Novel organosilicon compound and surface treatment agent and method for producing the same

Abstract

To provide a compound that can be used as a surface treatment agent having high adhesiveness to a wide range of base materials and excellent water resistance and salt water resistance.SOLUTION: There is provided a silane derivative of benzothiazole represented by general formula (I).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel organosilicon compound and a surface treatment agent, as well as a method for producing the same. [Background technology]

[0002] Regardless of whether the material is metal, plastic, or the like, the material constituting the base material of an article is often subjected to a surface treatment for the purpose of improving quality such as appearance, hardness, durability, and reliability, reducing running costs by improving repairability and energy saving, improving dimensional accuracy and secondary processability, and imparting further physical properties such as heat resistance, corrosion resistance, electrical properties, etc. In particular, in the surface treatment of metals, chrome plating, which has high corrosion resistance, has traditionally been used, but due to the toxicity of chrome, etc., replacement with alternative materials with higher environmental compatibility has been promoted.

[0003] Silicon compounds have been attracting attention as non-chromium surface treatment agents because they are abundant in the ground, pose little environmental problems, and form strong chemical bonds. For example, silicone has a strong siloxane bond, which is expected to provide heat resistance and water repellency. In addition, several materials using silane coupling agents as low molecular weight compounds have been developed (Patent Documents 1 to 7). Silane coupling agents are organosilicon compounds that have both a functional group reactive with organic substances and a hydrolyzable group in the molecule, and can form chemical bonds with both organic and inorganic substances. As such, they are expected to be used as surface treatment agents that are highly adaptable to the type of material, in addition to firmly binding organic and inorganic substances with different chemical properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2016-79130 A [Patent Document 2] Japanese Patent Application Publication No. 6-279461 [Patent Document 3] Japanese Patent Application Publication No. 6-279463 [Patent Document 4] Japanese Patent Application Publication No. 5-186479 [Patent Document 5] JP 2014-009190 A [Patent Document 6] JP 2015-010079 A [Patent Document 7] Special Publication No. 62-502468 Summary of the Invention [Problem to be solved by the invention]

[0005] Although environmental compatibility is improved by changing the surface treatment material from chromium, a metal, to silane, an organic compound, there is a demand for improving the salt water resistance and corrosion resistance of surface treatment agents in order to effectively protect substrates made of plastics and metals for electronics applications from water or corrosion. In addition, since the adhesive strength between the coating film of the surface treatment agent and the member differs between metals and resins, there may be members to which some surface treatment agents cannot be applied. In this respect, there is also a demand for surface treatment agents that can be applied to a wide range of members.

[0006] It is therefore an object of the present invention to provide a compound that can be used as a surface treatment agent having high adhesion to a wide range of substrates and excellent water resistance and salt water resistance. [Means for solving the problem]

[0007] According to the investigations conducted by the present inventors, they have succeeded in designing and synthesizing a silane compound having a benzothiazole ring in the compound, and have found that the compound can provide a silicone composition capable of solving the above-mentioned problems, which has led to the present invention. Effect of the Invention

[0008] The present invention provides a compound that can be used as a surface treatment agent having high adhesion to a wide range of substrates and excellent water resistance and salt water resistance. The following formula (I): [ka] [In the formula, R 1 is independently in each occurrence hydrogen or a monovalent organic group; R 2 is, independently in each occurrence, a substituted or unsubstituted monovalent hydrocarbon radical or [ka] is a group represented by R 3 , R 4 , R 5 , R 6 each independently represents a hydrogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, or a phenyl group, n is an integer from 1 to 3; k and l each independently represent an integer of 1 to 10; A is -O-, -S-, -Si(CH3)2-, -Si(OR 1 )2-, -NR 7 -, -N=, -C(=O)-, -C(=O)O- and -C(=O)NR 7 - (where R 7 is a hydrogen atom or a C1-6 alkyl group), and [SiR 8 R 9 O 2 / 2 ], [SiR 8 O 3 / 2 ] and [SiO 4 / 2 ](where R 8 and R 9 are each independently a methyl group or a phenyl group, or a bond to another group), and may be interrupted by one or more groups selected from the group consisting of siloxane groups represented by the following units: 2 When it appears as a group in 2is a substituted or unsubstituted monovalent hydrocarbon group, A is not a butylene, propylene, or ethylene group. A compound represented by the formula: [2] The compound of [1] above, wherein k and l are both 1. [3] R 3 , R 4 , R 5 and R 6 are all hydrogen. [4]R 2 independently in each occurrence, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, xylyl, naphthyl, benzyl, phenylethyl, phenylpropyl, vinyl, allyl, propenyl, butenyl, ethynyl, propynyl, [ka] and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms or the like (wherein A and R 3 ~R 6 is as defined in the above [1], any one of the compounds [1] to [3] above. [5]R 1 may independently in each occurrence be CH3-, C2H5-, C3H7-, CF3CH2-, CH3CO-, CH2=C(CH3)-, CH3CH2C(CH3)=N-, (CH3)2N-, (C2H5)2N-, CH2=C(OC2H5)-, (CH3)2C=C(OC8H 17 )- or [ka] and n is 2 or 3. [6]R 1is, independently at each occurrence, CH3- or C2H5-. The present invention also relates to a compound according to any one of the above [1] to [6] for use in surface treatment of a metal; a surface treatment agent comprising a compound according to any one of the above [1] to [6]; and a metal member the surface of which has been treated with a compound according to any one of the above [1] to [6]. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The compound of the present invention will be described in detail for each item below. In this specification, the term "to" indicating a range of values ​​is used to mean that the values ​​before and after the range are included as the lower and upper limits.

[0010] As used herein, "organic group" refers to a group containing carbon. The valence of an organic group is indicated by describing it as "n-valent", where n is any natural number. Thus, for example, a "monovalent organic group" refers to a carbon-containing group having only one bond. The bond may be possessed by an element other than carbon. Even if the valence is not specifically stated, a person skilled in the art can grasp the appropriate valence from the context.

[0011] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, and at least one hydrogen atom has been removed from the molecule. Such a hydrocarbon group is not particularly limited, and may be substituted with one or more substituents, and may be a hydrocarbon group having 1 to 20 carbon atoms, such as an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The preferred number of carbon atoms varies depending on the position of the structure having the hydrocarbon group in the compound, but is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 6. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have, at its terminal or in the molecular chain, one or more heteroatoms or a structure containing a heteroatom, such as a nitrogen atom (N), an oxygen atom (O), a sulfur atom (S), a phosphorus atom (P), a silicon atom (Si), an amide bond, a sulfonyl bond, a siloxane bond, a carbonyl group, or a carbonyloxy group.

[0012] As used herein, examples of the substituents of the "hydrocarbon group" include, but are not limited to, halogen atoms; C 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, 5-10 membered unsaturated heterocyclyl groups, C 6-10 Examples of the substituent include a group selected from an aryl group and a 5- to 10-membered heteroaryl group. When a group having a substituent is defined by specifying a range of the number of carbon atoms, such as "a substituted hydrocarbon group having 1 to 6 carbon atoms", the number of carbon atoms does not include the number of carbon atoms of the substituent.

[0013] In this specification, alkyl groups and phenyl groups may be unsubstituted or substituted unless otherwise specified. Substituents for such groups are not particularly limited, but include, for example, halogen atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups and C 2-6 alkynyl groups.

[0014] The present invention relates to an organosilicon compound represented by the following general formula (I): [ka] (The definitions of each group in the formula are as above.) The compound represented by the above general formula (I) can be, for example, 1 When R are different groups, 3 In the case where each of the substituents such as aryl, aryl, aryl and aryls is a hydrocarbon having an asymmetric carbon atom or an alkenyl group, some of the substituents may have stereoisomers. In the case where the organosilicon compound represented by the general formula (I) of the present invention has a structure having stereoisomers, it may have each isomer as a single species or may be a mixture of each isomer in any ratio.

[0015] R 1 is independently in each occurrence hydrogen or a monovalent organic group. The group R bonded to silicon through oxygen 1 R acts as a part that exerts adhesive properties with the substrate. 1 is a hydrogen atom or an alkyl or alkenyl group having 1 to 12 carbon atoms (wherein R' is an alkyl group having 1 to 6 carbon atoms, which may form a ring together with the carbon portion of the alkyl or alkenyl group) which may optionally have a -C(=O)-, -NR'- or -N=C(R')- group at its terminal and one or more hydrogen atoms may be substituted with a halogen or an alkoxy group, and specific R 1CH3-, C2H5-, C3H7-, CF3CH2-, CH3CO-, CH2=C(CH3)-, CH3CH2C(CH3)=N-, (CH3)2N-, (C2H5)2N-, CH2=C(OC2H5)-, (CH3)2C=C(OC8H 17 )- or [ka] In view of the ease of obtaining and preparing the compounds, including those commercially available, R 1 is preferably CH3- or C2H5-. 1 Depending on the value of n, there may be more than one R in one molecule. 1 Each occurrence of R can be independently a group falling within the scope of the above definitions. 1 may be the same or different.

[0016] R 2 is, independently in each occurrence, a substituted or unsubstituted monovalent hydrocarbon radical or [ka] (wherein A and R 3 ~R 6 is defined as follows. 2 Examples of R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a benzyl group, a phenylethyl group, a phenylpropyl group, a vinyl group, an allyl group, a propenyl group, a butenyl group, an ethynyl group, a propynyl group, the above-mentioned structures having a benzothiazole ring, and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms or the like. 2 Since the use of a group that is not bulky is preferable in terms of adhesion to the substrate, R is preferably a methyl group or an ethyl group. 2Depending on the value of n, there may be more than one R in one molecule. 2 Each occurrence of R can be independently a group falling within the scope of the above definitions. 2 may be the same or different.

[0017] R 3 , R 4 , R 5 , R 6 are each independently a hydrogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, or a phenyl group. 3 ~R 6 is a substituent of the benzothiazole ring. In the case of a structure having two or more benzothiazole rings in one molecule, each R 3 , R 4 , R 5 , R 6 may be different from each other. 3 , R 4 , R 5 and R 6 Preferably, at least one of them is hydrogen, more preferably, at least two of them are hydrogen, further preferably, at least three of them are hydrogen, and particularly preferably, all of them are hydrogen.

[0018] n is an OR bonded to silicon 1 It corresponds to the number of groups and is an integer from 1 to 3. OR 1 Since the group is involved in adhesion to the substrate, the value of n is preferably 2 or 3 from the viewpoint of obtaining high adhesion.

[0019] l is the -Si(OR 1 ) n (R 2 ) 3-n The value of l is 2 or more, i.e., -Si(OR 1 ) n (R 2 ) 3-nWhen there are multiple groups in one molecule, the adhesion to a substrate is further improved when the surface treatment agent is used. On the other hand, in terms of ease of design and preparation of the compound and ease of use, l is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

[0020] k is related to the number of benzothiazole rings contained in one molecule and is an integer of 1 to 10. Benzothiazole has sulfur and nitrogen, and has a plurality of points that show different coordination abilities with metals. Therefore, it is considered that it can exhibit rust prevention performance against substrates made of various metals. When the value of k is 2 or more, that is, when there are a plurality of benzothiazole rings in one molecule, the water resistance is further improved when used as a surface treatment agent. On the other hand, in terms of ease of preparation and ease of use, k is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

[0021] A is a spacer between the benzothiazole ring to which sulfur is bonded and silicon, and is -O-, -S-, -Si(CH3)2-, -Si(OR 1 )2-, -NR 7 -, -N=, -C(=O)-, -C(=O)O- and -C(=O)NR 7 - (where R 7 is a hydrogen atom or a C1-6 alkyl group), and [SiR 8 R 9 O 2 / 2 ], [SiR 8 O 3 / 2 ] and [SiO 4 / 2 A siloxane group composed of a combination of units represented by the formula: 8 and R 9 are each independently a methyl group or a phenyl group), A is a (k+l)-valent linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms, which may be interrupted by one or more groups selected from the group consisting of A, which is preferably a divalent hydrocarbon group having 2 to 20 carbon atoms and is selected from the group consisting of pentylene, hexylene, heptylene and octylene, k and l are both 1, and the group R 2is more preferably a linear group having 3 to 8 carbon atoms selected from propylene and butylene, except when A is a substituted or unsubstituted monovalent hydrocarbon group. A has a structure in which one or more hydrogen atoms have been removed from a monovalent hydrocarbon group or a group in which the monovalent hydrocarbon group is interrupted by a group such as -O-. Therefore, A is a divalent or higher group. Here, the group R 2 When A is included in the structure, A is a divalent group. The hydrocarbon group that is the main skeleton of A may be any of a linear, branched, or cyclic structure, or may be a combination of these. For example, it may have a structure in which linear groups extend radially from two or more positions of a cyclic structure such as benzene, cyclohexane, or cyclic siloxane, or may have a three-dimensional network structure in which multiple branched structures are combined.

[0022] Examples of the spacer group A consisting of only carbon and hydrogen include, but are not limited to, linear structures such as pentylene (-(CH2)5-), hexylene (-(CH2)6-), heptylene (-(CH2)7-), and octylene (-(CH2)8-), branched structures such as 1,1-ethylene (-CH(CH3)-), 1,2-propylene (CH2CHCH3), and 2,2-dimethyl-1,3-propylene (-CH2C(CH3)2CH2-), cyclic structures such as 1,3-cyclohexylene, 1,4-cyclohexylene, 1,4-cyclohexanedimethylene, phenylene, and naphthylene, and trivalent or higher groups obtained by removing hydrogen from any one or more of these structures. However, the present invention is not limited to these, provided that k and l are both 1 and the group R 2 is a substituted or unsubstituted monovalent hydrocarbon radical, A is not a butylene, propylene or ethylene radical; k and l are both 1, and the group R 2 is a substituted or unsubstituted monovalent hydrocarbon group, ethylene (-(CH2)2-), propylene (-(CH2)3-), and butylene (-(CH2)4-) become trivalent or higher groups by removing hydrogen from any one or more positions in these structures.

[0023] A is a compound whose hydrocarbon skeleton is -O-, -S-, -Si(CH3)2-, -Si(OR 1)2-, -NR 7 -, -N=, -C(=O)-, -C(=O)O- and -C(=O)NR 7 When it is interrupted by -N=, an N=C double bond is formed between the adjacent carbon and nitrogen. There is no limitation on the position of the interruption, and it may have a heterocyclic structure in which a part of the ring structure is interrupted, or it may have a form in which there is an interruption between the bond to the sulfur bonded to the benzothiazole ring and the terminal part of the hydrocarbon skeleton. For example, the spacer group A may have a structure having the above group at the terminal part of the group A, such as -O-CH2-, so long as a stable compound can be formed, and in this case, the oxygen may be bonded to either the sulfur or the silicon. Also, -Si(OR 1 The spacer group A may be interrupted by a structure combining a plurality of the above groups, such as represented by -O-, or may have a structure in which the hydrocarbon group is intermittently interrupted by oxygen, such as polyethylene glycol. Examples of the spacer group A being a hydrocarbon skeleton interrupted by some group include -(CH2)2O(CH2)2-, -(CH2)3O(CH2)3-, -(CH2)2S(CH2)2-, -(CH2)3S(CH2)3-, -(CH2)2O(CH2)2O(CH2)2-, -(C2H4O) n -, -(CH2)2Si(CH3)2(CH2)2-, -(CH2)2Si(OR 1 )2(CH2)2-, -(CH2)2NR 7 (CH2)2-, -(CH2)2C(=O)(CH2)2-, -(CH2)2C(=O)O(CH2)2-, -(CH2)2C(=O)NR 7Groups in which a part of a chain hydrocarbon is interrupted, such as (CH2)2-, -CH2C(=O)O(CH2)3O(CH2)3-, -CH2C(=O)O(CH2)3S(CH2)3-, -CH2C(=O)O(CH2)3OC(=O)CH2-, -CH2Si(CH3)2OSi(CH3)2-(CH2)2-, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, piperidine, pyran, morpholine, thiomorpholine, azepane, imidazole, pyrazole, Examples of such heterocyclic compounds include, but are not limited to, divalent groups in which any two hydrogen atoms of a heterocyclic compound such as oxazole, thiazole, pyridine, indole, quinoline, benzopyran, benzoxazole, benzothiazole, xanthene, or carbazole are replaced with bonds, groups having a structure in which a portion of a hydrocarbon chain is replaced with the above-mentioned heterocycle, such as pyridine-2,5-dimethylene, and trivalent or higher groups in which any one or more hydrogen atoms of these structures have been further removed.

[0024] The structure represented by A is [SiR 8 R 9 O 2 / 2 ], [SiR 8 O 3 / 2 ] and [SiO 4 / 2 A siloxane group composed of a combination of units represented by the formula: 8 and R 9 may be interrupted by a spacer, each of which is independently a methyl group or a phenyl group, or a bond to another group. That is, the compound of the present invention may optionally have a structure having a siloxane skeleton as a spacer. The structure of the spacer portion having a siloxane skeleton is not particularly limited, and may be any of the following: [SiR 8 R 9 O 2 / 2 ](D units), [SiR 8 O 3 / 2 ] (T units) and [SiO 4 / 2] (Q unit). For example, it may have a linear structure composed of only D units, a branched or cyclic structure by including T units, or a three-dimensional network structure by including Q units. Usually, a finite number of combinations of D units, T units, and Q units include at least two bond portions, but the portion where the siloxane skeleton bonds to other groups may be located in any part of each unit that constitutes the siloxane skeleton. When multiple D units form a cyclic structure, the group R 8 or R 9 can be bonded to other groups. For example, a group having a cyclic siloxane skeleton is a group having at least two groups R 8 is a bond to a hydrocarbon group such as an ethylene group, as shown below. [ka] (The wavy line in the formula is the part that bonds to other groups of the spacer.) The siloxane skeleton may be linked to a group that interrupts the hydrocarbon group, such as the -O- group. The chemical stability of the compound of general formula (I) is improved by containing a siloxane skeleton, and therefore the compound can be preferably used in applications where cold resistance and heat resistance are particularly required.

[0025] The structure represented by A is a benzothiazole ring and -Si(OR 1 ) n (R 2 ) 3-n In the case of a linear compound, the benzothiazole ring and -Si(OR 1 ) n (R 2 ) 3-n The groups represented by the formula: are usually located at both ends of the molecule, but a benzothiazole ring or -Si(OR 1 ) n (R 2 ) 3-nmay have a structure in which a group represented by R 2 is a group containing a benzothiazole ring, -Si(OR 1 ) n (R 2 ) 3-n In the case where the spacer has a branched or cyclic structure, the benzothiazole ring and the -Si(OR 1 ) n (R 2 ) 3-n The positional relationship of the groups represented by is not particularly limited.

[0026] A preferred embodiment of the compound of the present invention is a compound represented by the following formula (I-2). [ka] The above formula corresponds to the case where k and l are both 1 in formula (I), and R 1 ~R 6 and n is as defined above. A represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by a specific group.

[0027] A preferred embodiment of the compound of the present invention is a compound represented by the following formula (I-3). [ka] The above formula corresponds to the case where k and l are both 1 in formula (I) and A has a siloxane skeleton, and R 1 ~R 6 where n is as defined above, and m is an integer of 1 to 300. A' is a divalent hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by a specific group. The compound represented by formula (I-3) has a divalent linear siloxane group composed of D units.

[0028] A preferred embodiment of the compound of the present invention is a compound represented by the following formula (I-4). [ka] The above formula corresponds to the case where k and l are both 2 in formula (I) and A has a cyclic siloxane skeleton, and R 1 ~R 6 and n is as defined above. A" is a divalent hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by a specified group. In formula (I-4), the case where both k and l are 2 is exemplified, but it is understood that the case where the values ​​of k and l are 1 and 3, respectively, or k and l are independently 1 and the portion following A" is replaced with a methyl group, and compounds in which the positional relationship between the alkoxysilyl group and the group containing benzothiazole is arbitrarily rearranged are also included within the scope of the present invention.

[0029] Specific examples of the compound of the present invention include the following compounds, but the scope of the present invention is not limited to these. [ka] (In the above formula, the value of a is not particularly limited, but is preferably an integer of 1 to 300, more preferably 1 to 150, and particularly preferably 2 to 30; the value of m is not particularly limited, but is preferably an integer of 1 to 300, and more preferably 1 to 150.)

[0030] <Method for producing silane compounds> The compound of the present invention can be obtained by reacting mercaptobenzothiazole with silane. More specifically, it can be obtained by reacting a siloxane having a halogenated alkyl group with a salt of mercaptobenzothiazole. An example of a synthesis method with a simplified structure is shown below. In addition, a compound having a siloxane skeleton as a spacer group can be synthesized by reacting the compound obtained by the following method with polydimethylsiloxane. [ka]

[0031] The quantitative ratio of the mercaptobenzothiazole salt to the siloxane having a halogenated alkyl group can be appropriately set, but it is preferable that the amount of the siloxane having a halogenated alkyl group relative to the mercaptobenzothiazole salt is 0.5 to 1.5 mol, and particularly 0.8 to 1.2 mol.

[0032] In order to synthesize the compound of the present invention, a solvent may be used as necessary. The solvent is not particularly limited as long as it is non-reactive with the raw material compounds, and specific examples thereof include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and cyclohexane, ether solvents such as diethyl ether, tetrahydrofuran, and 1,4-dioxane, halogenated solvents such as chloroform and dichloromethane, amide solvents such as formamide, dimethylformamide, and N-methylpyrrolidone, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

[0033] The synthesis conditions of the compound of the present invention can be appropriately set, but when a solvent is used, the reaction temperature can be in the range of room temperature to the boiling point of the solvent. The reaction time is also affected by the temperature, but is usually about 1 to 12 hours.

[0034] <Surface treatment agent> The silane compound of the present invention can be used as a surface treatment agent for metals or plastics. When preparing the surface treatment agent, additives can be added according to a conventional method. Examples of additives that can be used include titanate compounds such as tetraethyl titanate and titanium acetyl titanate, silica such as spherical silica, chain silica, and aluminum-modified silica, salts or oxides of transition metals, compounds capable of generating phosphate ions such as polyphosphoric acid, diphosphoric acid, and sodium phosphate, resins such as acrylic resins, epoxy resins, polyolefins, polyurethanes, and polycarbonates, surfactants, leveling agents, wettability improvers, and antifoaming agents. In addition, silane compounds other than the above silane compounds, particularly silane compounds not having a benzothiazole ring, may be added. Examples of such compounds include compounds represented by the formula: R' a Si(OR”) 4-a(wherein R′ and R″ are each independently a monovalent hydrocarbon group, preferably methyl or ethyl, and a is an integer of 0 to 3, preferably 0 to 2). The amount of additives is not particularly limited as long as the compound of the present invention maintains its salt water and hot water resistance effect as a surface treatment agent. When additives are used, they can be used in a total amount of 500 parts by mass or less, preferably 200 parts by mass or less, and more preferably 100 parts by mass or less, per 100 parts by mass of the compound of the present invention.

[0035] The surface treatment agent of the present invention may contain a solvent to adjust the viscosity and facilitate uniform application to the substrate. In this case, the above silane compound may be dissolved in a suitable solvent to a desired concentration depending on the application and purpose. The solvent is preferably one that can dissolve the above silane compound, does not react with the silane compound, and is volatile. Specific examples of the solvent include water, an organic solvent that dissolves the above compound, or a mixed solvent of water and the organic solvent. Examples of the organic solvent include alcohol solvents such as methanol and ethanol, amide solvents such as formamide, N,N-dimethylformamide, pyrrolidone, and N-methylpyrrolidone, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, saturated hydrocarbon solvents such as pentane, hexane, and heptane, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and among these, methanol and ethanol are particularly preferred. The concentration of the solvent depends on the viscosity when made into a solution, and can be, for example, 80 parts by mass or less, preferably 50 parts by mass or less, and more preferably 40 parts by mass or less, relative to 100 parts by mass of the compound of the present invention.

[0036] The substrate to which the surface treatment agent containing the silane compound of the present invention is applied is not particularly limited in terms of its material. As the substrate, metals such as aluminum, copper, nickel, iron, brass, and stainless steel; engineering plastics such as epoxy resin, polyester resin such as polyethylene terephthalate and polybutylene terephthalate (PBT) resin, polycarbonate resin, acrylic resin, polyimide resin, phenolic resin, polyamide resin, polyphenylene sulfide (PPS) resin, and modified polyphenylene ether (PPE) resin; and glass can be used. In addition, if necessary, the wall surface of the gap may be subjected to a primer treatment according to a conventional method. The shape and thickness of the substrate are not particularly limited.

[0037] The surface treatment agent containing the silane compound of the present invention is applied to the surface of a part including a substrate in a predetermined thickness by a method such as dripping, pouring, casting, extrusion from a container, coating such as bar coating and roll coating, screen printing, dipping, brushing, spraying, dispensing, etc. These methods are known to those skilled in the art. The surface treatment agent may be applied entirely and uniformly on the surface of the part, or may be applied unevenly or partially, such as in lines, stripes, dots, etc. The application thickness of the surface treatment agent is usually 0.01 to 3 mm, preferably 0.05 to 2 mm. EXAMPLES

[0038] The composition of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the embodiments of these examples.

[0039] The compounds used in each of the Examples and Comparative Examples are as follows. The following compounds 1 to 13 formed yellow to brown coating films. In Comparative Example 1, 3-glycidoxypropyltrimethoxysilane, a compound having no benzothiazole ring, was used. [ka] [ka]

[0040] <Synthesis Example> The synthesis examples are shown below for reference. Each compound may be used in a concentrated state using a solvent such as xylene used in the preparation.

[0041] (Compound 2) 1000ml of xylene and 189.2g (1mol) of 2-mercaptobenzothiazole sodium (Tokyo Chemical Industry Co., Ltd.) were added to a 3000ml separable flask equipped with a nitrogen gas inlet tube and a condenser, and the mixture was stirred and dissolved under a nitrogen atmosphere, and 76.5g (1mol) of allyl chloride (Tokyo Chemical Industry Co., Ltd.) and an appropriate amount of an amine-based reaction catalyst were added, and the reaction was carried out at 120°C for 20 hours under a nitrogen stream. Chlorides and the like were then removed by filtration. The filtrate was then added to a 3000 ml flask equipped with a nitrogen gas inlet tube and a condenser, and 0.1 g of azobisisobutyronitrile (Tokyo Chemical Industry Co., Ltd.) was added, followed by stirring at room temperature for 5 minutes under a nitrogen atmosphere. 196.3 g (1 mol) of 3-mercaptopropyltrimethoxysilane was then added, and the mixture was heated to 50° C. while continuing to stir under a nitrogen atmosphere, and the reaction was continued for 6 hours. After filtration under a nitrogen atmosphere, xylene and the like were removed by distillation at 140° C. and 0.5 mmHg under reduced pressure, and 341 g (yield: 96%) of the target reactant, compound 2, was obtained. 1 Analysis by H-NMR revealed the following, confirming that it was the target compound. C6H4: 7.1ppm~7.8ppm, -Si(OCH3): 3.4ppm~3.5ppm, -S-CH2CH2 CH2 Si(OCH3)3: 0.6ppm~0.8ppm -S-CH2 CH2 CH2(OCH3)2Si-, -S-CH2 CH2 CH2-S-: 1.7ppm~2ppm -S- CH2 CH2CH2(OCH3)2Si-, -S‐ CH2 CH2CH2-S-: 3.2ppm~3.4ppm

[0042] (Compound 3) In the same manner as in the synthesis example of compound 2, 384 g (yield: 93%) of compound 3 was obtained by using 134.5 g (1 mol) of allyl chloroacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of allyl chloride. C6H4: 7.1ppm~7.8ppm, -Si(OCH3): 3.4ppm~3.5ppm, -S-CH2CH2 CH2 Si(OCH3)3, -S‐ CH2 CH2CH2-S-, -S- CH2 -C(O)-: 0.6ppm~0.9ppm -S-CH2 CH2 CH2Si(OCH3)3: 1.7ppm~2ppm -S- CH2 CH2CH2Si(OCH3)3-, -S‐ CH2 -C(O)-: 3.2ppm~3.4ppm -C(O)- CH2- : 4.0-4.3ppm,

[0043] (Compound 4) A 5000 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 600 g (2.59 mol) of 1,3-bis(chloromethyl)-tetramethyldisiloxane, 348.5 g (2.59 mol) of 1,1,3,3-tetramethyldisiloxane, and 4.7 g of trifluoromethanesulfonic acid, and stirred under a nitrogen stream for 6 hours. The mixture was diluted with 770 g of toluene, washed with water, dehydrated, and distilled to obtain 279 g of a toluene solution containing 41 wt% 1-chloromethyl-1,1,3,3-tetramethyldisiloxane. A 500 ml flask equipped with a nitrogen gas inlet tube and a condenser was charged with 70 g of toluene, 51.7 g (0.35 mol) of vinyltrimethoxysilane, and 1.54 g of platinum catalyst supported on alumina, and heated to 120°C under a nitrogen gas flow. 135 g (0.30 mol) of a toluene solution containing 41 wt% 1-chloromethyl-1,1,3,3-tetramethyldisiloxane was added dropwise over about 1 hour. The reaction was then carried out at 120°C for 2 hours to obtain a reaction solution. The reaction solution was cooled to room temperature and filtered. The excess vinyltrimethoxysilane and toluene were distilled off under reduced pressure and concentrated. 149.1 g of a toluene solution of 1-chloromethyl-1,1,3,3-tetramethyldisiloxane-vinyltrimethoxysilane reaction product was obtained. In a 2000ml flask equipped with a nitrogen gas inlet tube and a condenser, 77.3g (0.41mol) of 2-mercaptobenzothiazole sodium (Tokyo Chemical Industry Co., Ltd.), 400g of xylene, and an appropriate amount of amine-based reaction catalyst were added, and the temperature was raised to 120°C under a nitrogen stream. 149.1g of the toluene solution of the above-mentioned 1-chloromethyl-1,1,3,3-tetramethyldisiloxane-vinyltrimethoxysilane reaction product was added dropwise, and the reaction was carried out at 125°C for 3 hours. Next, the resulting reaction solution was filtered, and xylene and toluene were removed at 140°C and a reduced pressure of 0.5mmHg to obtain 131.1g of the target compound 4. The yield of this reaction was 98%. 1 Analysis by H-NMR revealed the following, confirming that it was the target compound. C6H4: 7.1ppm~7.8ppm, -Si(OCH3): 3.5ppm, Si-CH2-CH2-Si: 0.5~1ppm, -S-CH2-Si: 2.5ppm, CH3-Si-O-: -0.2ppm~0.2ppm

[0044] (Compound 8) In a 1000 ml flask equipped with a nitrogen gas inlet tube and a condenser, 100 g (0.22 mol) of polysiloxane silanol oligomer, HO(CH3)2Si-[O-Si(CH3)2]4-O-Si(CH3)2OH, 429.3 g (2.2 mol) of trimethoxysilylpropyl chloride, and an appropriate amount of condensation reaction catalyst were added, and the mixture was heated under a nitrogen stream at 80°C for 18 hours and then at 120°C for 2 hours. The excess trimethoxysilylpropyl chloride was removed at 140°C under a reduced pressure of 0.5 mmHg, yielding 168.1 g of ClCH2CH2CH2(OCH3)2Si-[O-Si(CH3)2]6-O-Si(OCH3)2CH2CH2CH2Cl. In a 500 ml flask equipped with a nitrogen gas inlet tube and a condenser, 34 g (0.18 mol) of 2-mercaptobenzothiazole sodium (Tokyo Chemical Industry Co., Ltd.), 180 g of xylene, 55 g (0.07 mol) of ClCH2CH2CH2(OCH3)2Si-[O-Si(CH3)2]6-O-Si(OCH3)2CH2CH2CH2Cl, and an appropriate amount of amine-based reaction catalyst were added and reacted at 130°C to 140°C for 10 hours. After filtration, the xylene was removed under reduced pressure of 140°C and 0.5 mmHg to obtain 72.6 g of the target compound 8. The yield of this reaction was 99%. 1 Analysis by H-NMR revealed the following, confirming that it was the target compound. C6H4: 7.1ppm~7.8ppm, -Si(OCH3): 3.4ppm~3.5ppm, CH3-Si-CH3: -0.2ppm~0.2ppm -S-CH2CH2 CH2 (OCH3)2Si-: 0.6ppm~0.8ppm -S-CH2 CH2 CH2(OCH3)2Si-: 1.8ppm~2ppm -S- CH2 CH2CH2(OCH3)2Si-: 3.2ppm~3.3ppm

[0045] (Compound 13) In a 2000 ml flask equipped with a nitrogen gas inlet tube and a condenser, 120 g (0.5 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane, 500 g of toluene, and an appropriate amount of alumina-supported platinum catalyst were appropriately charged, and the temperature was raised to 120°C under a nitrogen stream. A 40 wt% toluene solution of 155.4 g (1.05 mol) of vinyltrimethoxysilane and 80.3 g (1.05 mol) of allyl chloride (manufactured by Tokyo Chemical Industry) was dropped over about 1 hour. The reaction was then carried out at 120°C for 2 hours to obtain a reaction solution. The resulting reaction solution was cooled to room temperature and filtered. The excess vinyltrimethoxysilane, allyl chloride, and toluene were distilled off and concentrated at 140°C and a reduced pressure of 0.5 mmHg, obtaining 523 g of a toluene solution. 189.2g (1mol) of 2-mercaptobenzothiazole sodium (Tokyo Chemical Industry Co., Ltd.) was added to a 3000ml flask equipped with a nitrogen gas inlet tube and a condenser, 400g of xylene and an appropriate amount of an amine-based reaction catalyst were appropriately added, and the temperature was raised to 120°C under a nitrogen stream. 523g of the concentrated toluene solution described above was added dropwise, and the reaction was carried out at 125°C for 3 hours. Next, the resulting reaction solution was filtered, and xylene and toluene were removed at 140°C and a reduced pressure of 0.5mmHg to obtain 131.1g of the target compound 13. The yield of this reaction was 96%. 1 Analysis by H-NMR revealed the following, confirming that it was the target compound. C6H4: 7.1ppm~7.8ppm, -Si(OCH3): 3.5ppm, CH3-Si-: -0.2ppm~0.2ppm Si-CH2-CH2-Si: 0.5~1ppm, -S-CH2CH2 CH2 Si(OCH3)3: 0.6ppm~0.8ppm -S-CH2 CH2 CH2(OCH3)2Si-: 1.8ppm~2ppm, -S- CH2 CH2CH2(OCH3)2Si-: 3.2ppm~3.3ppm

[0046] The compounds of the Examples and Comparative Examples were evaluated by the following tests. The evaluation results in the following tests 1 to 5 are summarized in Table 1 together with the color tone of the compounds.

[0047] <1: Adhesiveness> Two sheets of electrolytic copper foil, aluminum alloy, zinc-plated steel sheet, and silver sheet, each measuring 50 x 50 mm, were prepared, and a xylene solution in which each compound was dissolved at a concentration of 5% was applied to one of the sheets, and then the sheets were dried to remove the solvent to prepare a coating (film). After bonding, the adhesion of each substrate was evaluated using a 1 mm square 25-square checkerboard test (adhesion was evaluated by the number of squares remaining after sticking Nitto Denko cellophane tape to the squares cut into 25 squares and peeling it off). In addition, the substrates to which each compound had been applied and the coating (film) had been prepared were immersed in 5% salt water (50°C) for 14 days, and a similar evaluation was attempted.

[0048] <2: Shear adhesive strength> The shear adhesive strength was measured for aluminum and copper coated with each compound using two different curing methods based on JIS K 6850. In one method, a 100:10 mixture of Epicoat 828 and tetramethylethylenediamine was used as the adhesive material, and cured under the following curing conditions: 1 hour at 100°C + 1 hour at 150°C. The adhesive strength was measured in kN / cm. 2 The other test used TSE382-C as the adhesive material and cured it at 23℃, 50% RH, and for 7 days. The adhesive strength was measured in MPa. The same test was also conducted after immersing these substrates in salt water for 14 days.

[0049] <3: Heat resistance evaluation> The heat resistance was evaluated by placing the copper foil coated with each compound in an atmosphere at 200°C for 30 minutes. The evaluation was performed by visually judging the change in color tone of the coating film, and was rated on the following 5-point scale. The higher the value, the higher the heat resistance. 5: No change 4: Slightly / little discolouration 3: Yellow discoloration 2: Discolored orange 1: Discolored to brown

[0050] <4: Moisture resistance evaluation> Moisture resistance was evaluated by placing copper foil coated with each compound in an atmosphere of 85°C and 85% relative humidity for 24 hours. Evaluation was performed by visually judging the change in color tone of the coating film, and was rated on the same 5-point scale as heat resistance. The higher the value, the higher the moisture resistance.

[0051] <5: Cold resistance cycle evaluation> The copper foil coated with each compound was placed in an atmosphere whose temperature changed from -40 to 180°C over the course of an hour, and this cycle was repeated 250 times. Evaluation was performed by visually judging whether cracks occurred in the coating film, and was rated on the following 5-point scale. The higher the value, the higher the evaluation. 5: No change 4: Only a few fine cracks are visible 3: A few fine cracks are observed 2: Cracks have appeared 1: Many cracks have occurred

[0052] [Table 1]

[0053] As shown in Table 1, the compounds of the present invention are superior in both adhesion and durability compared to compounds conventionally used as surface treatment agents. Compound 1 used in Comparative Example 3 has a similar structure to the compounds of the present invention, but is different from the compounds of the present invention, particularly in durability. This tendency is evident not only in the cold cycle resistance but also in the degree of decrease in shear adhesive strength after immersion in salt water.

[0054] <6: Appearance evaluation of substrate> For polychlorinated biphenyls (PCBs) and copper, samples were prepared by coating each compound and then immersed in 5% salt water (50°C) for 7 or 14 days, and the substrate was visually observed to see if any discoloration occurred. For PCB, in Examples 1 to 12, the substrate showed almost no discoloration within 7 days, and after 14 days, some of the substrates were slightly orange, while the compound in Comparative Example 1 showed a light brown color after 7 days, and the compound in Comparative Example 3 also showed a darker brown color than the Examples after 14 days. For copper plate, the compound in Comparative Example 1 showed some verdigris after 14 days, whereas the compounds in the Examples showed no verdigris and only some areas were light brown to brown. [Industrial Applicability]

[0055] The compound of the present invention has excellent adhesion to various substrates and durability, such as water resistance, and is useful as a surface treatment agent for substrates in various fields including electronics.

Claims

1. The following formula (I): 【Chemistry 1】 [In the formula, R １ is independently in each occurrence hydrogen or a monovalent organic group; R ２ is, independently in each occurrence, a substituted or unsubstituted monovalent hydrocarbon radical or 【Chemistry 2】 is a group represented by R ３ , R ４ , R ５ , R ６ are each independently a hydrogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, or a phenyl group; n is an integer from 1 to 3; k and l each independently represent an integer from 1 to 10; A is -O-, -S-, -Si(CH ３ ) ２ -, -Si(OR １ ) ２ --, --NR ７ -, -N=, -C(=O)-, -C(=O)O- and -C(=O)NR ７ - (where R ７ is a hydrogen atom or a C1-6 alkyl group), and [SiR ８ R ９ O ２／２ ], [SiR ８ O ３／２ ] and [SiO ４／２ ](where R ８ and R ９ are each independently a methyl group or a phenyl group, or a bond to another group), and may be interrupted by one or more groups selected from the group consisting of siloxane groups represented by the following units: ２ When it appears as a group in ２ is a substituted or unsubstituted monovalent hydrocarbon radical, A is not a butylene, propylene, or ethylene radical. A compound represented by the formula:

2. The compound of claim 1 , wherein k and l are both 1.

3. R ３ , R ４ , R ５ and R ６ The compound according to claim 1 , wherein all of are hydrogen.

4. R ２ independently in each occurrence, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, xylyl, naphthyl, benzyl, phenylethyl, phenylpropyl, vinyl, allyl, propenyl, butenyl, ethynyl, propynyl, 【Chemistry 3】 (wherein A and R ３ ~R ６ is as defined in claim 1), and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms or the like.

5. R １ may independently in each occurrence be CH ３ -, C ２ H ５ -, C ３ H ７ -, CF ３ CH ２ -, CH ３ CO-, CH ２ = C(CH ３ ) -, CH ３ CH ２ C (CH ３ )=N-, (CH ３ ) ２ N-, (C ２ H ５ ) ２ N-, CH ２ = C(OC ２ H ５ ) -, (CH ３ ) ２ C=C(OC ８ H １７ ) - or 【Chemistry 4】 2. The compound according to claim 1, wherein n is a group represented by the formula:

6. R １ may independently in each occurrence be CH ３ - or C ２ H ５ The compound according to claim 5, wherein

7. The compound according to claim 1, wherein the formula (I) or (II) is any one of the following compounds: 【Chemistry 5】 (In the above formula, the values ​​of a and m are each an integer from 1 to 300.)

8. A compound according to any one of claims 1 to 7 for the surface treatment of metals.

9. A surface treatment agent comprising the compound according to any one of claims 1 to 7.

10. A metal member, the surface of which is treated with the compound according to any one of claims 1 to 7.

Images