Non-fluorine-based composition and method for producing same, surface treatment agent, and article

Abstract

A non-fluorine-based composition according to the present invention contains: (A) a non-fluorine-based hydrocarbon terminal group-containing compound and / or a partially reacted condensate thereof, the compound having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms and a reactive silyl group, and optionally containing at least one atom selected from among oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and (B) a transition metal or a compound thereof contained at 100 to 4,000 ppm, in terms of mass of the transition metal, relative to component (A). The non-fluorine-based composition can form a cured coating that is less colored and transparent, and has excellent water repellency and abrasion resistance, despite being non-fluorine-based.

Description

Non-fluorinated compositions and methods for producing the same, surface treatment agents and articles

[0001] The present invention relates to a non-fluorine-based composition, and more particularly to a non-fluorine-based composition that forms a film with minimal discoloration, transparency, and excellent water repellency and abrasion resistance, a method for producing the same, a surface treatment agent comprising the non-fluorine-based composition and a solvent, and an article surface-treated with the surface treatment agent.

[0002] In recent years, the use of touch panels in displays such as smartphones and in-car displays has accelerated. However, because touch panels have exposed screens, they are frequently in direct contact with fingers and cheeks, making them prone to dirt and sebum buildup. Therefore, there is a growing demand for technologies that make the display surface less prone to fingerprints and easier to clean, in order to improve appearance and visibility. The development of materials that can meet these demands is highly desirable. In particular, since the surface of touch panel displays is prone to fingerprint smudges, there is a desire to provide a water- and oil-repellent layer. However, while conventional water- and oil-repellent layers have high water and oil repellency and are excellent at wiping away dirt, they lack sufficient abrasion resistance and have the problem of fingerprints being very noticeable when they do adhere to the surface.

[0003] Generally, fluoropolyether group-containing compounds have very low surface free energy, resulting in properties such as water and oil repellency, chemical resistance, lubricity, mold release, and antifouling. These properties are utilized industrially in a wide range of applications, including water, oil, and stain repellents for paper and textiles, lubricants for magnetic recording media, oil inhibitors and mold release agents for precision equipment, cosmetics, and protective films. However, these properties also mean non-stickiness and poor adhesion to other substrates; while they can be applied to substrate surfaces, achieving a strong bond between the film and the substrate is difficult.

[0004] Silane coupling agents are well-known for bonding organic compounds to substrate surfaces such as glass and cloth, and are widely used as coating agents for various substrate surfaces. A silane coupling agent has an organic functional group and a reactive silyl group (generally a hydrolyzable silyl group such as an alkoxysilyl group) in one molecule. The hydrolyzable silyl group undergoes a self-condensation reaction with moisture in the air to form a film. This film becomes a strong and durable coating because the hydrolyzable silyl group chemically and physically bonds with the surface of glass, metal, etc.

[0005] Therefore, compositions have been disclosed that use a fluoropolyether group-containing polymer obtained by introducing a hydrolyzable silyl group into a fluoropolyether group-containing compound, which can easily adhere to the substrate surface and form a coating on the substrate surface that has water-repellent and oil-repellent properties, chemical resistance, lubricity, mold release properties, and antifouling properties (Patent Documents 1 to 6: Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557, Japanese Unexamined Patent Publication No. 2012-072272, Japanese Unexamined Patent Publication No. 2012-157856, Japanese Unexamined Patent Publication No. 2013-136833, Japanese Unexamined Patent Publication No. 2015-199906).

[0006] A preferred method for introducing a hydrolyzable silyl group to the terminus of an organic compound is to introduce a 2-propenyl group (-CH2CH=CH2, commonly known as an allyl group) to the terminus of the starting compound molecule, and then react the compound to which the 2-propenyl group has been introduced with a hydrosilane compound to hydrosilylate it. Hydrosilylation addition reactions are carried out, for example, in the presence of a small amount of transition metal compound (Patent Document 7: Japanese Patent Application Publication No. 2019-044179).

[0007] However, the cured film formed by coating the surface of a substrate with a compound having a hydrolyzable silyl group at its terminus, obtained by hydrosilylation using the method described in Patent Document 7, does not necessarily have sufficient durability. Touch panels and the like are subjected to repeated friction from fingers, so the cured film formed on the surface of the substrate needs to have durability that can maintain its performance for a long period of time. In particular, touch panels used outdoors (digital signage such as vending machines and information boards), and in-vehicle touch panels require high durability for the cured film. In addition, the cured film applied to the substrate needs to have high transparency (Patent Document 8: Japanese Patent No. 6977767).

[0008] Furthermore, because fluorine-based compounds are difficult to decompose in nature and tend to accumulate in the environment, there has been a growing need for the development of surface protective agents for non-fluorine-based materials.

[0009] Japanese Patent Publication No. 2008-534696, Japanese Patent Publication No. 2008-537557, Japanese Unexamined Patent Publication No. 2012-072272, Japanese Unexamined Patent Publication No. 2012-157856, Japanese Unexamined Patent Publication No. 2013-136833, Japanese Unexamined Patent Publication No. 2015-199906, Japanese Unexamined Patent Publication No. 2019-044179, Japanese Patent No. 6977767

[0010] The present invention has been made in view of the above circumstances, and aims to provide a nonfluorine-based composition containing a hydrocarbon terminal group-containing compound that can form a hardened film with minimal discoloration, transparency, and excellent water repellency and abrasion resistance, a method for producing the same, a surface treatment agent containing the nonfluorine-based composition and a solvent, and an article surface-treated with the surface treatment agent.

[0011] As a result of diligent research to solve the above objectives, the present inventors have found that a surface treatment agent comprising (A) a nonfluorine-based hydrocarbon terminal group-containing compound and / or a partially reaction condensate thereof having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms and a reactive silyl group, which may contain at least one selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, and (B) a transition metal or a compound thereof: a nonfluorine-based composition comprising 100 to 4,000 ppm of the transition metal by mass relative to component (A) can form a hardened film that is nonfluorine-based (i.e., does not contain fluorine atoms in the molecule), has little coloration and transparency, and exhibits excellent water repellency, abrasion resistance, and especially steel wool abrasion resistance, thus leading to the present invention.

[0012] Accordingly, the present invention provides the following nonfluorine-based compositions, surface treatment agents and articles, and methods for producing nonfluorine-based compositions. [1] A nonfluorine-based hydrocarbon terminal group-containing compound and / or a partially reaction condensate thereof, comprising: (A) a linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, and a reactive silyl group; and (B) a transition metal or a compound thereof: 100 to 4,000 ppm by mass of the transition metal relative to component (A). [2] The nonfluorine-based composition according to [1], wherein the hydrocarbon terminal group-containing compound of component (A) is a compound represented by the following general formula (1). (In the formula, R 1 R may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, 2A is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U is a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; V is independently a single bond or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is independently a single bond, carbon atom, silicon atom, nitrogen atom, sulfur atom, or a 3- to 8valent organic group; Y is independently a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms; A is independently a monovalent reactive silyl group; k1 is an integer from 1 to 3; k2 is 0 or 1; k3 is an integer from 1 to 3; k1 + k2 + k3 is 3 or 4; and m is an integer from 1 to 7.) [3] In the above formula (1), A is the following general formula (2) A nonfluorine-based composition according to [2], wherein the group is represented by (wherein R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer from 1 to 3. [4] A nonfluorine-based composition according to [3], wherein in formula (2) above, X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and a dialkylamino group having 2 to 10 carbon atoms. [5] In formula (1) above, R 1 However, the following formula (In the formula, R AQ is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, or a carbamate group. Q' is a divalent group selected from the group consisting of a urea group and a divalent nitrogen-containing heterocyclic group, Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group, Q'' is independently a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, and R B R is a divalent hydrocarbon group having 1 to 29 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, C R is independent Aor a hydrogen atom, and p is an integer of 0 to 10. However, the total number of carbon atoms in each structure is 32 or less.) The non-fluorine-based composition according to any one of [2] to [4], which is any group represented by. [6] In the above formula (1), Y is an alkylene group having 1 to 20 carbon atoms which may contain at least one selected from an oxygen atom, a nitrogen atom and a sulfur atom, an alkylene group having 1 to 10 carbon atoms containing an arylene group having 6 to 8 carbon atoms, a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a silaalkylene structure, a silaarylene structure or a nitrogen-containing heterocyclic group, and a bond of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms The non-fluorine-based composition according to any one of [2] to [5], which is a group selected from the group consisting of divalent groups to which an alkylene group having 1 to 10 carbon atoms is bonded. [7] In the above formula (1), Z is a single bond, or a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 =(R 3 is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), a trivalent group represented by, -CR 4 =(R 4The nonfluorine-based composition according to any one of [2] to [6], wherein the group is a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; a linear or branched or cyclic trivalent to octavalent organopolysiloxane residue having 2 to 10 silicon atoms or 3 to 10 silicon atoms; a trivalent amide group; a trivalent carbamate group; a trivalent or tetravalent urea group; and a trivalent to octavalent nitrogen-containing heterocyclic group. [8] A nonfluorinated composition according to any one of [2] to [7], wherein in formula (1) above, U is a trivalent or tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group. [9] A nonfluorinated composition according to any one of [1] to [8], wherein (B) a transition metal or a compound thereof acts as a catalyst for a hydrosilylation addition reaction.

[10] A nonfluorinated composition according to any one of [1] to [9], wherein (B) a transition metal or a compound thereof is platinum or a platinum compound.

[11] A surface treatment agent characterized by comprising a non-fluorine composition described in any of [1] to

[10] and a solvent.

[12] An article surface-treated with the surface treatment agent described in

[11] .

[13] A method for producing a nonfluorine-based composition according to [1], comprising the step of mixing a compound (i) having an alkenyl group at its terminus and at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and a compound (ii) having an SiH group and a reactive silyl group, and carrying out a hydrosilylation addition reaction with compound (i) in the presence of a transition metal or a compound thereof in an amount of 100 ppm or more in terms of transition metal, to produce a nonfluorine-based hydrocarbon terminus-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and a reactive silyl group.

[14] A method for producing the nonfluorine-based composition according to

[13] , wherein the transition metal or its compound is platinum or a platinum compound.

[15] (I) A compound (i) having an alkenyl group at the terminus and at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms; and a compound (ii) having an SiH group and a reactive silyl group; and a hydrosilylation addition reaction being carried out in the presence of a transition metal or its compound in an amount of 0.01 ppm or more and less than 100 ppm in terms of transition metal relative to compound (i), thereby producing a nonfluorine-based hydrocarbon-terminated compound having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and a reactive silyl group. (II) A method for producing a nonfluorine-based composition according to [1], characterized by adding a transition metal or a compound thereof to the product obtained in step (I) in such a mass of the transition metal that it is 100 to 4,000 ppm relative to the obtained hydrocarbon-terminated compound and / or partially reacted condensate thereof.

[16] A method for producing a nonfluorine-based composition according to

[15] , wherein the transition metal or compound thereof is platinum or a platinum compound.

[0013] Articles surface-treated with a surface treatment agent containing the non-fluorine composition of the present invention have a cured film that is non-fluorine, yet exhibits minimal discoloration, transparency, and excellent water repellency and abrasion resistance.

[0014] [Non-fluorinated composition] The non-fluorinated composition of the present invention comprises (A) a non-fluorinated hydrocarbon terminal group-containing compound and / or a partially reaction condensate thereof having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, and a reactive silyl group, which may contain at least one selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and (B) a transition metal or a compound thereof, comprising 100 to 4,000 ppm by mass of the transition metal relative to component (A), and made of a material that does not contain fluorine atoms.

[0015] [Component (A)] Component (A) used in the nonfluorine-based composition of the present invention is a nonfluorine-based hydrocarbon terminal group-containing compound and / or a partially reaction condensate thereof, which may contain at least one selected from oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms, and which has at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, and a reactive silyl group.

[0016] The hydrocarbon terminal group-containing compound of component (A) has at least one hydrocarbon chain terminal group with a predetermined number of carbon atoms, thereby improving molecular mobility. As a result, the cured film of the surface treatment agent using the non-fluorine-based composition of the present invention containing the above compound exhibits water repellency and excellent abrasion resistance.

[0017] The hydrocarbon terminal group-containing compound is preferably a compound represented by the following general formula (1). (In the formula, R 1 R may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, 2 (where k1 is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U is a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; V is independently a single bond or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is independently a single bond, carbon atom, silicon atom, nitrogen atom, sulfur atom, or a trivalent to octavalent organic group; Y is independently a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms; A is independently a monovalent reactive silyl group; k1 is an integer from 1 to 3; k2 is 0 or 1; k3 is an integer from 1 to 3; k1 + k2 + k3 is 3 or 4; and m is an integer from 1 to 7.)

[0018] In the above formula (1), R 1This group may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, preferably 6 to 28 carbon atoms, more preferably 8 to 28 carbon atoms, and even more preferably 10 to 28 carbon atoms. Here, when at least one selected from oxygen, sulfur, nitrogen, and silicon atoms is included, it is preferable that it be included as a group such as an ether group, carbonyl (ketone) group, ester group, carbonate group, thioether group, sulfinyl group, sulfonyl group, thioester group, thiocarbonate group, thiocarbamate group, amino group, amide group, carbamate group, urea group, oxazole group, imidazole group, triazole group, cyanurate group, isocyanurate group, diorganosilylene group, organopolysiloxane residue, sylalkylene group, or sylarylene group.

[0019] R 1 The base represented by the following formula is preferred. (In the formula, R AQ is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, or a divalent nitrogen-containing heterocyclic group (divalent oxazole group, divalent imidazole group). Q' is a divalent group selected from the group consisting of a group (such as a divalent triazole group), Q' is a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, or a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group), and Q'' is a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, or R B R is a divalent hydrocarbon group having 1 to 29 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, C R is independent A (or a hydrogen atom, where p is an integer between 0 and 10. However, the total number of carbon atoms in each structure is 32 or less.)

[0020] In the above formula, R A R is a monovalent hydrocarbon group having 3 to 32 carbon atoms, preferably 6 to 28 carbon atoms, more preferably 8 to 28 carbon atoms, and may be linear, branched, cyclic, or a combination thereof. A For example, the following can be cited: (In the formula, x is an integer between 2 and 31, preferably between 5 and 27, more preferably between 7 and 27, and y and y' are integers of 1 or more such that the sum of the number of carbon atoms in each structure is 32 or less.)

[0021] In the above formula, Q is independently a divalent group selected from the group consisting of an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a divalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly a linear structure with 2 to 8 silicon atoms, or a branched or cyclic structure with 3 to 10 silicon atoms, particularly a branched or cyclic structure with 3 to 8 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, a carbamate group, a urea group, and a divalent nitrogen-containing heterocyclic group (such as a divalent oxazole group, a divalent imidazole group, or a divalent triazole group).

[0022] Here, the groups that bond to silicon atoms in diorganosilylene groups, sylalkylene structures, sylarylene structures, and organopolysiloxane residues are preferably alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkylene groups in the sylalkylene structures are preferably ethylene groups, propylene groups (trimethylene group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Moreover, the organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene and propylene groups.

[0023] Examples of such Q include those shown below. In the structure below, the left-hand coupling is R A or R B It is joined to the right side, and the joining hand is R B It combines with it. (In the formula, f is an integer between 2 and 4, and e is an integer between 1 and 9.)

[0024] In the above formula, Q' is a trivalent group selected independently from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a trivalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly a linear group having 2 to 8 silicon atoms, or a branched or cyclic group having 3 to 10 silicon atoms, particularly a trivalent amide group, or a trivalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, or a trivalent triazole group).

[0025] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0026] Examples of such Q' include those shown below. In the structure below, the left-hand coupling is R A or R B And the coupling on the right is R B And the other bonds are R C It combines with it. (In the formula, f is an integer between 2 and 4.)

[0027] In the above formula, Q'' is a tetravalent group independently selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0028] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0029] Examples of such Q'' include those shown below. In the structure below, the left-hand coupling is R A or R B And the coupling on the right is R B And the other bonds are R C It combines with it.

[0030] In the above formula, R B These are divalent hydrocarbon groups having 1 to 29 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, and the following are examples: (In the formula, z is an integer between 1 and 10.)

[0031] In the above formula, R C R is independent A Or it is a hydrogen atom. Note that R C R A If so, then R A It may be the same as or different from it.

[0032] In the above formula, p is an integer between 0 and 10, and is preferably 0, 1, or 2. However, R 1 The total number of carbon atoms in each structure is 32 or less.

[0033] This kind of R 1 The following are preferred for use. (In the formulas, x, y, y', and z are the same as above, except that the total number of carbon atoms in each structure is between 3 and 32.)

[0034] In the above formula (1), R 2 R is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms (methyl group, ethyl group). 2Preferably, the atoms are hydrogen atoms, chlorine atoms, hydroxyl groups, methyl groups, and ethyl groups.

[0035] In formula (1) above, U is a carbon atom, a silicon atom, a nitrogen atom, or a trivalent or tetravalent organic group. The trivalent or tetravalent organic group is preferably a trivalent or tetravalent group selected from a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic trivalent or tetravalent organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group (such as a trivalent cyanurate group, a trivalent isocyanurate group, and a trivalent triazine ring-containing group).

[0036] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0037] Examples of such U are shown below. In the structure below, it is preferable that the right-hand coupling bond connects to V.

[0038] In formula (1) above, V may independently contain a single bond or at least one selected from oxygen, nitrogen, and sulfur atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is a linking group connecting the U group and the Z group. When Z is a single bond, V is preferably a single bond. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 10 carbon atoms which may contain at least one selected from oxygen, nitrogen, and sulfur atoms, an alkylene group having 1 to 10 carbon atoms which includes an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms).

[0039] Examples of such V include, in addition to single bonds, the following. In the structure below, the bond on the left is bonded to U, and the bond on the right is bonded to Z. (In the formula, q is an integer between 1 and 10, r, s, and t are each integers between 1 and 8, the sum of r and s is an integer between 2 and 10, and the sum of r, s, and t is an integer between 3 and 10.)

[0040] In formula (1) above, Z is independently a single bond, a carbon atom, a silicon atom, a nitrogen atom, a sulfur atom, or a 3- to 8-valent organic group, and the 3- to 8-valent organic group is a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 = (R 3 (A trivalent group represented by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 = (R 4 Examples of 3-8 valent groups include trivalent groups represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms; linear 3-8 valent organopolysiloxane residues with 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or branched or cyclic 3-8 valent organopolysiloxane residues with 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms; trivalent amide groups; trivalent carbamate groups; trivalent or tetravalent urea groups; and 3-8 valent nitrogen-containing heterocyclic groups (such as trivalent cyanurate groups, trivalent isocyanurate groups, and trivalent or tetravalent triazine ring-containing groups).

[0041] The organopolysiloxane residue may have an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group, or a phenyl group, having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are linked by an alkylene group such as an ethylene group or a propylene group.

[0042] Examples of such Z bonds include, in addition to single bonds, those shown below. In the structure below, the bond on the left is bonded to V, and the other bonds are bonded to Y. (In the formula, f is an integer between 2 and 4.)

[0043] In formula (1) above, Y may independently contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, and is a linking group connecting the Z group and the A group. Examples of the divalent hydrocarbon group include, specifically, an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; an alkylene group having 1 to 10 carbon atoms including an arylene group having 6 to 8 carbon atoms (for example, an alkylene-arylene group having 7 to 18 carbon atoms); a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group; and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the binding site of a linear organopolysiloxane residue having 2 to 10 silicon atoms, particularly 2 to 8 silicon atoms, or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms, particularly 3 to 8 silicon atoms.

[0044] Here, the groups that bond to silicon atoms in diorganosilylene groups, sylalkylene structures, sylarylene structures, and organopolysiloxane residues are preferably alkyl groups such as methyl, ethyl, propyl, and butyl groups, or phenyl groups, having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, the alkylene groups in the sylalkylene structures are preferably ethylene groups, propylene groups (trimethylene group, methylethylene group), butylene groups (tetramethylene group, methylpropylene group), etc., having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Moreover, the organopolysiloxane residue may also contain a sylalkylene structure in which two silicon atoms are bonded by alkylene groups such as ethylene and propylene groups.

[0045] Examples of such Y groups include the following. In the structure below, the left-hand bond is bonded to Z, and the right-hand bond is bonded to A. It is preferable that there are two or more repeating units represented by (CH2) that bond to A. (In the formula, a is an integer between 1 and 10, b, c, and d are each integers between 1 and 8, the sum of b and c is an integer between 2 and 10, and the sum of b, c, and d is an integer between 3 and 10. e is an integer between 1 and 9, and f is an integer between 2 and 4.)

[0046] In formula (1) above, A is independently a monovalent reactive silyl group, and examples include monovalent groups such as hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups. Among these, hydroxyl group-containing silyl groups (silanol groups) and hydrolyzable silyl groups are preferred.

[0047] The following general formula (2) is used for hydroxyl group-containing silyl groups and hydrolyzable silyl groups. (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer from 1 to 3.) Or the following general formula (3) A base represented by (wherein n'' is a number from 0 to 3, and n'' is (3 - n'') / 2) is preferred.

[0048] In formula (2) above, R is independently an alkyl group such as a methyl group, ethyl group, propyl group, or butyl group having 1 to 4 carbon atoms, or a phenyl group, with the methyl group being preferred. Also, in formula (2) above, X is independently a hydroxyl group or a hydrolyzable group, and examples of such X include hydroxyl groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups; alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy groups; acyloxy groups having 1 to 10 carbon atoms such as acetoxy groups; alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy and cyclopentenyloxy groups; halogen groups such as chlor, bromo, and iodine groups; and dialkylamino groups having 2 to 10 carbon atoms such as dimethylamino and diethylamino groups. Among these, methoxy, ethoxy, isopropenoxy, and chlor groups are preferred. X may be the same or different.

[0049] In formula (3) above, n'' is a number from 0 to 3 (a positive number less than or equal to 3), preferably n'' < 3, and more preferably n'' = 0. In formula (3) above, when n'' = 3, general formula (1) above represents the molecular formula (structural formula) of the hydrocarbon terminal group-containing compound (monomer monomer), and in formula (3) above, when n'' < 3, general formula (1) above represents the compositional formula of the hydrocarbon terminal group-containing compound (polysilazane compound). In formula (3) above, n'' is (3 - n'') / 2, preferably 1.5.

[0050] In formula (1) above, k1 is an integer from 1 to 3, preferably 2 or 3; k2 is 0 or 1; k3 is an integer from 1 to 3, preferably 1 or 2; k1 + k2 + k3 is 3 or 4; when U is trivalent, k1 + k2 + k3 is 3; when U is tetravalent, k1 + k2 + k3 is 4. Also, m is an integer from 1 to 7, preferably 1 to 3.

[0051] The following structures are examples of the structure of the compound represented by the above formula (1). R in the above formula (1) 1 , R 2 By changing the combinations of U, V, Z, Y, A, k1, k2, k3, and m, several different hydrocarbon end-group-containing compounds can be obtained.

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065] (In the formula, x, y, y', z, q, r, s, a, b, c, d, e, and f are all independently the same as above.)

[0066] [(B) Component (Transition Metal or Compound thereof)] Examples of transition metals or compounds thereof used in the nonfluorine-based composition of the present invention include those that act as catalysts in the hydrosilylation addition reaction when preparing the hydrocarbon terminal group-containing compound of component (A) above (particularly the compound represented by formula (1)), the hydrolysis reaction of a hydrolyzable silyl group to a silanol group, and the dehydration condensation reaction between the silanol group and the hydroxyl group on the surface of the substrate (substrate-OH). Examples of transition metals or compounds thereof having such effects include transition metals of groups 8 to 10 or compounds containing such transition metals. Groups 8 to 10 are group numbers according to the IUPAC Inorganic Chemical Nomenclature Revision (1989).

[0067] Examples of transition metals in groups 8 to 10 or their compounds include ruthenium (Ru), iron (Fe), iridium (Ir), rhodium (Rh), cobalt (Co), platinum (Pt), nickel (Ni), palladium (Pd), and compounds thereof. Platinum or platinum compounds are particularly preferred because they exhibit high catalytic activity for the above-mentioned hydrosilylation addition reaction, hydrolysis reaction, and dehydration condensation reaction.

[0068] Examples of platinum compounds include chloroplatinic acid; complexes of platinum with olefins such as ethylene; complexes of platinum with alcohols or vinylsiloxanes; and metallic platinum supported on silica, alumina, carbon, etc. Other compounds besides platinum include, for example, RhCl(PPh3)3, RhCl(CO)(PPh3)2, and Ru3(CO) 12 Examples include IrCl(CO)(PPh3)2, Pd(PPh3)4, etc. In the above formulas, Ph represents a phenyl group.

[0069] Transition metals or their compounds may be used individually or in combination of two or more.

[0070] The amount of transition metal or its compound blended is 100 to 4,000 ppm by mass of the transition metal relative to component (A), preferably 100 to 2,000 ppm, and more preferably 100 to 1,000 ppm. If the amount of transition metal or its compound blended is within the above range, the resulting cured film will have transparency with minimal discoloration, and the durability of the cured film can be improved.

[0071] Furthermore, in the non-fluorinated composition of the present invention, the total amount of component (A) and component (B) is preferably 80 to 100% by mass of the entire non-fluorinated composition, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass. In addition, in the non-fluorinated composition of the present invention, examples of components other than components (A) and (B) include unreacted raw materials, by-products, co-catalysts, etc., as described in the manufacturing method described later.

[0072] [Method for producing the non-fluorine-based composition] Two methods can be exemplified below as methods for producing the non-fluorine-based composition of the present invention.

[0073] [Manufacturing Method 1] The first manufacturing method includes the following steps: A compound (i) having an alkenyl group at its terminus and at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms; and a compound (ii) having an SiH group and a reactive silyl group; and a hydrosilylation addition reaction being carried out in the presence of a transition metal or a compound thereof in an amount of 100 ppm or more in terms of transition metal relative to compound (i) to produce a nonfluorine-based hydrocarbon terminus-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and a reactive silyl group.

[0074] Compound (i), which has an alkenyl group at its terminus and at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, is preferably a compound represented by the following general formula (4). (In the formula, R 1 , R 2 U, V, Z, k1, k2, k3, k1+k2+k3, and m are the same as above, and Y' is a divalent hydrocarbon group that may independently contain a single bond or at least one atom selected from oxygen, nitrogen, sulfur, and silicon.

[0075] In formula (4) above, Y' may independently consist of a single bond or at least one selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom, preferably a divalent hydrocarbon group having 1 to 18 carbon atoms, the following being examples. In the structure below, the bond on the left is bonded to Z, and the bond on the right is bonded to a carbon atom. (In the formula, a' is an independent integer between 0 and 8, b and c are integers between 1 and 8, c' and d' are integers between 0 and 6, the sum of b and c' is an integer between 2 and 8, and the sum of b, c, and d' is an integer between 3 and 8. e is an integer between 1 and 9, and f is an integer between 2 and 4.)

[0076] Examples of compounds represented by formula (4) are listed below. (In the formula, x, y, y', z, q, r, s, a', b, and c' are all independently the same as above.)

[0077] The compound (ii) having an SiH group and a reactive silyl group is preferably a silane compound represented by the following general formula (5). (In the formula, R, X, and n are the same as above.)

[0078] Examples of silane compounds represented by the above formula (5) include trimethoxysilane, methyldimethoxysilane, triethoxysilane, triacetoxysilane, and trichlorosilane.

[0079] In manufacturing method 1, the amount of compound (ii) having an SiH group and a reactive silyl group used is preferably 1 to 6 moles, particularly 1.5 to 4 moles, per mole of alkenyl group in compound (i).

[0080] In manufacturing method 1, examples of transition metals or compounds thereof include those similar to the transition metals or compounds thereof (component (B)) used in the non-fluorinated composition of the present invention. Platinum or platinum compounds are preferred among these.

[0081] When using these transition metals or their compounds, they can be used in solid form when they are solid, but to obtain a more uniform cured film, they can be dissolved in a suitable solvent such as toluene or ethanol.

[0082] The amount of transition metal or its compound used is 100 ppm or more in terms of mass of the transition metal relative to compound (i), preferably 110 to 5,000 ppm, more preferably 120 to 4,000 ppm, even more preferably 200 to 3,000 ppm, and particularly preferably 300 to 2,000 ppm. If the amount of transition metal or its compound used is within the above range, the resulting cured film will have transparency with little discoloration, and the durability of the cured film can be improved.

[0083] In manufacturing method 1, a co-catalyst to accelerate the reaction may be added to the above reaction. Examples of such co-catalysts include organic acids (formic acid, acetic acid, etc.), organic nitrogen compounds (pyridine, tributylamine, formamide, etc.), organic sulfur compounds (dimethyl sulfide, etc.), and organic phosphorus compounds (triphenylphosphine, tributylphosphine). When a co-catalyst is used, the amount used is preferably 100 to 4,000 ppm, more preferably 100 to 2,000 ppm, and particularly preferably 100 to 1,000 ppm relative to compound (i).

[0084] In manufacturing method 1, a solvent may be used in the above reaction. Examples of solvents include hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), and ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether) Examples of solvents include diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate), and siloxane solvents (hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.). Among these, toluene, hexane, heptane, isooctane, isononane, cyclopentanone, dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate are preferred in terms of solubility and wettability. When using a solvent, the amount used is preferably 0 to 2,000 parts by mass, and more preferably 50 to 1,000 parts by mass, per 100 parts by mass of compound (i).

[0085] In manufacturing method 1, when mixing compound (i) and compound (ii) and carrying out a hydrosilylation addition reaction, the reaction conditions are preferably a temperature of 20 to 120°C, particularly 20 to 100°C, and a reaction time of 0.5 to 72 hours, particularly 1 to 36 hours.

[0086] By hydrosilylation addition of compound (i) and compound (ii), a nonfluorinated hydrocarbon end group-containing compound can be obtained, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and which has at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, and a reactive silyl group.

[0087] Specifically, a compound represented by formula (4) and a silane compound represented by formula (5) can be mixed and subjected to a hydrosilylation addition reaction in the presence of a specific amount of a transition metal or a compound thereof to produce a compound represented by formula (1) (particularly a compound having a hydrolyzable silyl group at the terminal).

[0088] Furthermore, in the case of compound (ii) above, for example, a silane compound represented by formula (5), if X is a halogen atom (for example, HSiCl3), the substituent (halogen atom) on the silyl group can then be converted to another hydrolyzable group, such as an alkoxy group like a methoxy group. Examples of reagents that can be used to convert the substituent (halogen atom) on the silyl group to another hydrolyzable group include C1-C10 alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, and orthoesters such as methyl orthoformate. The amount used is preferably 10 to 200 parts by mass, and more preferably 40 to 100 parts by mass, per 100 parts by mass of the addition reaction product of compound (i) and compound (ii) (for example, HSiCl3).

[0089] Subsequently, the desired non-fluorinated composition can be obtained by removing the solvent and unreacted substances under reduced pressure.

[0090] The obtained nonfluorine-based composition may contain a partially reacted condensate obtained by the partial reaction condensation of a reactive silyl group (specifically, a hydroxyl group-containing silyl group (silanol group), a hydrolyzable silyl group) of a hydrocarbon terminal group-containing compound of the specific structure described above (particularly, the compound represented by formula (1) above) (specifically, a partially (hydrolyzed) condensate obtained by condensing a hydroxyl group obtained by partially hydrolyzing the hydroxyl group of the compound represented by formula (1) above, or a hydrolyzable group of the compound represented by formula (1) above, using a previously known method). Here, "partially (hydrolyzed) condensate" refers to a partially condensed product or a partially hydrolyzed condensate. Furthermore, the obtained nonfluorine-based composition may contain unreacted raw materials, by-products, co-catalysts, etc., in the above reaction, to the extent that they do not impair the objectives of the present invention. However, the nonfluorine-based composition of the present invention does not contain a solvent.

[0091] Furthermore, the resulting non-fluorinated composition contains a transition metal or its compound in an amount of 100 to 4,000 ppm, preferably 100 to 2,000 ppm, and more preferably 100 to 1,000 ppm, relative to the mass of the hydrocarbon terminal group-containing compound of the specific structure described above (particularly the compound represented by formula (1) above) and / or its partially reacted condensate. In the present invention, the amount of the transition metal or its compound in the non-fluorinated composition can be measured, for example, by inductively coupled plasma atomic emission spectrometry (the same applies hereinafter).

[0092] [Manufacturing Method 2] The second manufacturing method includes the following steps (I) and (II). (I) A compound (i) having an alkenyl group at its terminus and at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and a compound (ii) having an SiH group and a reactive silyl group, and a hydrosilylation addition reaction being carried out in the presence of a transition metal or a compound thereof in an amount of 0.01 ppm or more and less than 100 ppm in terms of transition metal, thereby producing a nonfluorine-based hydrocarbon-terminated compound having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and a reactive silyl group. (II) A step of adding a transition metal or a compound thereof to the product obtained in step (I) in such a mass of the transition metal that it is 100 to 4,000 ppm relative to the obtained hydrocarbon terminal group-containing compound and / or its partially reacted condensate.

[0093] [Step (I)] In step (I) of manufacturing method 2, the reaction between compound (i), preferably the compound represented by formula (4), and compound (ii), preferably the silane compound represented by formula (5), can be carried out in the same manner as in manufacturing method 1, except for the amount of transition metal or the compound used.

[0094] In step (I) of manufacturing method 2, the amount of transition metal or its compound used is 0.01 ppm or more and less than 100 ppm in terms of the mass of the transition metal relative to the compound represented by formula (4) above, preferably 0.02 to 90 ppm, and more preferably 0.03 to 80 ppm. If the amount of transition metal or its compound used is within the above range, it is a sufficient amount of catalyst for the hydrosilylation reaction to proceed.

[0095] After the above reaction, the solvent and unreacted products are removed by distillation under reduced pressure. The above reaction yields a product containing a hydrocarbon terminal group-containing compound of the specific structure described above (particularly the compound represented by formula (1) above).

[0096] The above product may contain a partially reacted condensate obtained by the partial reaction condensation of a reactive silyl group (specifically, a hydroxyl group-containing silyl group (silanol group), a hydrolyzable silyl group) of a hydrocarbon terminal group-containing compound of the above-described specific structure (particularly the compound represented by formula (1) above) (specifically, a partially (hydrolyzed) condensate obtained by condensing a hydroxyl group obtained by partially hydrolyzing the hydroxyl group of the compound represented by formula (1) above, or a hydrolyzable group of the compound represented by formula (1) above, using a previously known method). Furthermore, the obtained product may contain unreacted raw materials, by-products, co-catalysts, etc., in the above reaction, to the extent that it does not impair the objective of the present invention. However, the above product does not contain a solvent.

[0097] [Step (II)] Next, a transition metal or its compound is added to the product obtained in Step (I) in an amount of 100 to 4,000 ppm, preferably 100 to 2,000 ppm, and more preferably 100 to 1,000 ppm, based on the mass of the transition metal relative to the obtained hydrocarbon terminal group-containing compound and / or its partially reacted condensate. By adding the transition metal or its compound within the above range, the resulting cured film will have transparency with less discoloration, and the durability of the cured film can be improved.

[0098] In manufacturing method 2, the transition metal or its compound used in the above reaction and the transition metal or its compound added in step (II) may be the same or different, but it is preferable that they be the same in that the catalytic action mechanism is identical.

[0099] [Surface Treatment Agent] The present invention provides a non-fluorine-based surface treatment agent containing the above-mentioned non-fluorine-based composition as a main component. The surface treatment agent preferably contains a solvent. Furthermore, the surface treatment agent of the present invention is made of a material that does not contain fluorine atoms.

[0100] In the surface treatment agent of the present invention, the amount of the non-fluorine-based composition is preferably 0.1 to 100% by mass, more preferably 0.15 to 80% by mass, and even more preferably 0.2 to 60% by mass. If the amount of the non-fluorine-based composition is within the above range, it is easy to handle as a diluent during coating.

[0101] The surface treatment agent preferably contains a solvent. Such solvents are preferably non-fluorinated solvents, and examples include hydrocarbon solvents (petroleum benzine, toluene, xylene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, octane (n-octane, isooctane, etc.), nonane (n-nonane, isononane, etc.)), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ether solvents (tetrahydrofuran (THF), dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), alcohol solvents (propylene glycol monomethyl ether, butanol, isopropanol, etc.), and ester solvents (ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate). Among these, toluene, hexane, heptane, isooctane, isononane, cyclopentanone, dipropyl ether, dibutyl ether, methylcyclopentyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate are preferred in terms of solubility, wettability, etc.

[0102] The above solvents may be mixed in two or more forms, and it is preferable that they uniformly dissolve the hydrocarbon end group-containing compounds (and their partially reacted condensates) in the nonfluorine-based composition. The optimal concentration of the nonfluorine-based composition when using the solvent varies depending on the processing method, and any amount that is easy to weigh is acceptable. However, when direct coating, it is preferable that the concentration is 0.01 to 100 parts by mass, particularly 0.05 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the above nonfluorine-based composition. When vapor deposition is performed, it is preferable that the concentration is 1 to 100 parts by mass, particularly 3 to 30 parts by mass, per 100 parts by mass of the total of the solvent and the above nonfluorine-based composition. In either coating case, 100 parts by mass refers to the case where the coating is performed without using a solvent.

[0103] The surface treatment agent of the present invention may optionally contain hydrolysis condensation catalysts, such as organotin compounds (e.g., dibutyltin dimethoxide, dibutyltin dilaurate), organotitanium compounds (e.g., tetra-n-butyl titanate, tetra-n-propyl titanate), organozirconium compounds (e.g., tetra-n-butyl zirconate, tetra-n-propyl zirconate), organic acids (e.g., acetic acid, methanesulfonic acid, carboxylic acid), inorganic acids (e.g., hydrochloric acid, sulfuric acid), and organic bases (e.g., amines, trialkylamines, nitrogen-containing cyclic compounds). Among these, acetic acid, tetra-n-butyl titanate, and dibutyltin dilaurate are particularly desirable. When using a hydrolysis condensation catalyst, the amount added is a catalytic amount, and is usually 0.001 to 5 parts by mass, particularly 0.1 to 1 part by mass, per 100 parts by mass of the above nonfluorine-based composition.

[0104] The surface treatment agent of the present invention further comprises the following general formula (6) SiR 5 n1-4 X 1 n1 (6) (wherein, R 5 X is independently a hydrogen atom or a monovalent hydrocarbon group having 1 or 2 carbon atoms, 1 (where n1 is an integer from 1 to 4, where n1 is independently a hydroxyl group or a hydrolyzable group.) This may include at least one silane compound represented by .

[0105] When the surface treatment agent of the present invention contains a silane compound represented by general formula (6), the silane compound represented by general formula (6) acts as a dehydrating agent that captures moisture in the surface treatment agent, thereby enabling the surface treatment agent to maintain its performance even after long-term storage.

[0106] In the above formula (6), R 5 R is independently a hydrogen atom or a monovalent hydrocarbon group having one or two carbon atoms. Examples of monovalent hydrocarbon groups having one or two carbon atoms include alkyl groups such as methyl and ethyl groups, and alkenyl groups such as vinyl groups. 5 Among these, methyl groups and vinyl groups are preferred.

[0107] In the above formula (6), X 1 X is independently a hydroxyl group or a hydrolyzable group. 1 Examples include hydroxyl groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups; alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy and methoxyethoxy groups; acyloxy groups having 1 to 10 carbon atoms such as acetoxy groups; alkenyloxy groups having 2 to 10 carbon atoms such as isopropenoxy and cyclopentenyloxy groups; halogen groups such as chlor, bromo, and iodine groups; and dialkylamino groups having 2 to 10 carbon atoms such as dimethylamino and diethylamino groups. Among these, methoxy, ethoxy, isopropenoxy, and chlor groups are preferred. 1 They may be the same or different.

[0108] In general formula (6), n1 is an integer from 1 to 4, preferably 3 or 4.

[0109] Particularly preferred examples of silane compounds represented by the above general formula (6) include the following compounds: Si(OCH3)4, Si(OC2H5)4, Si(OC3H7)4, Si(OC4H9)4, CH2=CHSi(OCH3)3, CH2=CHSi(OC2H5)3, CH2=CHSi(OC3H7)3, CH2=CHSi(OC4H9)3, CH2=CHSi(OCOCH3)3, CH3Si(OCH3)3, CH3Si(OC2H5)3, CH3Si(OC3H7)3, CH3Si(OC4H9)3, CH3Si(OCOCH3)3

[0110] In the surface treatment agent of the present invention, when a silane compound represented by formula (6) is incorporated, the amount incorporated is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total amount of the nonfluorine-based composition and the solvent. If the amount incorporated is below the lower limit of the above range, the amount of water in the surface treatment agent that the silane compound represented by formula (6) can capture will be limited to a small amount, and it will not be able to act sufficiently as a dehydrating agent, which may lead to a decrease in performance after long-term storage. If the amount incorporated exceeds the upper limit of the above range, the water repellency and abrasion resistance of the cured film obtained from the surface treatment agent may decrease.

[0111] The surface treatment agent of the present invention may further contain one or more nonfluorine-based materials selected from a paraffin compound (hereinafter referred to as paraffin oil) that is nonreactive with component (A) in the above nonfluorine-based composition, a polyol ester compound (hereinafter referred to as polyol ester oil) that is nonreactive with component (A) in the above nonfluorine-based composition, a silicone compound (hereinafter referred to as silicone oil) that is nonreactive with component (A) in the above nonfluorine-based composition, a halide ion, a silane coupling agent, and a compound containing an atom having a lone pair of electrons in its molecular structure, to the extent that the objectives of the present invention are not impaired.

[0112] The paraffin oils mentioned above include linear, branched, or cyclic paraffin oils with 2,000 or fewer carbon atoms. Specific examples of paraffin oils include liquid paraffin, paraffin wax, polyethylene, polypropylene, and PAO (polyalphaolefin). While paraffin oils that are liquid at room temperature (25°C) are preferred, solid paraffin oils can also be used.

[0113] In the surface treatment agent of the present invention, when paraffin oil is incorporated, the amount incorporated is preferably 0.001 to 80 parts by mass per 100 parts by mass of the total amount of the non-fluorine composition and the solvent.

[0114] Examples of the polyol ester oils mentioned above include polyol ester compounds consisting of condensates of di- to hexavalent alcohols and fatty acids having 3 to 22 carbon atoms. Specifically, examples of polyol ester compounds include di(2-ethylhexanoic acid) neopentyl glycol ester, di(oleic acid) neopentyl glycol ester, di(stearic acid) neopentyl glycol ester, tri(2-ethylhexanoic acid) trimethylolethane ester, tri(oleic acid) trimethylolethane ester, tri(stearic acid) trimethylolethane ester, tri(2-ethylhexanoic acid) trimethylolpropane ester, tri(oleic acid) trimethylolpropane ester, tri(stearic acid) trimethyl Examples include rolpropane esters, tri(2-ethylhexanoic acid) glycerol esters, tri(oleic acid) glycerol esters, tri(stearic acid) glycerol esters, tetra(2-ethylhexanoic acid) pentaerythritol esters, tetra(oleic acid) pentaerythritol esters, tetra(stearic acid) pentaerythritol esters, hexa(2-ethylhexanoic acid) dipentaerythritol esters, hexa(oleic acid) dipentaerythritol esters, and hexa(stearic acid) dipentaerythritol esters. Polyol ester oils that are liquid at room temperature (25°C) are preferred, but those that are solid can also be used.

[0115] In the surface treatment agent of the present invention, when polyol ester oil is incorporated, the amount incorporated is preferably 0.001 to 80 parts by mass per 100 parts by mass of the total amount of the non-fluorine composition and the solvent.

[0116] Examples of the above-mentioned silicone oils include linear, branched, or cyclic silicone oils having 2,000 or fewer siloxane bonds. Linear silicone oils may be so-called straight silicone oils and modified silicone oils. Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil. Examples of modified silicone oils include straight silicone oils modified with alkyl, aralkyl, polyether, higher fatty acid esters, etc. Examples of cyclic silicone oils include cyclic dimethylsiloxane oil. While it is preferable that the silicone oil is liquid at room temperature (25°C), solid silicone oils can also be used.

[0117] In the surface treatment agent of the present invention, when silicone oil is incorporated, the amount incorporated is preferably 0.001 to 80 parts by mass per 100 parts by mass of the total amount of the non-fluorine composition and the solvent.

[0118] The surface treatment agent of the present invention can be applied to a substrate by known methods such as brush coating, dip coating, spray coating, spin coating, wipe coating, squeegee coating, die coating, inkjet method, flow coating, roll coating, cast coating, Langmuir-Projet method, gravure coating, CVD, sputtering, and vapor deposition. The heating method during vapor deposition can be either resistance heating or electron beam heating, and is not particularly limited.

[0119] The curing conditions for the surface treatment agent of the present invention vary depending on the curing method. For example, in the case of direct coating (brushing, dipping, spraying, etc.), it is preferable to use a curing temperature of 25 to 200°C, particularly 25 to 150°C, for 30 minutes to 36 hours, and especially 1 to 24 hours. When applied by vapor deposition, it is desirable to use a curing temperature of 20 to 200°C for 1 to 24 hours. Curing may also be performed under humid conditions. Furthermore, for example, when using a hydrocarbon terminal group-containing compound having a hydrolyzable silyl group, in spray coating, diluting it in a solvent with water added beforehand and allowing hydrolysis, i.e., generating Si-OH, before spray coating results in faster curing after coating.

[0120] The thickness of the cured film is appropriately selected depending on the type of substrate, but is usually 0.1 to 100 nm, and particularly 1 to 50 nm. The film thickness can be measured by methods such as spectroscopic reflectance measurement, X-ray reflectance measurement, spectroscopic ellipsometry measurement, and X-ray fluorescence measurement.

[0121] The substrate to be treated with the surface treatment agent of the present invention is not particularly limited and may be made of various materials such as paper, cloth, metals and their oxides, glass, plastics, ceramics, and quartz. SiO2-treated glass and film are particularly preferred.

[0122] The surface treatment agent of the present invention can form a hardened film with a high level of water repellency and abrasion resistance that does not impair the appearance of the substrate (for example, in the case of a transparent substrate, it does not impair the transparency of the substrate).

[0123] [Articles] Articles treated with the surface treatment agent of the present invention include car navigation systems, mobile phones, smartphones, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game consoles, eyeglass lenses, camera lenses, lens filters, sunglasses, medical devices such as endoscopes, photocopiers, PCs, liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, anti-reflective films, and other optical articles and electronic components. The surface treatment agent of the present invention is particularly useful as a water-repellent layer for touch panel displays, anti-reflective films, eyeglass lenses, and the like.

[0124] Furthermore, the surface treatment agent of the present invention is useful as an antifouling coating for sanitary products such as bathtubs and washbasins, an antifouling coating for windows or tempered glass of automobiles, trains, and aircraft, headlamp covers, etc., a water-repellent coating for exterior building materials, a stain-preventing coating for kitchen building materials, an antifouling and anti-sticker / graffiti coating for telephone booths, a coating to prevent dirt from adhering to works of art, etc., and a stain-preventing coating for compact discs, DVDs, etc. In addition, the non-fluorine-based composition of the present invention can be suitably used as a mold release agent or paint additive for molds, a resin modifier, a fluidity modifier or dispersibility modifier for inorganic fillers, and a lubricity enhancer for tapes, films, etc.

[0125] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, the mol amount of the compound is, with respect to the measured mass of the target compound, 1 The value was calculated by dividing by the molecular weight of the polymer identified by 1H-NMR analysis. The mass of the obtained non-fluorinated composition was measured using a balance. The mass of platinum obtained was calculated by subtracting the amount of platinum lost during the reaction from the amount of platinum added. The amount of platinum lost was calculated assuming that platinum was lost in the same proportion as the raw materials in the total amount lost during the reaction. The mass of the obtained compound was obtained by subtracting the mass of platinum obtained above from the mass of the obtained non-fluorinated composition. The mass ratio of platinum to the obtained compound was calculated by dividing the mass of platinum obtained by the mass of the obtained compound. Furthermore, the film thickness was measured using spectroscopic ellipsometry with a spectroscopic ellipsometer.

[0126] [Synthesis Example 1] In the reaction vessel, the following formula (A) 1.00 g (1.65 × 10) of the compound represented by -3 mol), toluene 1.00 g, triethoxysilane 0.815 g (4.96 x 10 -3 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 8.00 × 10 -3g (Pt content of 400 ppm relative to the compound represented by formula (A)) was mixed and aged at 80°C for 24 hours. Thereafter, the solvent and unreacted products were removed by vacuum distillation to obtain 1.24 g of the non-fluorine composition (1.239610 g of compound, 3.9 × 10⁶ of platinum). -4 g) was obtained. The mass ratio of platinum to the obtained compound was 315 ppm in terms of platinum equivalent.

[0127] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B).

[0128] [Synthesis Example 2] In the reaction vessel, the following formula (A) 1.00 g (1.65 × 10) of the compound represented by -3 mol), triethoxysilane 0.815 g (4.96 x 10 -3 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 4.00 × 10 -2 g (with a Pt content of 2,000 ppm relative to the compound represented by formula (A)) was mixed and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.22 g of a non-fluorinated composition (1.218084 g of compound, 0.001916 g of platinum). The mass ratio of platinum to the obtained compound was 1,573 ppm in terms of platinum.

[0129] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B).

[0130] [Synthesis Example 3] In the reaction vessel, the following formula (A) 1.00 g (1.65 × 10) of the compound represented by -3 mol), toluene 1.00 g, triethoxysilane 0.815 g (4.96 x 10 -3 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 3.00 × 10 -3g (with a Pt content of 150 ppm relative to the compound represented by formula (A)) was mixed and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.20 g of a non-fluorinated composition (1.199858 g of compound, 0.000142 g of platinum). The mass ratio of platinum to the obtained compound was 118 ppm in terms of platinum.

[0131] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B).

[0132] [Synthesis Example 4] In the reaction vessel, the following formula (A) 1.00 g (1.65 × 10) of the compound represented by -3 mol), triethoxysilane 0.815 g (4.96 x 10 -3 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 7.60 × 10 -2 g (with a Pt content of 3,800 ppm relative to the compound represented by formula (A)) was mixed and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.25 g of a non-fluorinated composition (1.246276 g of compound, 0.003724 g of platinum). The mass ratio of platinum to the obtained compound was 2,988 ppm in terms of platinum.

[0133] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B).

[0134] [Synthesis Example 5] In the reaction vessel, the following formula (C) 1.00 g (2.06 × 10) of the compound represented by -3 mol), trimethoxysilane 2.26 g (1.85 x 10) -2 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 6.00 × 10 -2g (Pt content: 3,000 ppm with respect to the compound represented by formula (C)) was mixed and aged at 80 °C for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.70 g of a non-fluorine-based composition (1.697097 g of the compound and 0.002903 g of platinum). The mass ratio of platinum with respect to the obtained compound was 1,711 ppm in terms of platinum.

[0135] The obtained compound 1 was confirmed to have a structure represented by the following formula (D) by 1H-NMR.

[0136] [Synthesis Example 6] In a reaction vessel, 1.00 g (1.35 × 10 mol) of the compound represented by the following formula (E), 1.00 g of toluene, 0.987 g (8.08 × 10 -3 mol) of trimethoxysilane, and 2.00 × 10 -3 g of a toluene solution of a platinum / vinylsiloxane complex (Pt content: 5 mass%) (Pt content: 1,000 ppm with respect to the compound represented by formula (E)) were mixed and aged at 80 °C for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.25 g of a non-fluorine-based composition (1.249060 g of the compound and 0.000940 g of platinum). The mass ratio of platinum with respect to the obtained compound was 752 ppm in terms of platinum. -2

[0137] The obtained compound 1 was confirmed to have a structure represented by the following formula (F) by 1H-NMR.

[0138] [Synthesis Example 7] In a reaction vessel, 1.00 g (1.37 × 10 mol) of the compound represented by the following formula (G), 1.00 g of toluene, 0.501 g (4.11 × 10 -3 mol) of trimethoxysilane, and 1.60 × 10 -3 g of a toluene solution of a platinum / vinylsiloxane complex (Pt content: 5 mass%) -2g (Pt content: 800 ppm with respect to the compound represented by formula (G)) was mixed and aged at 80 °C for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.13 g of a non-fluorine-based composition (1.129226 g of the compound and 0.000774 g of platinum). The mass ratio of platinum to the obtained compound was 685 ppm in terms of platinum.

[0139] The obtained compound 1 was confirmed to have the structure represented by the following formula (H) by 1H-NMR.

[0140] [Synthesis Example 8] In a reaction vessel, 1.00 g (1.82×10 mol) of the compound represented by the following formula (I), 1.00 g of toluene, 0.668 g (5.47×10 -3 mol) of trimethoxysilane, and 3.00×10 -3 g of a toluene solution of a platinum / vinylsiloxane complex (Pt content: 5% by mass) (Pt content: 1,500 ppm with respect to the compound represented by formula (I)) were mixed and aged at 80 °C for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.21 g of a non-fluorine-based composition (1.208517 g of the compound and 0.001483 g of platinum). The mass ratio of platinum to the obtained compound was 1,227 ppm in terms of platinum. -2 g (Pt content: 1,500 ppm with respect to the compound represented by formula (I)) were mixed and aged at 80 °C for 24 hours. Thereafter, the solvent and unreacted substances were distilled off under reduced pressure to obtain 1.21 g of a non-fluorine-based composition (1.208517 g of the compound and 0.001483 g of platinum). The mass ratio of platinum to the obtained compound was 1,227 ppm in terms of platinum.

[0141] The obtained compound 1 was confirmed to have the structure represented by the following formula (J) by 1H-NMR.

[0142] [Synthesis Example 9] In a reaction vessel, 1.00 g (1.39×10 mol) of the compound represented by the following formula (K), 0.509 g (4.16×10 -3 mol) of trimethoxysilane, and 7.00×10 -3 g of a toluene solution of a platinum / vinylsiloxane complex (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: 5% by mass) (Pt content: -2 ​g (with a Pt content of 3,500 ppm relative to the compound represented by formula (K)) was mixed and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.10 g of a non-fluorinated composition (1.096718 g of compound, 0.003282 g of platinum). The mass ratio of platinum to the obtained compound was 2,993 ppm in terms of platinum.

[0143] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (L).

[0144] [Synthesis Example 10] In the reaction vessel, the following formula (M) 1.00 g (2.38 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 0.509 g (4.16 x 10 -3 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 4.00 × 10 -3 g (with a Pt content of 200 ppm relative to the compound represented by formula (M)) was mixed and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.28 g of a non-fluorinated composition (1.279802 g of compound, 0.000198 g of platinum). The mass ratio of platinum to the obtained compound was 155 ppm in terms of platinum.

[0145] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (N).

[0146] [Synthesis Example 11] In the reaction vessel, the following formula (O) 1.00 g (1.96 × 10) of the compound represented by -3 mol), toluene 1.00 g, trimethoxysilane 2.15 g (1.76 x 10 -2 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 5.00 × 10 -2g (with a Pt content of 2,500 ppm relative to the compound represented by formula (O)) was mixed and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.64 g of a non-fluorinated composition (1.637627 g of compound, 0.002383 g of platinum). The mass ratio of platinum to the obtained compound was 1,455 ppm in terms of platinum.

[0147] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (P).

[0148] [Synthesis Example 12] In the reaction vessel, the following formula (A) 1.00 g (1.65 × 10) of the compound represented by -3 mol), triethoxysilane 0.815 g (4.96 x 10 -3 A toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) was mixed with 0.120 g (Pt content of 6,000 ppm relative to the compound represented by formula (A)) and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.16 g of a non-fluorinated composition (1.154553 g of compound, 0.005447 g of platinum). The mass ratio of platinum to the obtained compound was 4,718 ppm in terms of platinum.

[0149] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B).

[0150] [Synthesis Example 13] In the reaction vessel, the following formula (A) 1.00 g (1.65 × 10) of the compound represented by -3 mol), toluene 1.00 g, triethoxysilane 0.815 g (4.96 x 10 -3 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 4.00 × 10 -5g (with a Pt content of 2 ppm relative to the compound represented by formula (A)) was mixed and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.26 g of a non-fluorinated composition (1.259998 g of compound, 0.000002 g of platinum). The mass ratio of platinum to the obtained compound was 1.57 ppm in terms of platinum.

[0151] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B).

[0152] [Synthesis Example 14] In the reaction vessel, the following formula (A) 1.00 g (1.65 × 10) of the compound represented by -3 mol), toluene 1.00 g, triethoxysilane 0.815 g (4.96 x 10 -3 mol), and a toluene solution of platinum / vinylsiloxane complex (Pt content: 5% by mass) 1.00 × 10 -3 g (with a Pt content of 50 ppm relative to the compound represented by formula (A)) was mixed and aged at 80°C for 24 hours. Subsequently, the solvent and unreacted materials were removed by vacuum distillation to obtain 1.24 g of a non-fluorinated composition (1.239951 g of compound, 0.000049 g of platinum). The mass ratio of platinum to the obtained compound was 39 ppm in terms of platinum.

[0153] The resulting compound was 1 ¹H-NMR confirmed that the structure is represented by the following formula (B).

[0154] [Example 1] The non-fluorine-based composition obtained in Synthesis Example 1 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[0155] [Example 2] The nonfluorine-based composition obtained in Synthesis Example 2 was dissolved in isooctane to a concentration of 10% by mass to prepare a surface treatment agent.

[0156] [Example 3] The non-fluorine-based composition obtained in Synthesis Example 3 was dissolved in dibutyl ether to a concentration of 15% by mass to prepare a surface treatment agent.

[0157] [Example 4] The non-fluorine-based composition obtained in Synthesis Example 4 was dissolved in dibutyl ether to a concentration of 60% by mass to prepare a surface treatment agent.

[0158] [Example 5] The non-fluorine-based composition obtained in Synthesis Example 5 was dissolved in toluene to a concentration of 5% by mass to prepare a surface treatment agent.

[0159] [Example 6] The nonfluorine-based composition obtained in Synthesis Example 6 was dissolved in isononane to a concentration of 30% by mass to prepare a surface treatment agent.

[0160] [Comparative Example 1] The non-fluorine-based composition obtained in Synthesis Example 12 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[0161] [Comparative Example 2] The non-fluorine-based composition obtained in Synthesis Example 13 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[0162] [Comparative Example 3] The non-fluorine-based composition obtained in Synthesis Example 14 was dissolved in toluene to a concentration of 20% by mass to prepare a surface treatment agent.

[0163] Formation of a hardened film of the surface treatment agent: Glass (Corning Gorilla Glass (product code: Gorilla III, size: 100 mm x 50 mm x 0.7 mm)) whose outermost surface was coated with SiO2 to a thickness of 10 nm under the following conditions was subjected to vacuum deposition (equipment: ULVAC KIKO, product code: VTR-350M) of each surface treatment agent prepared in the above examples and comparative examples (processing conditions: pressure: 2.0 x 10 -2 A cured film with a thickness of 3-7 nm was formed by curing in an atmosphere of Pa, heating temperature: 700°C, 80°C, and 80% relative humidity for 1 hour, and then in an atmosphere of 25°C, 50% relative humidity for 12 hours. [SiO2 layer deposition conditions] Deposition apparatus: OTFC-1300 (Optolan Co., Ltd.) Deposition material: SiO2 Deposition chamber pressure: 0.015 Pa Deposition rate: 0.8 nm / s Deposition film thickness: 10 nm

[0164] The water repellency, abrasion resistance, and coloration of the substrate were evaluated for the glass with a hardened coating using the method described below.

[0165] Evaluation of Water Repellency The contact angle (water repellency) of the hardened film formed on the glass prepared as described above was measured using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement was performed by photographing the droplet 1 second after dropping with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using FAMAS, the contact angle analysis software attached to the contact angle meter, to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results are shown in Table 1. In this invention, a good (water-repellent) water contact angle was defined as 90° or higher (the same applies hereafter). [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame threshold level: Automatic

[0166] Abrasion Resistance Evaluation The glass with the hardened coating prepared as described above was rubbed every 1,000 times using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.) under the following conditions. The contact angle (water repellency) of the hardened coating with water was measured in the same manner as described above, and the number of times the water contact angle fell below 80° was counted to evaluate abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (number of times the water contact angle fell below 80°) are shown in Table 1. [Steel Wool Abrasion Resistance Test Conditions] Steel wool: Bonster #0000 Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 500 gf / cm 2

[0167] Evaluation of substrate coloration (appearance evaluation): The appearance (color) of the substrate on which the cured film was formed was observed visually. The results are shown in Table 1.

[0168] The surface treatment agent in Comparative Example 1, which had a higher platinum content than the non-fluorine composition of the present invention, formed a colored cured film. The surface treatment agents in Comparative Examples 2 and 3, which had a lower platinum content than the non-fluorine composition of the present invention, formed a cured film with poor abrasion resistance. In contrast, the surface treatment agents in Examples 1 to 6, which contained the non-fluorine composition of the present invention, were able to form a cured film with less coloration, transparency, and excellent water repellency and abrasion resistance.

[0169]

[0170] [Example 7] The nonfluorine-based composition obtained in Synthesis Example 2 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0171] [Example 8] The non-fluorine-based composition obtained in Synthesis Example 3 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0172] [Example 9] The nonfluorine-based composition obtained in Synthesis Example 4 was dissolved in isononane to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0173] [Example 10] The nonfluorine-based composition obtained in Synthesis Example 7 was dissolved in a hexane / isooctane mixture (mass ratio 50 / 50) to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0174] [Example 11] The nonfluorine-based composition obtained in Synthesis Example 8 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0175] [Example 12] The nonfluorine-based composition obtained in Synthesis Example 9 was dissolved in butyl acetate to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0176] [Example 13] The nonfluorine-based composition obtained in Synthesis Example 10 was dissolved in ethylcyclohexane to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0177] [Example 14] The non-fluorine-based composition obtained in Synthesis Example 11 was dissolved in dibutyl ether to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0178] [Comparative Example 4] A surface treatment agent was prepared by dissolving the nonfluorine-based composition obtained in Synthesis Example 12 in toluene to a concentration of 0.2% by mass.

[0179] [Comparative Example 5] A surface treatment agent was prepared by dissolving the nonfluorine-based composition obtained in Synthesis Example 13 in toluene to a concentration of 0.2% by mass.

[0180] [Comparative Example 6] The non-fluorine-based composition obtained in Synthesis Example 14 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0181] The surface treatment agents prepared in the above examples and comparative examples were spray-coated onto glass (Corning Gorilla Glass (product code: Gorilla III, size: 100 mm x 50 mm x 0.7 mm)) to form a cured film of the surface treatment agent. The film was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film with a thickness of 3 to 7 nm.

[0182] The water repellency, abrasion resistance, and appearance of the substrate were evaluated for the glass with a hardened coating using the method described below.

[0183] Evaluation of Water Repellency The contact angle (water repellency) of the hardened film formed on the glass prepared as described above was measured using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement was performed by photographing the droplet 1 second after dropping with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using FAMAS, the contact angle analysis software attached to the contact angle meter, to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results are shown in Table 2. In this invention, a good (water-repellent) water contact angle was defined as 90° or higher (the same applies hereafter). [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame threshold level: Automatic

[0184] Abrasion Resistance Evaluation The glass with the hardened coating prepared as described above was rubbed every 1,000 times using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.) under the following conditions. The contact angle (water repellency) of the hardened coating with water was measured in the same manner as described above, and the number of times the water contact angle fell below 80° was counted to evaluate abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (number of times the water contact angle fell below 80°) are shown in Table 2. [Steel Wool Abrasion Resistance Test Conditions] Steel wool: Bonster #0000 Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 500 gf / cm 2

[0185] Evaluation of substrate coloration (appearance evaluation): The appearance (color) of the substrate on which the cured film was formed was observed visually. The results are shown in Table 2.

[0186] The surface treatment agent in Comparative Example 4, which had a higher platinum content than the non-fluorine composition of the present invention, formed a colored cured film. The surface treatment agents in Comparative Examples 5 and 6, which had a lower platinum content than the non-fluorine composition of the present invention, formed a cured film with poor abrasion resistance. In contrast, the surface treatment agents in Examples 7 to 14, which contained the non-fluorine composition of the present invention, were able to form a cured film with less coloration, transparency, and excellent water repellency and abrasion resistance.

[0187]

[0188] [Example 15] The nonfluorine-based composition obtained in Synthesis Example 2 was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0189] [Example 16] A toluene solution of a platinum / vinylsiloxane complex (Pt content: 5% by mass) was mixed with the nonfluorine-based composition obtained in Synthesis Example 3 so that the mass ratio of platinum to the compound obtained in Synthesis Example 3 was 2,000 ppm. The resulting nonfluorine-based composition was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0190] [Example 17] A toluene solution of a platinum / vinylsiloxane complex (Pt content: 5% by mass) was mixed with the nonfluorine-based composition obtained in Synthesis Example 14 so that the mass ratio of platinum to the compound obtained in Synthesis Example 14 was 2,000 ppm. The resulting nonfluorine-based composition was dissolved in toluene to a concentration of 0.2% by mass to prepare a surface treatment agent.

[0191] [Comparative Example 7] A surface treatment agent was prepared by dissolving the nonfluorine-based composition obtained in Synthesis Example 13 in toluene to a concentration of 0.2% by mass.

[0192] The surface treatment agents prepared in the above examples and comparative examples were spray-coated onto glass (Corning Gorilla Glass (product code: Gorilla III, size: 100 mm x 50 mm x 0.7 mm)) to form a cured film of the surface treatment agent. The film was then cured for 1 hour at 80°C and 80% relative humidity, and then for 12 hours at 25°C and 50% relative humidity to form a cured film with a thickness of 3 to 7 nm.

[0193] The water repellency, abrasion resistance, and appearance of the substrate were evaluated for the glass with a hardened coating using the method described below.

[0194] Evaluation of Water Repellency The contact angle (water repellency) of the hardened film formed on the glass prepared as described above was measured using a Drop Master contact angle meter (Kyowa Interface Science Co., Ltd., DMo-701SA) (droplet: 2 μl, temperature: 25°C, relative humidity: 40%). The measurement was performed by photographing the droplet 1 second after dropping with a CCD camera connected to the contact angle meter, and then analyzing the droplet image using FAMAS, the contact angle analysis software attached to the contact angle meter, to measure the contact angle between the glass substrate and the droplet. The contact angle was calculated using the θ / 2 method. The analysis conditions are as follows. The results are shown in Table 3. In this invention, a good (water-repellent) water contact angle was defined as 90° or higher (the same applies hereafter). [Analysis Conditions] Method: Droplet method (θ / 2 method) Droplet recognition: Automatic Droplet recognition line (distance from needle tip): 50 dots Algorithm: Automatic Image mode: Frame threshold level: Automatic

[0195] Abrasion Resistance Evaluation The glass with the hardened coating prepared as described above was rubbed every 1,000 times using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.) under the following conditions. The contact angle (water repellency) of the hardened coating with water was measured in the same manner as described above, and the number of times the water contact angle fell below 80° was counted to evaluate abrasion resistance. The test environment conditions were 25°C and 40% relative humidity. The results (number of times the water contact angle fell below 80°) are shown in Table 3. [Steel Wool Abrasion Resistance Test Conditions] Steel wool: Bonster #0000 Contact area: 1 cm 2 Distance traveled (one way): 40 mm; Speed: 4,800 mm / min; Load: 500 gf / cm 2

[0196] Evaluation of substrate coloration (appearance evaluation): The appearance (color) of the substrate on which the cured film was formed was observed visually. The results are shown in Table 3.

[0197] The surface treatment agent in Comparative Example 7, which had a lower platinum content than the non-fluorine composition of the present invention, formed a cured film with poor abrasion resistance. In contrast, the surface treatment agents in Examples 15 to 17, which contained the non-fluorine composition of the present invention, were able to form a cured film with minimal discoloration, transparency, and excellent water repellency and abrasion resistance. It was also found that similar results could be obtained even if a transition metal compound was added after compound synthesis, as long as the non-fluorine composition met the requirements of the present invention.

[0198]

Claims

(A) A nonfluorinated hydrocarbon end group-containing compound and / or a partially reacted condensate thereof having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, and a reactive silyl group, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and (B) Transition metal or its compound: 100 to 4,000 ppm in terms of the mass of the transition metal relative to component (A) A non-fluorinated composition containing the following: The nonfluorine-based composition according to claim 1, wherein the hydrocarbon terminal group-containing compound of component (A) is a compound represented by the following general formula (1). (In the formula, R 1 R may independently contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and may be linear, branched, cyclic, or a combination thereof, and is a monovalent hydrocarbon group having 3 to 32 carbon atoms, 2 (where k1 is a hydrogen atom, halogen atom, hydroxyl group, siloxy group, amino group, thiol group, or a monovalent hydrocarbon group having 1 or 2 carbon atoms; U is a carbon atom, silicon atom, nitrogen atom, or a trivalent or tetravalent organic group; V is independently a single bond or a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, and sulfur atoms; Z is independently a single bond, carbon atom, silicon atom, nitrogen atom, sulfur atom, or a trivalent to octavalent organic group; Y is independently a divalent hydrocarbon group which may contain at least one selected from oxygen, nitrogen, sulfur, and silicon atoms; A is independently a monovalent reactive silyl group; k1 is an integer from 1 to 3; k2 is 0 or 1; k3 is an integer from 1 to 3; k1 + k2 + k3 is 3 or 4; and m is an integer from 1 to 7.) 　 In the above equation (1), A is the following general equation (2) (In the formula, R is independently an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is independently a hydroxyl group or a hydrolyzable group, and n is an integer from 1 to 3.) The non-fluorinated composition according to claim 2, wherein the group is represented by . 　 The nonfluorine-based composition according to claim 3, wherein in formula (2) above, X is selected from the group consisting of a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkoxyalkoxy group having 2 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a halogen group, and a dialkylamino group having 2 to 10 carbon atoms. 　 In the above formula (1), R 1 However, the following formula (In the formula, R A Q is a monovalent hydrocarbon group having 3 to 32 carbon atoms, which may be linear, branched, cyclic, or a combination thereof, and Q is independently an oxygen atom, a sulfur atom, a divalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a diorganosilylene group, a sylalkylene structure or sylarylene structure, and a linear or branched or cyclic divalent organopolysiloxane residue having 2 to 10 silicon atoms, or having 3 to 10 silicon atoms, a carbonyl (ketone) group, an ester group, a carbonate group, a sulfinyl group, a sulfonyl group, a thioester group, a thiocarbonate group, a thiocarbamate group, an amino group, an amide group, or a carbamate group. Q' is a divalent group selected from the group consisting of a urea group and a divalent nitrogen-containing heterocyclic group, Q' is independently a trivalent group selected from the group consisting of a nitrogen atom, a trivalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, and a trivalent nitrogen-containing heterocyclic group, Q'' is independently a tetravalent group selected from the group consisting of a silicon atom, a tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, and R B R is a divalent hydrocarbon group having 1 to 29 carbon atoms, which may be independently single-bonded, linear, branched, or cyclic, C R is independent A (or a hydrogen atom, where p is an integer between 0 and 10. However, the total number of carbon atoms in each structure is 32 or less.) The non-fluorine-based composition according to claim 2, wherein the group is any of those represented by . 　 The nonfluorine-based composition according to claim 2, wherein Y in formula (1) above is a group selected from the group consisting of an alkylene group having 1 to 20 carbon atoms which may contain at least one selected from oxygen atoms, nitrogen atoms, and sulfur atoms; an alkylene group having 1 to 10 carbon atoms which includes an arylene group having 6 to 8 carbon atoms; a divalent group in which alkylene groups having 1 to 8 carbon atoms are bonded to each other via a diorganosilylene group, a sylalkylene structure, a sylarylene structure, or a nitrogen-containing heterocyclic group; and a divalent group in which an alkylene group having 1 to 10 carbon atoms is bonded to the binding site of a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic organopolysiloxane residue having 3 to 10 silicon atoms. 　 In the above formula (1), Z is a single bond, or a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, -SiR 3 = (R 3 is a trivalent group represented by a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms), -CR 4 = (R 4 is a trivalent group represented by a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms), a linear organopolysiloxane residue having 2 to 10 silicon atoms or a branched or cyclic trivalent to octavalent organopolysiloxane residue having 3 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent to octavalent nitrogen-containing heterocyclic group-containing group, and the non-fluorine-based composition according to claim 2, which is a trivalent to octavalent group selected from the group consisting of 　 The nonfluorine-based composition according to claim 2, wherein in formula (1) above, U is a trivalent or tetravalent group selected from the group consisting of a carbon atom, a silicon atom, a nitrogen atom, a trivalent or tetravalent cyclic hydrocarbon group having 6 to 8 carbon atoms, a linear or branched or cyclic trivalent or tetravalent organopolysiloxane residue having 2 to 10 silicon atoms, a trivalent amide group, a trivalent carbamate group, a trivalent or tetravalent urea group, and a trivalent or tetravalent nitrogen-containing heterocyclic group. (B) The non-fluorinated composition according to claim 1, wherein a transition metal or a compound thereof acts as a catalyst for a hydrosilylation addition reaction. (B) The non-fluorinated composition according to claim 1, wherein the transition metal or its compound is platinum or a platinum compound. 　 A surface treatment agent characterized by comprising a non-fluorine-based composition according to any one of claims 1 to 10 and a solvent. 　 An article surface-treated with the surface treatment agent described in claim 11. 　 A method for producing a nonfluorinated composition according to claim 1, comprising the steps of: mixing a compound (i) having an alkenyl group at its terminus and at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms; and a compound (ii) having an SiH group and a reactive silyl group; and carrying out a hydrosilylation addition reaction with compound (i) in the presence of a transition metal or a compound thereof in an amount of 100 ppm or more in terms of transition metal, thereby producing a nonfluorinated hydrocarbon terminus-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and a reactive silyl group. 　 A method for producing a non-fluorinated composition according to claim 13, wherein the transition metal or its compound is platinum or a platinum compound. (I) A compound (i) having an alkenyl group at its terminus and at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms; and a compound (ii) having an SiH group and a reactive silyl group; and a hydrosilylation addition reaction being carried out with compound (i) in the presence of a transition metal or a compound thereof in an amount of 0.01 ppm or more and less than 100 ppm in terms of transition metal, thereby producing a nonfluorine-based hydrocarbon terminus-containing compound having at least one linear, branched, or cyclic monovalent hydrocarbon group having 3 to 60 carbon atoms, which may contain at least one selected from oxygen, sulfur, nitrogen, and silicon atoms, and a reactive silyl group. (II) Adding a transition metal or a compound thereof to the product obtained in step (I) in such a mass of the transition metal that it is 100 to 4,000 ppm relative to the obtained hydrocarbon-terminated compound and / or its partially reacted condensate. A method for producing the non-fluorinated composition according to claim 1, characterized by containing the following: 　 A method for producing a non-fluorinated composition according to claim 15, wherein the transition metal or its compound is platinum or a platinum compound.

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