains, oxybutylene chains, and styrene chains, but oxypropylene chains are preferred among them.

[0123] Specific examples of nonionic dispersants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, and alkanes (C). １２ -C １６ ) Thiol, sorbitan monofatty acid (C ７ -C １９ ) or alkyl (C １２ -C １８ This includes 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.

[0124] The proportion of polyoxyethylene blocks can be 5 to 80% by weight, for example 30 to 75% by weight, and particularly 40 to 70% by weight, relative to the molecular weight of the nonionic dispersant (copolymer). The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example 500 to 3,000. The nonionic dispersant may be a single type or a mixture of two or more types. The nonionic dispersant may be a mixture of a compound with an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound with an HLB of 15 or more. Specifically, it is preferable to select from polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene, polyoxypropylene with HLBs of 1 to 18, or sorbitan fatty acid esters, glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene sorbitan fatty acid esters with HLB values ​​of less than 7.

[0125] [Cationic Dispersant] The dispersant may contain a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound that does not have an amide group.

[0126] The cationic dispersant may be of low molecular weight (for example, molecular weight of 2000 or less, particularly 10000 or less) or high molecular weight (for example, 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, 100000 or less, 7500 or less, 50000 or less, 250000 or less, 750 or less, or 250 or less.

[0127] Cationic dispersants may be aliphatic or aromatic, such as ammonium salts (e.g., quaternary ammonium salts). Cationic dispersants may also be oxyethylene-added ammonium salts. Specifically, examples include amine salt type dispersants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazoline; quaternary ammonium salt type dispersants such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, and benzethonium chloride; and polymeric cationic dispersants such as polyquaternium-1 to 47.

[0128] Low molecular weight cationic dispersants are R ２１ -N ＋ (-R ２２ ) (-R ２３ ) (-R ２４ ) X － [In the formula, R ２１ , R ２２ , R ２３ and R ２４ R is a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, and X is an anionic group. The compound may be represented by [ ]. ２１ , R ２２ , R ２３ and -R ２４ Specific examples of X are alkyl groups (e.g., methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogens (e.g., chlorine) and acids (e.g., hydrochloric acid, acetic acid). The cationic dispersant may be a monoalkyltrimethylammonium salt (alkyl group with 4 to 40 carbon atoms).

[0129] Specifically, low molecular weight cationic dispersants are defined by formula: R １ ｐ -N ＋ R ２ ｑ X － [In the formula, R １ is C12 or higher (for example, C １２ ~C ５０ ) is a linear and / or branched aliphatic (saturated and / or unsaturated) group, R ２(CH) is an H or C1-C4 alkyl group, a benzyl group, a polyoxyethylene group (number of oxyethylene groups e.g., 1 (especially 2, particularly 3) to 50) ３ , C ２ H ５ (particularly preferred) where X is a halogen atom (e.g., chlorine), or C １ ~C ４ fatty acid salts, or C １ ~C ４ It is a sulfonate of , where p is 1 or 2, q is 2 or 3, and p + q = 4. It may be an ammonium salt represented by ]. １ The number of carbon atoms may be 12 to 50, for example, 12 to 30.

[0130] 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, etc.

[0131] The polymeric cationic dispersant may be various polymers (e.g., polyquaternium-1 to 47) having cationic groups (e.g., ammonium groups, quaternary ammonium groups). Examples of polymeric cationic dispersants include cationized starch, cationized cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propylhydroxyethylcellulose chloride), cationized guar gum, cationized xanthan gum, chitosan, and other cationized natural products (especially cationized sugars); 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 methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine, and quaternized vinylimidazole.

[0132] [Anionic Dispersant] The dispersant may contain an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant does not have to contain an anionic dispersant.

[0133] 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, 25000 or less, 750 or less, or 250 or less.

[0134] Examples of anionic dispersants include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfone fatty acid salts, N-acyl amino acid type dispersants, phosphate mono or diester type dispersants, and sulfosuccinate esters.

[0135] [Amphoteric Dispersant] The dispersant may contain an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0136] 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, 25000 or less, 750 or less, or 250 or less.

[0137] Examples of amphoteric dispersants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, these include lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[0138] [Inorganic Dispersant] The dispersant may contain an inorganic dispersant.

[0139] The average primary particle size of the inorganic dispersant may be 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 μm or larger, 10 μm or larger, or 25 μm or larger, and may also be 100 μm or smaller, 50 μm or smaller, 10 μm or smaller, 1 μm or smaller, 500 nm or smaller, or 300 nm or smaller. The average primary particle size can be measured, for example, by observation with a microscope (scanning electron microscope or transmission electron microscope). The inorganic dispersant may also be hydrophilic particles.

[0140] Examples of inorganic dispersants include polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; silicates such as calcium metasilicate; sulfates such as calcium sulfate and barium sulfate; and hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0141] [Amount of dispersant] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 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.

[0142] [Liquid Medium] The surface modifier in this disclosure may include a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The surface modifier may be a dispersion or a solution. The surface modifier in this disclosure is water-dispersible and may be in the form of a water-dispersible composition containing at least water.

[0143] Examples of organic solvents include esters (e.g., esters with 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (e.g., ketones with 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (e.g., alcohols with 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (e.g., toluene and xylene), and petroleum solvents (e.g., alkanes with 5 to 10 carbon atoms, specifically naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may contain compounds having at least one hydroxyl group (e.g., polyols such as alcohols and glycol-based solvents, ethers of polyols (e.g., monoethers)). These may be used individually or in combination of two or more.

[0144] [Amount of liquid medium] The amount of liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the liquid-repellent compound. Alternatively, it may be 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.

[0145] 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, or 3000 parts by weight or less, 2000 parts by weight or less, 1000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less, per 1 part by weight of the liquid-repellent compound.

[0146] The amount of organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1000 parts by weight or more, per 1 part by weight of the liquid-repellent compound, or 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.

[0147] [Silicone] The surface modifier in this disclosure may include silicone (polyorganosiloxane). By including silicone, it is possible to achieve good liquid repellency in addition to good texture and durability.

[0148] As the silicone, known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified, epoxy-modified, carboxy-modified, methylhydrogen silicone, etc.). The silicone may also be a silicone wax having waxy properties. These may be used alone or in combination of two or more.

[0149] The weight-average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may also be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[0150] [Amount of Silicone] The amount of silicone may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 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.

[0151] [Wax] The surface modifier in this disclosure may include wax. Including wax can provide good liquid repellency to the substrate.

[0152] Examples of waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable waxes, and mineral waxes. Paraffin wax is preferred. Specific examples of compounds that constitute the wax include n-alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane) and n-alkenes (e.g., 1-eicosene, 1-docosene, 1-tricocene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The number of carbon atoms in the compounds that constitute the wax is preferably 20 to 60, for example, 25 to 45. The molecular weight of the wax may be 200 to 2000, for example, 250 to 1500 or 300 to 1000. These may be used alone or in combination of two or more.

[0153] The melting point of the wax may be 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, preferably 55°C or higher, and more preferably 60°C or higher. The melting point of the wax is measured in accordance with JIS K 2235-1991.

[0154] [Amount of wax] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of the liquid-repellent compound, or 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.

[0155] [Organic Acids] The surface modifiers of the present disclosure may contain organic acids. Known organic acids can be used. Preferred organic acids include carboxylic acids, sulfonic acids, sulfinic acids, etc., with carboxylic acids being particularly preferred. Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred. In the present disclosure, one organic acid may be used, or two or more may be used in combination. For example, formic acid and acetic acid may be used in combination.

[0156] [Amount of Organic Acid] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more per 100 parts by weight of the liquid-repellent compound, or 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 surface modifier is 3 to 10, for example 5 to 9, particularly 6 to 8. The surface modifier may be acidic (pH 7 or less, for example 6 or less).

[0157] [Curing agent] The surface modifier of this disclosure may contain a curing agent (an active hydrogen-reactive compound or an active hydrogen-containing compound).

[0158] The curing agent (crosslinking agent) in the surface modifier can cure the liquid-repellent compound well. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the liquid-repellent compound. Examples of the active hydrogen-reactive compound are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds, and hydrazide compounds. Examples of the active hydrogen-containing compound are hydroxyl group-containing compounds, amino group-containing compounds, carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds, and melamine compounds.

[0159] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound 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.

[0160] 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, and 2,6-diiso These include aliphatic diisocyanates such as cyanatomethyl caproate, lysine ester triisocyanates, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used alone or in combination of two or more.

[0161] Examples of alicyclic polyisocyanates include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used individually or in combination of two or more.

[0162] Examples of aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates and aromatic aliphatic triisocyanates. Specific examples of aromatic aliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethylxylylene diisocyanate) or mixtures thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used individually or in combination of two or more.

[0163] 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, etc. These may be used alone or in combination of two or more thereof.

[0164] 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 thereof.

[0165] These polyisocyanates can be used singly or in combination of two or more kinds. 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 surface modifier.

[0166] The blocking agent blocks the free isocyanate groups. The blocked polyisocyanate compound can regenerate isocyanate groups and easily react with hydroxyl groups, for example, by heating to 100 °C or higher, for example, ially 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 kinds.

[0167] Epoxy compounds are compounds that contain an epoxy group. Examples of epoxy compounds include epoxy compounds containing a polyoxyalkylene group, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether. Chloromethyl group-containing compounds are compounds that contain a chloromethyl group. Examples of chloromethyl group-containing compounds include chloromethyl polystyrene. Carboxyl group-containing compounds are compounds that contain a carboxyl group. Examples of carboxyl group-containing compounds include (poly)acrylic acid and (poly)methacrylic acid.

[0168] Specific examples of ketone group-containing compounds include (poly)diacetone acrylamide and diacetone alcohol. Specific examples of hydrazide compounds include hydrazine, carbohydrazide, and adipic acid hydrazide. Specific examples of melamine compounds include melamine resin and methyl etherified melamine resin.

[0169] [Amount of curing agent] The amount of curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, or 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, per 100 parts by weight of the liquid-repellent compound, or 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.

[0170] [Other Components] Surface modifiers may contain other components besides those listed above. Examples of other components include polysaccharides, paper strength enhancers, flocculants, yield enhancers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength enhancers, fillers, antistatic agents, preservatives, UV absorbers, antibacterial agents, deodorizers, fragrances, etc. These may be used alone or in combination of two or more.

[0171] In addition to the above-mentioned components, other components include other water-repellent and / or oil-repellent agents, dispersants, texture modifiers, softeners, flame retardants, paint fixatives, wrinkle inhibitors, drying speed modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, insect repellents, defoamers, shrinkage inhibitors, wrinkle inhibitors, shape-retaining agents, drape-retaining agents, ironing improvers, whitening agents, whitening agents, fabric softening clay, color transfer inhibitors such as polyvinylpyrrolidone, polymer dispersants, stain removers, scum dispersants, fluorescent whitening agents such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Chinopearl CBS-X, manufactured by Ciba Specialty Chemicals), dye fixatives, and color-fading inhibitors such as 1,4-bis(3-aminopropyl)piperazine. In addition, enzymes such as cellulase, amylase, protease, lipase, and keratinase can be used as stain removers and fiber surface modifiers; silk protein powder can be used as a foam inhibitor and to impart the texture and functionality of silk, such as moisture absorption and release properties; surface modifiers or emulsified dispersions thereof (e.g., K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Solubble S (Ichimaru Falcos)); and anti-fouling agents (e.g., nonionic polymer compounds consisting of alkylene terephthalate and / or alkylene isophthalate units and polyoxyalkylene units (e.g., FR627 manufactured by Go-o Chemical Industry), SRC-1 manufactured by Clariant Japan, etc.) can be incorporated. These may be used individually or in combination of two or more.

[0172] [Polysaccharides] Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofibers, cellulose nanofibers, and pullulan. Polysaccharides may be substituted modified polysaccharides (excluding the liquid-repellent compounds mentioned above), and in particular, modified polysaccharides to which hydroxyl groups or cationic groups have been introduced.

[0173] [Paper Strength Enhancers, Flocculants, Yield Enhancers, or Coagulants] Examples of paper strength enhancers, flocculants, yield enhancers, or coagulants include styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, alkylenedichloride-polyalkylene polyamine condensates, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0174] [Sizing agents] Examples of sizing agents include cellulose-reactive sizing agents, such as rosin-based sizing agents like rosin soap, rosin-based emulsions / dispersions, cellulose-reactive sizing agents, such as emulsions / dispersions of acid anhydrides like alkyl and alkenyl succinic anhydrides (ASA), alkenyl and alkyl ketene dimers (AKD) and polymers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as copolymers of styrene and acrylate.

[0175] [Antistatic Agents] Examples of antistatic agents include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, alanine and its derivatives; and nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, polyethylene glycol and its derivatives. These may also be ion-conductive polymers obtained by polymerizing or copolymerizing monomers having cationic, anionic, or amphoteric ion-conductive groups. These may be used alone or in combination of two or more.

[0176] [Preservatives] Preservatives are mainly used to enhance preservative and bactericidal properties and maintain preservation during long-term storage. Examples of preservatives include isothiazolone-type organosulfur compounds, benzisothiazolone-type organosulfur compounds, benzoic acids, and 2-bromo-2-nitro-1,3-propanediol.

[0177] [UV absorbers] UV absorbers are chemicals that have the effect of protecting against ultraviolet rays. They absorb ultraviolet rays and convert them into infrared rays, visible light, etc., and release them. Examples of UV absorbers include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.

[0178] [Antibacterial agents] Antibacterial agents are components that suppress the growth of bacteria on fibers and also suppress the generation of unpleasant odors derived from microbial decomposition products. Examples of antibacterial agents include cationic disinfectants such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine.

[0179] [Deodorizers] Examples of deodorizers include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, and aminocarboxylic acid metal complexes (such as the zinc complex of trisodium methylglycinediacetate described in International Publication No. 2012 / 090580).

[0180] [Amount of other components] The amount of each or total amount of other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the liquid-repellent compound, or 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.

[0181] <Method for manufacturing modified textile or paper products> The method for manufacturing a product modified with a surface modifier in this disclosure includes a processing step of modifying a substrate with the surface modifier described above.

[0182] "Treatment" means applying a surface modifier to a substrate by immersion, spraying, coating, etc. Through treatment, the liquid-repellent compound, which is the active ingredient of the surface modifier, adheres to the interior and / or surface of the substrate. Here, adhesion may be physical or chemical, and for example, the liquid-repellent compound may be physically or chemically modified (by reaction) the hydroxyl groups present in the substrate (fibers, paper, glass, etc.).

[0183] [Substrate] The substrate to be modified by the surface modifier in this disclosure is not limited, but is preferably a textile product or a paper product, particularly a paper product.

[0184] The surface modifiers in this disclosure impart liquid repellency to a substrate (e.g., a fibrous substrate, a paper substrate) and can function as at least one selected from the group consisting of water repellents, oil repellents, oil-resistant agents, and water-resistant agents. A substrate modified with a surface modifier in this disclosure is, for example, oil-resistant paper or water-resistant paper.

[0185] Examples of base materials for textile products include natural animal and plant fibers such as cotton, linen, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers; or blends thereof. Textile products include woven fabrics, knitted fabrics, and nonwoven fabrics; fabrics in the form of clothing (e.g., water-repellent clothing, e.g., raincoats) and carpets; however, fibers, yarns, and intermediate textile products (e.g., slivers or rovings) in their pre-fabric state may also be treated.

[0186] Examples of base materials for paper products include paper made from bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp, recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard or deinked paper, as well as containers and molded bodies made of paper. Specific examples of paper products include food packaging materials, food containers, gypsum board base paper, coated base paper, medium-grade paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, neutral printing and writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (molded containers), etc. Preferred examples include food packaging materials and food containers.

[0187] The substrates to be modified with the surface modifiers of this disclosure are not limited to textile products or paper products, but can also include stone, filters (e.g., electrostatic filters), dust masks, fuel cell components (e.g., gas diffusion electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.

[0188] When the substrate is glass, the manufactured glass product may be an optical component. A layer (or film), such as a hard coat layer or an anti-reflective layer, may be formed on the surface (outermost layer) of the glass substrate. Either a single-layer anti-reflective layer or a multi-layer anti-reflective layer may be used for the anti-reflective layer. An example of an inorganic material that can be used for the anti-reflective layer is SiO₂. ２ SiO, ZrO ２ , TiO ２ ,TiO,Ti ２ O ３ Ti ２ O ５ Al ２ O ３ Ta ２ O ５ , CEO ２ , MgO, Y ２ O ３ , SnO ２ MgF ２ WO ３These are some examples. These inorganic materials may be used individually or in combination of two or more (for example, as a mixture). When a multilayer anti-reflective layer is used, the outermost layer is SiO ２ It is preferable to use and / or SiO. If the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode, such as indium tin oxide (ITO) or indium zinc oxide, may be present on a part of the surface of the substrate (glass). The substrate may also have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, and a liquid crystal display module, depending on its specific specifications.

[0189] [Processing Method] The surface modifier of the present disclosure can be applied to a substrate as a processing agent (especially a surface modifier) ​​by conventionally known methods. The processing method may involve dispersing and diluting the surface modifier of the present disclosure in an organic solvent or water as necessary, and then applying it to the interior and / or surface of the substrate by known methods such as immersion coating, spray coating, foam coating, etc., and drying. After drying, a product with the solid components of the surface modifier attached is obtained. If necessary, it may also be applied together with a suitable crosslinking agent and curing may be performed. The surface modifier of the present disclosure may also be used in combination with various additives as necessary, such as water-repellent and / or oil-repellent agents, anti-slip agents, antistatic agents, texture modifiers, softeners, antibacterial agents, flame retardants, paint fixatives, anti-wrinkle agents, drying rate modifiers, crosslinking agents, film-forming aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insecticides, and defoaming agents. Examples of various additives may be the same as those described under "other components" in the above explanation. The concentration of the surface modifier in the treatment agent that comes into contact with the substrate may be changed as appropriate depending on the application, but may be 0.01 to 10% by weight, for example, 0.05 to 5% by weight.

[0190] The surface modifier can be applied to the substrate by any known method for modifying the substrate with a liquid. The substrate may be immersed in the surface modifier, or the solution may be applied to or sprayed onto the substrate. The modified substrate is preferably dried and cured by heating 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 this disclosure, good performance can be obtained even with low-temperature heating (e.g., 100°C to 140°C). In this disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes. When the textile product is paper, the surface modifier may be applied to the paper, or the solution may be applied to or sprayed onto the paper, or it may be mixed with the pulp slurry before papermaking to modify it. The modification may be external or internal. Alternatively, the surface modifier may be applied to the textile product by a cleaning method, for example, by washing or dry cleaning.

[0191] [Modification of paper products] Examples of paper substrates include paper, paper containers, and molded articles made of paper (e.g., pulp molds). The liquid-repellent compounds of this disclosure adhere well to paper substrates.

[0192] Paper can be manufactured using conventionally known papermaking methods. Either an internal modification method, in which a surface modifier is added to the pulp slurry before papermaking, or an external modification method, in which a surface modifier is applied to the paper after papermaking, can be used.

[0193] The size press of the external modification method can also be classified as follows according to the coating method. One coating method is the so-called pond-type two-roll size press that supplies a coating liquid (size liquid) to a nip formed by passing paper between two rubber rolls, creates a coating liquid reservoir called a pond, and passes the paper through this coating liquid reservoir to coat the size liquid on both sides of the paper. The other coating methods are the gate roll type that applies the size liquid by a surface transfer type, and the rod metering size press. In the pond-type two-roll size press, the size liquid easily penetrates to the inside of the paper, and in the surface transfer type, the size 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 compared to the pond-type two-roll size press, and the coating layer formed on the surface is more than that of 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 modified in this way can exhibit excellent oil resistance and water resistance, etc. by undergoing heat modification that can take an arbitrary temperature range up to 300 °C, for example up to 200 °C, particularly in the temperature range of 80 °C to 180 °C, depending on the properties of the paper, after simple drying at room temperature or high temperature.

[0194] The internal modification method may mean a modification method of adding a surface modifier to the pulp slurry before papermaking. As the internal modification method, it may include one or more of the steps of adding a surface modifier to the pulp slurry and stirring and mixing, suction-dehydrating the pulp composition prepared in this step through a reticular body of a predetermined shape to deposit the pulp composition to form an intermediate pulp mold, and molding and drying the intermediate pulp mold with a heated mold to obtain paper, a container made of paper, or a molded body made of paper, but it is not limited to this. The modified paper may optionally be heat-modified depending on the properties of the paper after simple drying at room temperature or high temperature. The temperature of the heat modification may be 150 °C or higher, 180 °C or higher, or 210 °C or higher, and may be 300 °C or lower, 250 °C or lower, or 200 °C or lower, particularly 80 °C to 180 °C. By performing heat modification within such a temperature range, excellent oil resistance and water resistance, etc. can be exhibited.

[0195] This disclosure can be used in gypsum board base paper, coated base paper, medium quality paper, general liners and cores, neutral pure white roll paper, neutral liners, rust-preventive liners and metal interleaving paper, kraft paper, and the like. It can also be used in 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.

[0196] Any of the following can be used as pulp raw materials: bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp; bleached or unbleached high-yield pulps such as crushed wood pulp, mechanical pulp or thermomechanical pulp; or recycled paper pulp such as recycled newspaper, recycled magazine, recycled corrugated cardboard, or deinked recycled paper. In addition, mixtures of the above pulp raw materials with synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.

[0197] The water resistance of paper can be improved by adding a sizing agent. Examples of sizing agents include cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (e.g., acidic rosin-based sizing agents, neutral rosin-based sizing agents). The amount of sizing agent may be 0.01 to 5% by weight relative to the pulp.

[0198] If necessary, the paper may be treated with additives used in papermaking, such as starch, modified starch, carboxymethylcellulose, polyamide polyamine-epichlorohydrin resin (paper strength enhancers), flocculants, fixatives, yield enhancers, dyes, fluorescent dyes, slime control agents, and defoamers, in amounts commonly used in papermaking. Starch and modified starch are preferred. If necessary, surface modifiers such as starch, polyvinyl alcohol, dyes, coating colors, and anti-slip agents can be applied to the paper using a size press, gate roll coater, bill blade coater, calender, etc.

[0199] In the case of external addition, the amount of liquid-repellent compound contained in the coating layer is 0.01 to 2.0 g / m². ２ , especially 0.1 to 1.0 g / m ２Preferably, the coating layer is formed of a surface modifier and starch and / or modified starch. The solid content of the paper surface modifier in the coating layer is 2 g / m². ２ The following is preferable:

[0200] In the internal addition process, it is preferable to mix the surface modifier with the pulp such that the amount of surface modifier is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, and particularly 0.2 to 5.0 parts by weight, per 100 parts by weight of pulp used to form the paper.

[0201] In external application, oil resistance can also be imparted to paper by using a so-called pound-type two-roll size press process, in which the processing liquid is stored between the rolls and the base paper is passed through the processing liquid between the rolls at an arbitrary roll speed and nip pressure.

[0202] In external modification, the paper substrate may contain additives such as sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants. The additives may be nonionic, cationic, anionic, or amphoteric. The ionic charge density of the additives is -10,000 to 10,000 μeq / g, preferably -4,000 to 8,000 μeq / g, and more preferably -1,000 to 7,000 μeq / g. Additives such as sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants (solid content or active ingredients) can generally be used in an amount of 0.1 to 10% by weight (e.g., 0.2 to 5.0% by weight) relative to the pulp. In the case of a paper substrate containing cationic additives (e.g., sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants), the surface modifier is preferably anionic.

[0203] In internal modification, it is preferable to papermake a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (for example, sizing agents, paper strength enhancers, flocculants, yield enhancers or coagulants, etc.) and liquid-repellent compounds can be added to the pulp slurry. Examples of additives (e.g., sizing agents, paper strength enhancers, flocculants, yield enhancers, or coagulants) include alkyl ketene dimers, alkenyl succinic anhydride, styrene polymers (styrene / maleic acid polymers, styrene / acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimines, melamine-formaldehyde polymers, polyamidoamine-epichlorohydrin polymers, polyacrylamide polymers, polyamine polymers, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensates, alkylenedichloride-polyalkylene polyamine condensates, dicyandiamide-formaldehyde condensates, dimethyldiallylammonium chloride polymers, and olefin / maleic anhydride polymers.

[0204] [Pretreatment of Textile Products] Textile products may be pretreated before being modified with the surface modifiers of this disclosure. Pretreatment of textile products can impart excellent durability to the textile products after modification with the surface modifiers.

[0205] Examples of pretreatments for textile products include cationization by reaction with reactive quaternary ammonium salts, anionization by sulfonation, carboxylation, phosphorylation, etc., acetylation, benzoylation, carboxymethylation, grafting, tannic acid treatment, and polymer coating after anionization.

[0206] The method for pre-treating textile products is not limited, but conventionally known methods can be used. The pre-treatment solution may be diluted by dispersing it in an organic solvent or water as needed, and then applied to the interior and / or surface of the textile product by known methods such as immersion coating, spray coating, or foam coating, followed by drying. The pH and temperature of the pre-treatment solution may be adjusted according to the desired degree of treatment. As an example of a method for pre-treating textile products, a method of pre-treating textile products with the above-mentioned treatment agent will be described in detail below.

[0207] The pretreatment method for textile products involves applying -SO to the fibers. ３ M １ (In the formula, M １ (represents a monovalent cation) a monovalent group represented by -COOM ２ (In the formula, M ２ A monovalent group represented by (where represents a monovalent cation), and -O-P(O)(OX １ ) (OX ２ ) (wherein, X １ and X ２ The process may include a step of adding one or more functional groups (hereinafter sometimes referred to as "specific functional groups") selected from the group consisting of monovalent groups (each representing a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).

[0208] M １ Examples include H, K, Na, or ammonium ions which may have substituents. ２ Examples include H, K, Na, or ammonium ions which may have substituents. １ or X ２ If it is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, and more preferably an alkyl group having 4 to 12 carbon atoms.

[0209] Fibers containing the above-mentioned specific functional groups (hereinafter sometimes referred to as "functional group-containing fibers") can be prepared, for example, by the following methods: (i) A compound having the above-mentioned specific functional group is attached to a fiber material. Note that the attachment of the compound may be such that a portion of the compound and a portion of the fiber are chemically bonded, to the extent that a sufficient amount of the above-mentioned specific functional group remains. (ii) Fibers are prepared in which the above-mentioned specific functional group is directly introduced into the material constituting the fiber.

[0210] (i) For example, a functional group-containing fiber can be obtained by a functional group introduction step in which the fiber material is treated with a pretreatment solution containing one or more compounds having the above-mentioned specific functional group.

[0211] There are no particular restrictions on the material of the fiber material, and examples include natural fibers such as cotton, linen, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; and composite fibers and blended fibers thereof. The fiber material may take any form, such as fibers (tow, sliver, etc.), yarn, knitted fabrics (including interwoven fabrics), woven fabrics (including interwoven fabrics), and nonwoven fabrics.

[0212] In this embodiment, from the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use a fiber material containing polyamide and polyester as a base material. In particular, it is preferable to use nylon such as nylon 6 and nylon 6,6, polyester such as polyethylene terephthalate (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.

[0213] Above - SO ３ M １ As a compound having this property, phenolic polymers can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.

[0214] [In the formula, X ２ Ha-SO ３ M ３ (In the formula, M ３ (where represents a monovalent cation) or a group represented by the following general formula, where n is an integer between 20 and 3000.

[0215] [In the formula, M ４ This represents a monovalent cation.

[0216] The above M ３ Examples include H, K, Na, or ammonium ions which may have substituents.

[0217] The above M ４ Examples include H, K, Na, or ammonium ions which may have substituents.

[0218] The compound represented by the above general formula may, for example, be a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.

[0219] Above - COOM ２ Examples of compounds having this property include polycarboxylic acid polymers.

[0220] As polycarboxylic acid polymers, for example, polymers synthesized by conventionally known radical polymerization methods using acrylic acid, methacrylic acid, maleic acid, etc. as monomers, or commercially available polymers can be used.

[0221] One method for producing polycarboxylic acid polymers is to add a radical polymerization initiator to an aqueous solution of the monomer and / or its salt, and heat the reaction at 30 to 150°C for 2 to 5 hours. At this time, alcohols such as methanol, ethanol, isopropyl alcohol, or aqueous solvents such as acetone may be added to the aqueous solution of the monomer and / or its salt. Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators formed by combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.

[0222] In radical polymerization, copolymerizable monomers can be used in addition to the monomers mentioned above. Examples of copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, as well as acrylamide, acrylates, and methacrylates. Acrylates and methacrylates are preferably those having a hydrocarbon group with 1 to 3 carbon atoms, which may have substituents such as hydroxyl groups. Examples of such acrylates or methacrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, and propyl methacrylate. These copolymerizable monomers may be used individually or in combination of two or more.

[0223] The carboxyl groups in the polycarboxylic acid polymer may be free or neutralized by alkali metals or amine compounds. Examples of alkali metals include sodium, potassium, and lithium, while examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.

[0224] The weight-average molecular weight of the polycarboxylic acid polymer is preferably 1,000 to 20,000, and more preferably 3,000 to 15,000, from the viewpoint of obtaining good water repellency in the resulting textile product.

[0225] For polycarboxylic acid polymers, commercially available products such as "NeoCrystal 770" (manufactured by Nikka Chemical Co., Ltd., product name) and "Cellopol PC-300" (manufactured by Sanyo Chemical Industries, Ltd., product name) can be used.

[0226] The above -O-P(O)(OX １ ) (OX ２ Examples of compounds having the following are phosphate ester compounds represented by the following general formula. [In the formula, X １ or X ２ This is synonymous with the above, X ３ This represents an alkyl group having 1 to 22 carbon atoms.

[0227] As the phosphate ester compound mentioned above, phosphate monoesters, diesters, and triesters in which the alkyl ester portion has an alkyl group having 1 to 22 carbon atoms, as well as mixtures thereof, can be used.

[0228] From the viewpoint of obtaining good water repellency in the resulting textile product, it is preferable to use lauryl phosphate esters and decyl phosphate esters.

[0229] For the phosphate ester compound, commercially available products such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.

[0230] The pretreatment solution containing one or more compounds having the above-mentioned specific functional groups can, for example, be an aqueous solution of the compounds described above. The pretreatment solution may also contain acids, alkalis, surfactants, chelating agents, etc.

[0231] Methods for treating fibrous materials with the above-mentioned pretreatment solution include, for example, padding, immersion, spraying, and coating. For padding, for example, methods using padding equipment described on pages 396-397 of the Dictionary of Textile Dyeing and Processing (published in 1963 by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (published in 1975 by Jikkyo Shuppan Co., Ltd.) can be used. For coating, for example, methods using coating machines described on pages 473-477 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senshi-sha) can be used. For immersion, for example, methods using batch-type dyeing machines described on pages 196-247 of the General Catalog of Dyeing and Finishing Equipment (published in 1981 by Senshi-sha) can be used, and liquid flow dyeing machines, air flow dyeing machines, drum dyeing machines, winch dyeing machines, washer dyeing machines, cheese dyeing machines, etc. can be used. Examples of spray treatments include air sprays that atomize the treatment solution using compressed air, and air sprays that use a hydraulic atomization system. The concentration of the treatment solution and the treatment conditions such as heat treatment after application can be adjusted as appropriate, taking into consideration the purpose, performance, and other conditions. If the pretreatment solution contains water, it is preferable to dry it to remove the water after it has been applied to the fiber material. There are no particular restrictions on the drying method, and either a dry heat method or a wet heat method may be used. There are no particular restrictions on the drying temperature, but for example, drying at room temperature to 200°C for 10 seconds to several days is sufficient. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180°C for about 10 seconds to 5 minutes.

[0232] Furthermore, if the fiber material is to be dyed, the pretreatment with the pretreatment solution may be performed before dyeing or in the same bath as the dyeing. However, if reducing soaping is performed, there is a risk that the compounds having the specific functional groups adsorbed during the process (for example, phenolic polymer compounds, etc.) may be removed. Therefore, it is preferable to perform the pretreatment after reducing soaping following dyeing.

[0233] The treatment temperature during the immersion process can be 60 to 130°C. The treatment time can be 5 to 60 minutes.

[0234] In the functional group introduction step using the pretreatment solution, it is preferable to treat the material in such an amount that the amount of compound having the specified functional group attached is 1.0 to 7.0 parts by weight per 100 parts by weight of the fiber material. Within this range, a high level of both durable water repellency and texture can be achieved.

[0235] The pretreatment solution is preferably adjusted to a pH of 3 to 5. pH adjustment can be done using pH adjusting agents such as acetic acid or malic acid.

[0236] In the pretreatment solution, salt can also be used in combination to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.

[0237] In the functional group introduction step using the pretreatment solution, it is preferable to remove any compounds having the specified functional groups that have been excessively treated. One method of removal is washing with water. By performing sufficient removal, it is possible to suppress the inhibition of the development of water repellency in the subsequent water-repellent treatment, and in addition, the texture of the resulting textile product will be good. Furthermore, it is preferable to thoroughly dry the resulting functional group-containing fibers before contacting them with the above-mentioned treatment agent.

[0238] (ii) Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fiber include cationic dyeable polyester (CD-PET).

[0239] From the viewpoint of obtaining good water repellency in the resulting textile product, the functional group-containing fibers preferably have a surface zeta potential of -100 to -0.1 mV, and more preferably -50 to -1 mV. The surface zeta potential of the fibers can be measured, for example, using the zeta potential and particle size measurement system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).

[0240] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0241] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0242] [Example 1] <Evaluation of water repellency: Measurement of water contact angle> To evaluate the water repellency of the surface modifier of the present disclosure, the static contact angle of water was measured. Specifically, a solution containing 1% by mass of oleanolic acid in chloroform was prepared, and this solution was placed on a silicon substrate and a film was fabricated by spin coating at 2000 rpm for 25 seconds. After annealing the obtained film, water was dropped onto it and the contact angle was measured. The contact angle was measured in a 25°C environment using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.). Specifically, the surface-modified substrate to be measured was placed horizontally, 2 μL of water was dropped onto its surface from a microsyringe, and the static contact angle was measured by capturing a still image 1 second after dropping with a video microscope.

[0243] [Examples 2-16] The contact angle was measured in the same manner as in Example 1, except that oleanolic acid was replaced with the compounds shown in Examples 2-16 of Table 1.

[0244] Table 1 shows the compounds used in Examples 1 to 16, as well as the results of measuring the contact angle (°) with water. Brasscasterol was purchased from Tama Biochemical Co., Ltd., and the other compounds were purchased from Tokyo Chemical Industry Co., Ltd.

Claims

A surface modifier containing isoprenoid compounds. The surface modifier according to claim 1, wherein the isoprenoid compound is a terpene or a terpenoid. 　 The terpene is a compound selected from the group consisting of monoterpenes, sesquiterpenes, diterpenes, sesterterpenes, triterpenes, sesquaterpenes, tetraterpenes, and pentaterpenes. The surface modifier according to claim 2, wherein the terpenoid is a compound selected from the group consisting of monoterpenoids, sesquiterpenoids, diterpenoids, sesterterpenoids, triterpenoids, sesquaterpenoids, tetraterpenoids, and pentaterpenoids. 　 The surface modifier according to any one of claims 1 to 3, wherein the isoprenoid compound is a steroid compound. 　 The surface modifier according to claim 4, wherein the steroid compound is a sterol compound. 　 The surface modifier according to any one of claims 1 to 5, wherein the isoprenoid compound is vitamin D. 　 The isoprenoid compound has 15 to 70 carbon atoms, according to any one of claims 1 to 6. 　 The isoprenoid compound is given by the following formula: 　　　 R １４ -(-CR １１ =CR １２ -R １３ -) ｎ -R １４ (I) [In the formula, R １１ and R １２ is, in each occurrence, independently a hydrogen atom or a C １－１２ alkyl group, R １３ Each occurrence is independently of a single bond or C １－１２ It is an alkylene group, R １４ Each of them is independent of C １－４０ It is a hydrocarbon group, n is an integer between 1 and 100. A surface modifier according to any one of claims 1 to 7, wherein the compound is represented by [formula]. The surface modifier according to claim 8, wherein n is 4 or greater. 　 The isoprenoid compound is a surface modifier according to any one of claims 1 to 9, wherein the isoprenoid compound has a ring structure. 　 The surface modifier according to claim 10, wherein the ring structure has 4 to 10 membered rings. 　 The surface modifier according to claim 10 or 11, wherein the ring structure includes an unsaturated structure. 　 The surface modifier according to any one of claims 10 to 12, wherein the ring structure is a condensed polycyclic structure containing four or more rings. 　 The aforementioned ring structure is given by the following formula: A surface modifier according to any one of claims 10 to 13, comprising a structure (II) which may include unsaturated bonds between adjacent ring member carbons. 　 The surface modifier according to claim 14, wherein the structure (II) has at least one methyl group at the C10 and C13 positions and contains a double bond between the carbon at the C7 position and the carbon at the C8 position. 　 The surface modifier according to claim 15, wherein the structure (II) further has an -OH group at the C3 position. 　 The above structure (II) further has -O-C(=O)R at the C3 position. ２ 、 -C (=O) -OR ２ or -O-C (=O) OR ２ [In the formula, R ２ C １－４０ It is a hydrocarbon group. A surface modifier according to claim 15 or 16, having a group represented by . R ２ C ３－２０ The surface modifier according to claim 17, wherein the alkyl group is... 　 The aforementioned ring structure is given by the following formula: A surface modifier according to any one of claims 10 to 18, comprising a structure (III) which may include unsaturated bonds between adjacent ring member carbons. 　 The surface modifier according to claim 19, wherein the structure (III) has two methyl groups at the C4 position, at least one methyl group at the C8, C10, and C20 positions, and includes a double bond between the carbon at the C12 position and the carbon at the C13 position. Furthermore, the surface modifier according to claim 20, having a -COOH group at the C17 position. Furthermore, the surface modifier according to claim 20 or 21, having a monovalent hydrocarbon group at the C20 position. A surface modifier according to any one of claims 1 to 22, wherein the isoprenoid compound is derived from a natural product. The isoprenoid compound is selected from the group consisting of β-carotene, squalene, β-caryophyllene, oleanolic acid, stearyl glycyrrhetinate, brassicasterol, stigmasterol, cholesterol, cholecalciferol, β-sitosterol, ergosterol, cholesteryl oleate, cholesteryl myristart, cholesteryl stearate, cholesterol butyrate, cholesteryl linoleate, cholesterol benzoate, cholesteryl decanoate, cholesterol-5-en-3-ol, and cholesteryl oleyl carbonate, as described in any one of claims 1 to 23. The isoprenoid compound is selected from the group consisting of β-carotene, oleanolic acid, stearyl glycyrrhetinate, brassicasterol, stigmasterol, cholesterol, cholecalciferol, β-sitosterol, ergosterol, cholesteryl oleate, cholesteryl myristart, cholesteryl stearate, cholesterol butyrate, cholesteryl linoleate, cholesterol benzoate, and cholesteryl decanoate, as described in any one of claims 1 to 24. A surface modifier according to any one of claims 1 to 25, which is an aqueous dispersion composition. A surface modifier according to any one of claims 1 to 26, comprising one or more selected from the group consisting of surfactants, silicones, waxes, organic acids, and curing agents. A surface modifier according to any one of claims 1 to 27, for use in textile products or paper products. 　 A product modified with a surface modifier according to any one of claims 1 to 28. 　 The product according to claim 29, which is a textile product or a paper product. 　 A method for producing a modified product, comprising the step of modifying a substrate with a surface modifier according to any one of claims 1 to 28. 　 The manufacturing method according to claim 31, wherein the modification is an internal modification.

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