Mixed composition

文档序号：1909353 发布日期：2021-11-30 浏览：23次中文

阅读说明：本技术 混合组合物 (Mixed composition ) 是由德田真芳樱井彩香伊藤友宏于 2020-04-01 设计创作，主要内容包括：本发明的组合物是选自下述式(G1)表示的金属化合物和其缩合物中的至少1种金属化合物(G)、聚硅氮烷(F)以及包含硅氧烷链的化合物(H)的混合组合物。M(R～(g10))-(r)(A～(g1))-(m-r)(G1)[式(G1)中,M表示Al、Fe、In、Ge、Hf、Si、Ti、Sn、Zr或Ta,R～(g10)表示含有烃链的基团或氢原子,r为0或1。多个A～(g1)各自独立地表示水解性基团,m与金属原子M对应地为3～5的整数]。(The composition of the present invention is a mixed composition of at least 1 metal compound (G) selected from the group consisting of metal compounds represented by the following formula (G1) and condensates thereof, polysilazane (F), and a compound (H) containing a siloxane chain. M (R) g10 ) r (A g1 ) m‑r (G1) [ In the formula (G1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, R g10 Represents a group containing a hydrocarbon chain or a hydrogen atom, and r is 0 or 1. A plurality of A g1 Each independently represents a hydrolyzable group,m is an integer of 3 to 5 corresponding to the metal atom M]。)

1. A mixed composition comprising at least 1 metal compound (G) selected from the group consisting of metal compounds represented by the following formula (G1) and condensates thereof, polysilazane (F), and a compound (H) having a siloxane chain,

M(R^g10)_r(A^g1)_m-r (G1)

in the formula (G1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, R^g10Represents a group containing a hydrocarbon chain or a hydrogen atom, r is 0 or 1, a plurality of A^g1Each independently represents a hydrolyzable group, and M is an integer of 3 to 5 in correspondence with the metal atom M.

2. The composition according to claim 1, wherein the mass ratio of the siloxane chain-containing compound (H) to the metal compound (G) is 5 to 95% based on the total mass of the polysilazane (F), the siloxane chain-containing compound (H), and the metal compound (G).

3. The composition according to claim 1 or 2, wherein the polysilazane (F) has a structural unit represented by the following formula (F1),

in the formula (f1), R^f11、R^f12And R^f13Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alkylsilyl group.

4. The composition of claim 3, wherein polysilazane (F) has R in formula (F1)^f11And R^f12At least one of the (a) structural units is a hydrocarbon group having 1 to 10 carbon atoms (f 2).

5. The composition according to claim 4, wherein polysilazane (F) further has a structural unit represented by the following formula (F3) in addition to the structural unit (F2),

in the formula (f3), R^f31And R^f32Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y^fRepresents a 2-valent hydrocarbon group having 1 to 10 carbon atoms, and multiple X' s^fEach independently represents a hydrolyzable group.

6. The composition according to any one of claims 1 to 5, wherein the compound (H) containing a siloxane chain is a compound represented by the following formula (H1),

in the formula (H1), R^h1Represents a molecular chain having a trialkylsilyl group and a siloxane chain, A^h1Each independently represents a hydrolyzable group, Z^h1Represents a molecular chain having a trialkylsilyl group and a siloxane chain, a group having a siloxane skeleton, or a group having a hydrocarbon chain, R^h1And Z^h1The hydrogen atom contained in the trialkylsilyl group(s) may be substituted with a fluorine atom, and x represents an integer of 0 to 3.

7. The compound according to claim 6, wherein in the formula (H1), R^h1Is a group represented by the following formula (s3),

in the formula (s3), R is plural^s1Each independently represents a hydrocarbon group or a trialkylsiloxy group, the hydrogen atom contained in the hydrocarbon group or the trialkylsiloxy group may be substituted by fluorineThe number of atoms,

plural R^s2Each independently represents an alkyl group having 1 to 10 carbon atoms,

n1 represents an integer of 1 or more,

Z^s1represents-O-or a 2-valent hydrocarbon group, the-CH contained in the 2-valent hydrocarbon group₂-may be substituted by-O-,

Y^s1represents a single bond or-Si (R)^s2)₂－L^s1-, the L^s1Represents a 2-valent hydrocarbon group, the-CH contained in the 2-valent hydrocarbon group₂-may be substituted by-O-.

8. The composition according to any one of claims 1 to 7, wherein the total amount of polysilazane (F), the compound (H) having a siloxane chain, and the metal compound (G) is 0.2 mass% or more and less than 2.6 mass%.

9. The composition according to any one of claims 1 to 8, wherein the amount of the compound (H) containing a siloxane chain is less than 0.3 mass%.

10. The composition according to any one of claims 1 to 9, for use in an intermediate layer between a substrate and a liquid repellent layer.

11. The composition of claim 10, wherein the liquid repellent layer is a film formed by a dehydration condensation reaction of silanol groups.

Technical Field

The present invention relates to a polysilazane, a compound containing a siloxane chain, and a mixed composition of metal compounds.

Background

In various display devices, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like, the following problems may occur due to adhesion of droplets to the surface of a substrate: contamination or corrosion of the substrate, and further, performance degradation due to the contamination or corrosion. Therefore, in these fields, the surface of the substrate is required to have good liquid repellency.

Patent document 1 describes a coating composition obtained by mixing an organosilicon compound in which at least 1 trialkylsilyl-containing molecular chain and at least 1 hydrolyzable group are bonded to a silicon atom, and a metal compound in which a hydrolyzable group is bonded to a metal atom, and discloses that a coating film obtained from the coating composition has both water-oil repellency, light resistance, and heat resistance. Patent document 2 describes a composition obtained by mixing an organosilicon compound having at least 1 trialkylsilyl group and 2 or more hydrolyzable silicon groups with a metal compound having at least 1 hydrolyzable group bonded to a metal atom, and discloses that the composition can provide a coating film having good heat resistance and light resistance in addition to water repellency.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2016/068138

Patent document 2: japanese patent laid-open publication No. 2017-119849

Disclosure of Invention

However, in patent documents 1 and 2, there is room for study in terms of abrasion resistance. In addition, there are also problems as follows: when the coating agent is cured to form a coating film, heating is required for forming the coating film at a practical speed.

As a result of intensive studies to solve the above problems, the present inventors have found that by using a mixed composition of polysilazane, a compound containing a siloxane chain, and a metal compound as a coating agent for an intermediate layer between a base material and a liquid-repellent layer (composition for forming an intermediate layer), the abrasion resistance when formed into a coating film can be improved without impairing the liquid-repellent property, and the coating film can be cured at a practical speed preferably at room temperature, and have completed the present invention. The present invention is as follows.

[1] A mixed composition comprising at least 1 metal compound (G) selected from the group consisting of metal compounds represented by the following formula (G1) and condensates thereof, polysilazane (F), and a compound (H) having a siloxane chain.

M(R^g10)_r(A^g1)_m-r (G1)

[ In the formula (G1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, R^g10Represents a group containing a hydrocarbon chain or a hydrogen atom, and r is 0 or 1. A plurality of A^g1Each independently represents a hydrolyzable group, and M is an integer of 3 to 5 corresponding to the metal atom M]

[2] The composition according to [1], wherein the mass ratio of the siloxane chain-containing compound (H) to the metal compound (G) is 5 to 95% based on the total mass of the polysilazane (F), the siloxane chain-containing compound (H), and the metal compound (G).

[3] The composition according to [1] or [2], wherein the polysilazane (F) has a structural unit represented by the following formula (F1).

[ formula (f1), R^f11、R^f12And R^f13Each independently represents a hydrogen atom, a C1-10 hydrocarbon group which may have a substituent, or an alkylsilyl group]

[4]According to [3]The composition, wherein the polysilazane (F) has the formula (F1) as R^f11And R^f12At least one of the (a) structural units is a hydrocarbon group having 1 to 10 carbon atoms (f 2).

[5] The composition according to [4], wherein the polysilazane (F) further has a structural unit represented by the following formula (F3) in addition to the structural unit (F2).

[ formula (f3), R^f31And R^f32Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, Y^fRepresents a 2-valent hydrocarbon group having 1 to 10 carbon atoms, and multiple X' s^fEach independently represents a hydrolyzable group]

[6] The composition according to any one of [1] to [5], wherein the compound (H) containing a siloxane chain is a compound represented by the following formula (H1).

[ formula (H1) wherein R^h1Represents a molecular chain having a trialkylsilyl group and a siloxane chain, A^h1Each independently represents a hydrolyzable group, Z^h1Represents a molecular chain having a trialkylsilyl group and a siloxane chain, a group having a siloxane skeleton, or a group having a hydrocarbon chain, R^h1And Z^h1The hydrogen atom contained in the trialkylsilyl group (a) may be substituted by a fluorine atom, and x represents an integer of 0 to 3]

[7]According to [6]Wherein, in the above formula (H1), R^h1Is a group represented by the following formula (s 3).

[ in the formula (s3), a plurality of R^s1Each independently represents a hydrocarbon group or a trialkylsiloxy group, the hydrogen atom contained in the hydrocarbon group or the trialkylsiloxy group may be substituted by a fluorine atom,

plural R^s2Each independently represents an alkyl group having 1 to 10 carbon atoms,

n1 represents an integer of 1 or more,

Z^s1represents-O-or a 2-valent hydrocarbon group, the 2-valent hydrocarboncontaining-CH in radicals₂-may be substituted by-O-.

Y^s1Represents a single bond or-Si (R)^s2)₂－L^s1-, the L^s1Represents a 2-valent hydrocarbon group, the-CH contained in the 2-valent hydrocarbon group₂Can be substituted by-O-]

[8] The composition according to any one of [1] to [7], wherein the total amount of the polysilazane (F), the compound (H) having a siloxane chain, and the metal compound (G) is 0.2% by mass or more and less than 2.6% by mass.

[9] The composition according to any one of [1] to [8], wherein the amount of the compound (H) containing a siloxane chain is less than 0.3% by mass.

[10] The composition according to any one of [1] to [9], which is used for an intermediate layer between a substrate and a liquid repellent layer.

[11] The composition according to [10], wherein the liquid-repellent layer is a film formed by a dehydration condensation reaction of silanol groups.

The mixed composition may further include a substance obtained by a reaction after mixing, for example, during storage.

By using the mixed composition of the present invention as the intermediate layer-forming composition, a coating film having excellent abrasion resistance can be provided. In addition, as a preferable aspect, when the mixed composition of the present invention is used as the composition for forming an intermediate layer, the coating film can be cured at a practical speed even at room temperature.

Detailed Description

Hereinafter, polysilazane (F), a compound (H) having a siloxane chain, and a metal compound (G) will be described in this order.

1. Polysilazanes (F)

The polysilazane (F) in the present invention is not particularly limited as long as it is a compound having a silicon-nitrogen bond, and preferably has a structural unit represented by the following formula (F1).

[ formula (f1), R^f11、R^f12And R^f13Each independently represents a hydrogen atom, a C1-10 hydrocarbon group which may have a substituent, or an alkylsilyl group]

As R^f11～R^f13Examples of the hydrocarbon group having 1 to 10 carbon atoms include straight-chain saturated aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; a branched saturated aliphatic hydrocarbon group such as an isopropyl group, a sec-butyl group, a tert-butyl group, a methylpentyl group, an ethylpentyl group, a methylhexyl group, an ethylhexyl group, a propylhexyl group, and a tert-octyl group; cyclic saturated aliphatic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; unsaturated aliphatic hydrocarbon groups such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, and 3-butenyl; aromatic hydrocarbon groups such as phenyl, naphthyl, p-tert-butylphenyl, tolyl, xylyl, cumyl, mesityl, 2, 6-diethylphenyl, and 2-methyl-6-ethylphenyl; and a combination of the above-exemplified hydrocarbon groups such as alkylcycloalkyl, cycloalkylalkyl and aralkyl groups.

Examples of the substituent that the hydrocarbon group having 1 to 10 carbon atoms may have include a halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a nitro group; an amino group; a cyano group; a thiol group; an epoxy group; epoxy propoxy; (meth) acryloyloxy; a heteroaryl group having 6 to 12 ring atoms; alkoxy groups having 1 to 3 carbon atoms such as methoxy and ethoxy; and aryloxy groups having 6 to 12 carbon atoms forming a ring.

As R^f11～R^f13The hydrocarbon group having 1 to 10 carbon atoms is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an unsubstituted straight-chain saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, still more preferably an unsubstituted methyl group, ethyl group, propyl group or butyl group, and most preferably a methyl group.

As R^f11～R^f13Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, and triisosilyl groupPropylsilyl, tri-tert-butylsilyl, methyldiethylsilyl, dimethylsilyl, diethylsilyl, methylsilyl, ethylsilyl and the like.

The polysilazane (F) preferably has R in the formula (F1)^f11And R^f12At least one of which is an organic polysilazane, which is a structural unit (f2) containing a hydrocarbon group having 1 to 10 carbon atoms. In addition, R^f13Preferably a hydrogen atom.

The polysilazane (F) more preferably further has a structural unit represented by the following formula (F3) in addition to the structural unit (F2).

As R^f31And R^f32The hydrocarbyl group having 1 to 10 carbon atoms is represented by the formula^f11～R^f13The same groups as those described for the hydrocarbon group having 1 to 10 carbon atoms are shown. Among them, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable, a linear saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a methyl group, an ethyl group, a propyl group, or a butyl group is even more preferable.

As Y^fThe 2-valent hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 to 2 carbon atoms. The 2-valent hydrocarbon group is preferably a chain, and when the group is a chain, the group may be either linear or branched. The above-mentioned 2-valent hydrocarbon group is preferably a 2-valent aliphatic hydrocarbon group, and is preferably an alkanediyl group. Examples of the 2-valent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.

Further, a part of-CH contained in the above-mentioned 2-valent hydrocarbon group₂-may be substituted by-O-. At this time, 2-CHs are continued₂Do not take at the same timeWith the substitution-O-, of-CH adjacent to the Si atom₂-will not be substituted with-O-. 2 or more-CH₂When the substituent is-O-, the number of carbon atoms between-O-and-O-is preferably 2 to 4, more preferably 2 to 3. Examples of the group in which a part of the 2-valent hydrocarbon group is substituted with-O-include a group having a (poly) ethylene glycol unit and a group having a (poly) propylene glycol unit.

As X^fThe hydrolyzable group represented by (a) is not particularly limited as long as it is a group which provides a hydroxyl group (silanol group) by hydrolysis, and examples thereof include alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; a hydroxyl group; an acetoxy group; a chlorine atom; isocyanate groups, and the like. Among them, preferred is an alkoxy group having 1 to 4 carbon atoms, and more preferred is an alkoxy group having 1 to 2 carbon atoms. Multiple X^fMay be the same or different, preferably the same.

SiX of the above formula (f3)^f ₃The content of the base is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more, based on 100% by mass of the polysilazane (F). The upper limit is not limited, and may be 50 mass% or less, 40 mass% or less, or 30 mass% or less.

When the polysilazane (F) is an organopolysiloxane, the content ratio of hydrogen atoms of Si-H to hydrocarbon groups having 1 to 10 carbon atoms bonded to Si can be appropriately selected, and for example, the molar ratio of hydrocarbon groups/hydrogen atoms is 0.1 to 50, preferably 0.2 to 10. The molar ratio of these can be calculated by NMR measurement or the like.

The amount of the polysilazane (F) is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, and even more preferably 0.3 mass% or more, and further preferably 2.5 mass% or less, more preferably 2 mass% or less, even more preferably 1.5 mass% or less, and even more preferably 1 mass% or less, based on 100 mass% of the entire composition.

2. Compound (H) comprising a siloxane chain

The compound (H) containing a siloxane chain in the present invention is not particularly limited as long as it is a compound having at least 1 siloxane bond, and the siloxane chain may be linear or branched, and is preferably linear.

The siloxane chain preferably includes a dialkylsiloxane chain, and more preferably includes a linear dialkylsiloxane chain. The siloxane chain may further contain a 2-valent group other than a siloxane bond, and the 2-valent group may be a 2-valent hydrocarbon group or a part of methylene (-CH) in the 2-valent hydrocarbon group₂-) a group substituted with an oxygen atom, and-O-, etc.

The terminal of the siloxane chain is preferably bonded with a silyl group. The silyl group is a group having 3 substituents bonded to a silicon atom, and examples of the substituents include a hydrogen atom, a hydrocarbon chain-containing group, an alkylsiloxy group, and a hydrolyzable group.

The hydrocarbon chain-containing group is a group having a hydrocarbon chain in at least a part thereof, and usually consists only of a hydrocarbon group (hydrocarbon chain), and may be a part of methylene group (-CH) of the hydrocarbon chain, if necessary₂-) is substituted with a group of oxygen atoms. In addition, methylene (-CH) groups adjacent to Si atoms₂-) is not substituted by an oxygen atom, and additionally, 2 methylene groups (-CH) are consecutive₂-) are not simultaneously substituted with oxygen atoms.

The number of carbon atoms of the hydrocarbon chain-containing group means the number of carbon atoms constituting the hydrocarbon group (hydrocarbon chain) in the oxygen-unsubstituted hydrocarbon chain-containing group, and means that the oxygen atom is assumed to be methylene (-CH) in the oxygen-substituted hydrocarbon chain-containing group₂-) and the number of carbon atoms counted.

Hereinafter, unless otherwise specified, the hydrocarbon chain-containing group will be described by taking an oxygen-unsubstituted hydrocarbon chain-containing group (i.e., a 1-valent hydrocarbon group) as an example, and any of the descriptions may be used to describe a methylene group (-CH) constituting the hydrocarbon chain-containing group₂-) are partially substituted with oxygen atoms.

When the hydrocarbon chain-containing group is a hydrocarbon group, the number of carbon atoms is preferably 1 to 3, more preferably 1. The hydrocarbon chain-containing group may be branched or straight. The hydrocarbon chain-containing group is preferably a group containing a saturated or unsaturated aliphatic hydrocarbon chain, and more preferably a group containing a saturated aliphatic hydrocarbon chain. As the group containing a saturated aliphatic hydrocarbon chain, a saturated aliphatic hydrocarbon group (alkyl group) is more preferable. Examples of the saturated aliphatic hydrocarbon group include methyl, ethyl, and propyl groups.

A part of methylene groups (-CH) of saturated aliphatic hydrocarbon groups₂-) is substituted with an oxygen atom, specifically, a group having a (poly) ethylene glycol unit, and the like can be exemplified.

The hydrolyzable group may be any group that can provide a hydroxyl group (silanol group) by hydrolysis, and examples thereof include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, and butoxy; a hydroxyl group; an acetoxy group; a chlorine atom; isocyanate groups, and the like. Among them, preferred is an alkoxy group having 1 to 6 carbon atoms, more preferred is an alkoxy group having 1 to 4 carbon atoms, and still more preferred is an alkoxy group having 1 to 2 carbon atoms.

Examples of the above-mentioned alkylsiloxy group include monoalkylsiloxy group, dialkylsiloxy group and trialkylsiloxy group, and among them, trialkylsiloxy group is preferable. Examples of the trialkylsiloxy group include a trimethylsiloxy group, a triethylsilyloxy-tripropylsilyloxy group and the like.

When 1 silicon atom has a plurality of substituents, the plurality of substituents may be the same or different.

At least 1 hydrolyzable group-bonded silicon atom is preferably bonded to the end of the siloxane chain, more preferably 2 or more hydrolyzable groups-bonded silicon atoms are bonded, and still more preferably 3 hydrolyzable groups are bonded to the end of the siloxane chain. The silicon atom to which the hydrolyzable group is bonded may be bonded to one end of the siloxane chain, may be bonded to both ends of the siloxane chain, and is preferably bonded only to one end side.

More preferably, at both ends of the siloxane chain, any of a silyl group (trialkoxysilyl group) having 3 alkoxy groups as substituents, a silyl group (trialkylsilyl group) having 3 alkyl groups as substituents, and a silyl group (tris (trialkylsiloxy) silyl group) having 3 trialkylsiloxy groups as substituents is bonded, and particularly preferably, a trialkoxysilyl group is bonded at one end side, and a trialkylsilyl group or a tris (trialkylsiloxy) silyl group is bonded at the other end side.

A more preferred embodiment of the siloxane chain-containing compound (H) of the present invention is a compound in which a molecular chain having a trialkylsilyl group and a siloxane chain (hereinafter, this molecular chain may be referred to as "molecular chain (ts 1)") is bonded to at least 1 silicon atom (hereinafter, this silicon atom may be referred to as "central silicon atom").

In the compound (H) containing a siloxane chain, the number of molecular chains (ts1) bonded to the central silicon atom is 1 or more, preferably 3 or less, more preferably 2 or less, and particularly preferably 1.

The central silicon atom of the compound (H) having a siloxane chain may be bonded with a hydrolyzable group, a siloxane skeleton-containing group having a smaller number of atoms than the molecular chain (ts1), or a hydrocarbon chain-containing group having a hydrocarbon chain having a smaller number of carbon atoms than the molecular chain (ts1), in addition to the molecular chain (ts 1).

Specifically, the compound (H) containing a siloxane chain is preferably a compound represented by the following formula (H1).

In the formula (H1), R^h1Represents a molecular chain having a trialkylsilyl group and a siloxane chain, A^h1Each independently represents a hydrolyzable group, Z^h1Represents a molecular chain having a trialkylsilyl group and a siloxane chain, a group having a siloxane skeleton or a group having a hydrocarbon chain, R^h1And Z^h1The hydrogen atom contained in the trialkylsilyl group(s) may be substituted with a fluorine atom, and x represents an integer of 0 to 3.

R^h1The molecular chain (ts1)) having a trialkylsilyl group and a siloxane chain has a structure containing a trialkylsilyl groupThe alkyl group is bonded to the 1-valent group of the structure at the end of the siloxane chain. The alkyl group of the trialkylsilyl-containing group may be substituted with a fluoroalkyl group.

The above-mentioned trialkylsilyl group-containing group is a group containing at least 1 trialkylsilyl group, preferably 2 or more, and more preferably 3 trialkylsilyl groups. The trialkylsilyl group-containing group is preferably a group represented by the formula (s 1).

In the formula (s1), R is plural^s1Each independently represents a hydrocarbon group or a trialkylsiloxy group, and a hydrogen atom contained in the hydrocarbon group or the trialkylsiloxy group may be substituted with a fluorine atom. Denotes the bonding site.

In the above formula (s1), R is preferably^s1At least 1 of (a) is trialkylsiloxy, or R^s1All are alkyl groups.

R^s1When the alkyl group is a hydrocarbon group, the number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2. R^s1When the hydrocarbon group is a hydrocarbon group, an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Plural R^s1May be the same or different, preferably the same. R^s1When all are hydrocarbyl (especially alkyl), 3R^s1The total number of carbon atoms of (a) is preferably 9 or less, more preferably 6 or less, and still more preferably 4 or less. Preferably 3R^s1At least 1 of (A) is methyl, more preferably at least 2 are methyl, and particularly preferably 3R^s1All are methyl groups.

As R^s1Examples of the group (trialkylsilyl group) all of which are hydrocarbon groups (alkyl groups) include groups represented by the following formulae. In the formula, a represents a bonding site.

Examples of the trialkylsiloxy group include R^s1Groups in which oxygen atoms are bonded to silicon atoms of groups (trialkylsilyl groups) all of which are hydrocarbon groups (alkyl groups). In the above formula (s1), R is preferably^s1At least 1 of them is a trialkylsiloxy group, more preferably 2 or more, further preferably 3R^s1Is trialkylsiloxy.

As R^s1At least 1 of them is a trialkylsiloxy group, and examples thereof include groups represented by the following formulae.

In the molecular chain (ts1), a group containing a trialkylsilyl group is preferably bonded to the terminal (free end side) of the siloxane chain, particularly to the terminal (free end side) of the main chain (longest linear chain) of the siloxane chain.

The silicone chain to which the trialkylsilyl group-containing group is bonded preferably includes a linear dialkylsilicone chain, as in the case of the silicone chain described above. The siloxane chain may contain a 2-valent hydrocarbon group. Even if a part of the siloxane chain is a 2-valent hydrocarbon group, the remainder is a dialkylsiloxane chain, and therefore the chemical-physical durability of the obtained coating film is good.

The siloxane chain is preferably a group represented by the formula (s 2).

In the formula (s2), R is plural^s2Each independently represents an alkyl group having 1 to 10 carbon atoms. Z^s1represents-O-or a 2-valent hydrocarbon group, the-CH contained in the 2-valent hydrocarbon group₂-may be substituted by-O-. Y is^s1Represents a single bond or-Si (R)^s2)₂－L^s1－。L^s1Represents a 2-valent hydrocarbon group, the-CH contained in the 2-valent hydrocarbon group₂-may be substituted by-O-. The left-hand side indicates the bonding site to the central silicon atom,the right-hand side indicates the bonding site to the trialkylsilyl-containing group. n1 represents an integer of 1 or more.

R^s2The number of carbon atoms of (A) is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.

n1 is preferably 1 to 100, more preferably 1 to 80, further preferably 1 to 60, further preferably 1 to 50, and particularly preferably 1 to 30.

Z^s1Or L^s1The number of carbon atoms of the 2-valent hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The 2-valent hydrocarbon group is preferably a chain, and when the group is a chain, the group may be either linear or branched. The above-mentioned 2-valent hydrocarbon group is preferably a 2-valent aliphatic hydrocarbon group, and is preferably an alkanediyl group. Examples of the above-mentioned 2-valent hydrocarbon group include a methylene group, an ethylene group, a propylene group, and a butylene group.

Further, a part of-CH contained in the above-mentioned 2-valent hydrocarbon group₂-may be substituted by-O-. At this time, 2-CHs are continued₂Not simultaneously substituted by-O-, CH adjacent to Si atom₂-will not be substituted with-O-. 2 or more-CH₂When the substituent is-O-, the number of carbon atoms between-O-and-O-is preferably 2 to 4, more preferably 2 to 3. Examples of the group in which a part of the 2-valent hydrocarbon group is substituted with-O-include a group having a (poly) ethylene glycol unit and a group having a (poly) propylene glycol unit.

In the above formula (s2), Z is preferably Z^s1is-O-, Y^s1Is a single bond, i.e. the siloxane chain consists only of repeating dialkylsiloxy groups. When the dialkylsiloxane chain is composed of only repeating dialkylsiloxy groups, the chemical-physical durability of the obtained coating film is good.

Examples of the siloxane chain included in the molecular chain (ts1) include siloxane chains represented by the following formulae. Wherein q1 represents an integer of 1 to 60, and represents a bonding site to a central silicon atom or a trialkylsilyl group-containing group.

The total number of atoms constituting the molecular chain (ts1) is preferably 24 or more, more preferably 40 or more, further preferably 50 or more, and further preferably 5000 or less, more preferably 4000 or less, further preferably 2000 or less, further more preferably 1200 or less, particularly preferably 700 or less, and most preferably 250 or less.

The molecular chain (ts1) is preferably a group represented by the following formula (s 3).

In the formula (s3), R^s1、R^s2、Z^s1、Y^s1N1 is as defined above. Denotes the bonding site to the central silicon atom.

The molecular chain (ts1) is preferably a group represented by the following formula (s 3-1), more preferably a group represented by the following formula (s 3-1-1).

In the formulae (s 3-1) and (s 3-1-1), R^s2、Y^s1、Z^s1N1 is as defined above. R^s3Represents an alkyl group having 1 to 4 carbon atoms. Denotes the bonding site to the central silicon atom.

R^s3The number of carbon atoms of the alkyl group is preferably 1 to 3, more preferably 1 to 2. Further, in the formula (s 3-1) and the formula (s 3-1-1), -Si (R)^s3)₃R contained in (1)^s3The total number of carbon atoms of (a) is preferably 9 or less, more preferably 6 or less, and still more preferably 4 or less. Further, -Si (R)^s3)₃R contained in^s3In (1), preferably at least1R^s3Is methyl, preferably 2 or more R^s3Is methyl, particularly preferably 3R^s3All are methyl groups.

Further, the molecular chain (ts1) is more preferably a group represented by the following formula (s 3-2), and particularly preferably a group represented by the following formula (s 3-2-1).

In the formulae (s 3-2) and (s 3-2-1), R^s2、Y^s1、Z^s1N1 is as defined above. R^s4Represents an alkyl group having 1 to 4 carbon atoms. Denotes the bonding site to the central silicon atom.

As R^s4Examples of the alkyl group having 1 to 4 carbon atoms include the above-mentioned R^s3The preferable ranges of the groups mentioned in (1) above are also the same.

As the molecular chain (ts1), a group represented by the formula (s 3-I) can be mentioned. In the formula (s 3-I), a bonding site to the central silicon atom is represented.

[ Table 1]

	Z^s30	R^s20	n30	Y^s30	R^s30
						(s3-I-1)	-O-	CH₃-*	1～60	-	(CH₃)₃SiO-*
(s3-I-2)	-O-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	(CH₃)₃SiO-*
						(s3-I-3)	-O-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	(CH₃)₃SiO-*
(s3-I-4)	-O-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	(CH₃)₃SiO-*
						(s3-I-5)	-O-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	(CH₃)₃SiO-*
(s3-I-6)	-CH₂-	CH₃-*	1～60	-	(CH₃)₃SiO-*
						(s3-I-7)	-CH₂-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	(CH₃)₃SiO-*
(s3-I-8)	-CH₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	(CH₃)₃SiO-*
						(s3-I-9)	-CH₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	(CH₃)₃SiO-*
(s3-I-10)	-CH₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	(CH₃)₃SiO-*
						(s3-I-11)	-(CH₂)₂-	CH₃-*	1～60	-	(CH₃)₃SiO-*
(s3-I-12)	-(CH₂)₂-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	(CH₃)₃SiO-*
						(s3-I-13)	-(CH₂)₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	(CH₃)₃SiO-*
(s3-I-14)	-(CH₂)₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	(CH₃)₃SiO-*
						(53-I-15)	-(CH₂)₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	(CH₃)₃SiO-*
(s3-I-16)	-(CH₂)₃-	CH₃-*	1～60	-	(CH₃)₃SiO-*
						(s3-I-17)	-(CH₂)₃-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	(CH₃)₃SiO-*
(s3-I-18)	-(CH₂)₃-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	(CH₃)₃SiO-*
						(s3-I-19)	-(CH₂)₃-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	(CH₃)₃SiO-*
(s3-I-20)	-(CH₂)₃-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	(CH₃)₃SiO-*
						(s3-I-21)	-(CH₂)₄-	CH₃-*	1～60	-	(CH₃)₃SiO-*
(s3-I-22)	-(CH₂)₄-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	(CH₃)₃SiO-*
						(s3-I-23)	-(CH₂)₄-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	(CH₃)₃SiO-*
(s3-I-24)	-(CH₂)₄-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	(CH₃)₃SiO-*
						(s3-I-25)	-(CH₂)₄-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	(CH₃)₃SiO-*

[ Table 2]

	Z^s30	R^s20	n30	Y^s30	R^s30
						(s3-I-26)	-O-	CH₃-*	1～60	-	CH₃-*
(s3-I-27)	-O-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	CH₃-*
						(s3-I-28)	-O-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	CH₃-*
(s3-I-29)	-O-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	CH₃-*
						(s3-I-30)	-O-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	CH₃-*
(s3-I-31)	-CH₂-	CH₃-*	1～60	-	CH₃-*
						(s3-I-32)	-CH₂-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	CH₃-*
(s3-I-33)	-CH₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	CH₃-*
						(s3-I-34)	-CH₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	CH₃-*
(s3-I-35)	-CH₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	CH₃-*
						(s3-I-36)	-(CH₂)₂-	CH3-*	1～60	-	CH₃-*
(s3-I-37)	-(CH₂)₂-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	CH₃-*
						(s3-I-38)	-(CH₂)₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	CH₃-*
(s3-I-39)	-(CH₂)₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	CH₃-*
						(s3-I-40)	-(CH₂)₂-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	CH₃-*
(s3-I-41)	-(CH₂)₃-	CH₃-*	1～60	-	CH₃-*
						(s3-I-42)	-(CH₂)₃-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	CH₃-*
(s3-I-43)	-(CH₂)₃-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	CH₃-*
						(s3-I-44)	-(CH₂)₃-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	CH₃-*
(s3-I-45)	-(CH₂)₃-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	CH₃-*
						(s3-I-46)	-(CH₂)₄-	CH₃-*	1～60	-	CH₃-*
(s3-I-47)	-(CH₂)₄-	CH₃-*	1～60	-Si(CH₃)₂-CH₂-	CH₃-*
						(s3-I-48)	-(CH₂)₄-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₂-	CH₃-*
(s3-I-49)	-(CH₂)₄-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₃-	CH₃-*
						(s3-I-50)	-(CH₂)₄-	CH₃-*	1～60	-Si(CH₃)₂-(CH₂)₄-	CH₃-*

N30 shown in tables 1 and 2 is preferably 1 to 30.

Next, for A in the formula (H1)^h1The description is given. A. the^h1Each independently is a hydrolyzable group as long as it is a group which provides a hydroxyl group (silanol group) by hydrolysis, and examples thereof include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; a hydroxyl group; an acetoxy group; a chlorine atom; isocyanate groups, and the like. Among them, preferred is an alkoxy group having 1 to 6 carbon atoms, more preferred is an alkoxy group having 1 to 4 carbon atoms, and still more preferred is an alkoxy group having 1 to 2 carbon atoms.

Z in the formula (H1)^h1Represents a molecular chain having a trialkylsilyl group and a siloxane chain, a group having a siloxane skeleton, or a group having a hydrocarbon chain. Z^h1When the molecular chain has a trialkylsilyl group and a siloxane chain, the above-mentioned R is mentioned^h1The same molecular chain.

Z^h1In the case of a group having a siloxane skeleton, the group having a siloxane skeleton is a 1-valent group having a siloxane unit (Si-O-), and preferably has a smaller number than R^h1Molecular chain of (A), (B)ts 1). Thus, the siloxane skeleton-containing group is shorter in length than the molecular chain (ts1) or small in steric breadth (volume size). The siloxane backbone-containing group may comprise a 2-valent hydrocarbon group.

The group having a siloxane skeleton is preferably a group represented by the following formula (s 4).

In the formula (s4), R^s2、Z^s1And Y^s1The same as above. R^s5Represents a hydrocarbon group or a hydroxyl group, the-CH contained in the hydrocarbon group₂-may be substituted by-O-, and the hydrogen atom contained in the hydrocarbon group may be substituted by a fluorine atom. n3 represents an integer of 0 to 5. Denotes the bonding site to the central silicon atom.

As R^s5Examples of the hydrocarbyl group include^s1The hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. The number of carbon atoms is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.

n3 is preferably 1 to 5, more preferably 1 to 3.

The total number of atoms of the groups having a siloxane skeleton is preferably 600 or less, more preferably 500 or less, further preferably 350 or less, further more preferably 100 or less, particularly preferably 50 or less, most preferably 30 or less, and further preferably 10 or more. In addition, R^h1Molecular chain (ts1) of (A) and Z^h1The difference in the number of atoms of the siloxane skeleton-containing group(s) in (b) is preferably 10 or more, more preferably 20 or more, preferably 1000 or less, more preferably 500 or less, and even more preferably 200 or less.

Specific examples of the group having a siloxane skeleton include groups represented by the following formulae.

Z^h1In the case of a hydrocarbon chain-containing group, provided that the number of carbon atoms in the hydrocarbon chain moiety is less than that constituting R^h1The number of atoms of the molecular chain (ts1) in (b) may be any. In addition, the number of carbon atoms of the longest linear chain of the hydrocarbon chain is preferably smaller than the number of carbon atoms of the longest linear chain constituting the molecular chain (ts 1). Examples of the hydrocarbon chain-containing group include the same groups as those exemplified above.

X in the formula (H1) is preferably 2 or less, more preferably 0 or 1, and still more preferably 0.

The compound (H) containing a siloxane chain represented by formula (H1) is preferably a compound represented by formula (H2).

In the formula (H2), R^s1、R^s2、Z^s1、Y^s1、n1、A^h1、Z^h1And x are as defined above.

The siloxane chain-containing compound (H) represented by the formula (H2) is preferably a compound represented by the following formula (H2-1), more preferably a compound represented by the formula (H2-1-1).

In the formulae (H2-1) and (H2-1-1), R^s2、R^s3、Y^s1、Z^s1、n1、A^h1The same as above.

The siloxane chain-containing compound (H) represented by the formula (H2) is more preferably a compound represented by the following formula (H2-2), and particularly preferably a compound represented by the formula (H2-2-1).

In the formulae (H2-2) and (H2-2-1), R^s2、R^s4、Y^s1、Z^s1、n1、A^h1The same as above.

Specific examples of the compound (H) having a siloxane chain represented by formula (H2) include compounds represented by formula (H-I).

[ Table 3-1 ]

A^h10

Z^s10

R^s20

n10

Y^s10

R^s10

(H-I-1)

C₂H₅O-*

*-O-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-2)

C₂H₅O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-3)

C₂H₅O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-4)

C₂H₅O-*

*-O-*

CH3-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-5)

C₂H₅O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH2)₄-*

(CH₃)₃SiO-*

(H-I-6)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-7)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-8)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-9)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-10)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

(H-I-11)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-12)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-13)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-14)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-15)

C₂H₅O-*

*-(CH2)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

(H-I-16)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-17)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-18)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-19)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-20)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

(H-I-21)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-22)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-23)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-24)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-25)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

[ tables 3-2]

A^h10

Z^s10

R^s20

n10

Y^s10

R^s10

(H-I-26)

CH₃O-*

*-O-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-27)

CH₃O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-28)

CH₃O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-29)

CH₃O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-30)

CH₃O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

(H-I-31)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-32)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-33)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-34)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-35)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

(H-I-36)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-37)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-38)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-39)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-40)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

(H-I-41)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-42)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-43)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-44)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-45)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

(H-I-46)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

(CH₃)₃SiO-*

(H-I-47)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

(CH₃)₃SiO-*

(H-I-48)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

(CH₃)₃SiO-*

(H-I-49)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

(CH₃)₃SiO-*

(H-I-50)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

(CH₃)₃SiO-*

[ Table 4-1]

A^h10

Z^s10

R^s20

n10

Y^s10

R^s10

(H-I-51)

C₂H₅O-*

*-O-*

CH₃-*

1～60

CH₃-*

(H-I-52)

C₂H₅O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-53)

C₂H₅O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-54)

C₂H₅O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

CH₃-*

(H-I-55)

C₂H₅O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

(H-I-56)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

CH₃-*

(H-I-57)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-58)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-59)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

CH₃-*

(H-I-60)

C₂H₅O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

(H-I-61)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-*

1～60

CH₃-*

(H-I-62)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-63)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-64)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

CH₃-*

(H-I-65)

C₂H₅O-*

*-(CH₂)₂-*

CH₃-^*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

(H-I-66)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

CH₃-*

(H-I-67)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-68)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-69)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

CH₃-*

(H-I-70)

C₂H₅O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

(H-I-71)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

CH₃-*

(H-I-72)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-73)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-74)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

CH₃-*

(H-I-75)

C₂H₅O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

[ tables 4-2]

A^h10

Z^s10

R^s20

n10

Y^s10

R^s10

(H-I-76)

CH₃O-*

*-O-*

CH₃-*

1～60

CH₃-*

(H-I-77)

CH₃O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-78)

CH₃O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-79)

CH₃O-*

*-O-*

CH₃-*

1～60

“Si(CH₃)₂One (CH)₂)₃One Feng

CH₃A

(H-I-80)

CH₃O-*

*-O-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

(H-I-81)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

CH₃-*

(H-I-82)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-83)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

*-si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-84)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH2)₃-*

CH₃-*

(H-I-85)

CH₃O-*

*-CH₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

(H-I-86)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

CH₃-*

(H-I-87)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～6D

*-si(CH₃)₂-CH₂-*

CH₃-*

(H-I-88)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-89)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

CH₃-*

(H-I-90)

CH₃O-*

*-(CH₂)₂-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

(H-I-91)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

CH₃-*

(H-I-92)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-93)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-94)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-si(CH₃)₂-(CH₂)₃-*

CH₃-*

(H-I-95)

CH₃O-*

*-(CH₂)₃-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

(H-I-96)

CH₃O-*

*-(CH2)₄-*

CH₃-*

1～60

CH₃-*

(H-I-97)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-CH₂-*

CH₃-*

(H-I-98)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₂-*

CH₃-*

(H-I-99)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₃-*

CH₃-*

(H-I-100)

CH₃O-*

*-(CH₂)₄-*

CH₃-*

1～60

*-Si(CH₃)₂-(CH₂)₄-*

CH₃-*

The compound (H) containing a siloxane chain is more preferably a compound represented by the following formula (H3) or the following formula (H4).

[ in the formula (H3), n2 is an integer of 1 to 60 ]

[ in the formula (H4), n4 is an integer of 1 to 60 ]

N2 and n4 are preferably integers of 2 or more, more preferably integers of 3 or more, more preferably integers of 50 or less, still more preferably integers of 45 or less, still more preferably integers of 30 or less, and particularly preferably integers of 25 or less.

The number average molecular weight (Mn) of the compound (H) containing a siloxane chain is preferably 300 or more, more preferably 350 or more, further preferably 400 or more, and preferably 5200 or less, more preferably 4000 or less, further preferably 3500 or less, further preferably 3200 or less, particularly preferably 3000 or less, and most preferably 2500 or less.

The number average molecular weight (Mn) can be measured, for example, by Gel Permeation Chromatography (GPC) under the following conditions. As the pretreatment, it is preferable to use a solution obtained by dissolving the sample in an eluent and then filtering the solution through a 0.45 μm membrane filter as a measurement solution.

[ measurement conditions ]

The device comprises the following steps: shimadzu LC-10

Column: oligopore, PLGel MIXED-D

Eluent: toluene

Flow rate: 1.0-mL/min

A detector: RI detector

Column temperature: 35 deg.C

Injection amount: 50 μ L

Molecular weight standard: standard polystyrene 110000, 100000, 43000, 38000, 6000, 2600, 600

The amount of the compound (H) containing a siloxane chain is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, further preferably 0.03% by mass or more, and further preferably 1.0% by mass or less, more preferably 0.5% by mass or less, further preferably less than 0.3% by mass, further preferably 0.2% by mass or less, and particularly preferably 0.15% by mass or less, based on 100% by mass of the entire composition.

The amount of the above-mentioned compound (H) containing a siloxane chain can be adjusted at the time of preparing the composition. The amount of the compound (H) containing a siloxane chain can be calculated from the analysis result of the composition. In the present specification, when the ranges of the amounts and mass ratios of the respective components are described, the ranges can be adjusted in the preparation of the composition, as in the above.

In the composition of the present invention, the use of a predetermined amount of the compound (H) containing a siloxane chain improves the coatability when the composition is brought into contact with a substrate.

Examples of the method for synthesizing the compound (H) having a siloxane chain include the methods described in Japanese patent laid-open publication No. 2017-201009.

3. Metal Compound (G)

The metal compound (G) of the present invention is at least 1 selected from the group consisting of metal compounds represented by the following formula (G1) and condensates thereof.

M(R^g10)_r(A^g1)_m-r (G1)

The metal compound represented by the formula (G1) is a compound in which at least a hydrolyzable group A is bonded to a metal atom M^g1The compound of (1). In the present specification, "metal" is used to mean a semimetal such as Si or Ge.

The metal atom M is preferably Al, Si, Ti, Sn, or Zr, more preferably Al, Si, Ti, or Zr, and further preferably Si.

As A^g1The hydrolyzable group represented by (a) is not particularly limited as long as it is a group which provides a hydroxyl group (e.g., silanol group) by hydrolysis, and examples thereof include alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; a hydroxyl group; an acetoxy group; a chlorine atom; isocyanate groups, and the like. Among them, preferred is an alkoxy group having 1 to 6 carbon atoms, more preferred is an alkoxy group having 1 to 4 carbon atoms, and still more preferred is an alkoxy group having 1 to 2 carbon atoms.

R^g10The hydrocarbon chain-containing group is a group having at least a part of a hydrocarbon group, and usually consists only of a hydrocarbon group (hydrocarbon chain), and may be a part of methylene group (-CH) of the hydrocarbon chain, if necessary₂-) is substituted with a group of oxygen atoms. In addition, a methylene group (-CH) adjacent to the metal atom M₂-) is not substituted by an oxygen atom, and additionally, 2 methylene groups (-CH) are consecutive₂-) are not simultaneously substituted with oxygen atoms.

When the hydrocarbon chain-containing group is a hydrocarbon group, the number of carbon atoms is preferably 1 to 18, more preferably 1 to 10, still more preferably 1 to 6, and yet more preferably 1. The hydrocarbon chain-containing group may be branched or straight. The hydrocarbon chain-containing group is preferably a group containing a saturated or unsaturated aliphatic hydrocarbon chain, and more preferably a group containing a saturated aliphatic hydrocarbon chain. The saturated aliphatic hydrocarbon chain-containing group is more preferably a saturated aliphatic hydrocarbon group. Saturated aliphatic hydrocarbon groups include, for example, methyl, ethyl, propyl, and the like.

M is the valence of the metal atom M, and is 3 In the case where the metal atom M is a 3-valent metal such as Al, Fe, In, 4 In the case where the metal atom M is a 4-valent metal such as Ge, Hf, Si, Ti, Sn, Zr, or 5 In the case where the metal atom M is a 5-valent metal such as Ta.

Examples of the metal compound represented by the formula (G1) include a metal compound in which r is 0, that is, a metal atom M to which only a hydrolyzable group a is bonded^g1Metal compound G11; or r ═ 1, i.e., 1 hydrocarbon chain-containing group or hydrogen atom and 2 or more hydrolyzable groups A bonded to the metal atom M^g1Metal compound G12.

3-1. Metal compound G11

As the metal atom M to which only the hydrolyzable group A is bonded^g1Specific examples of the metal compound G11 include trialkoxyaluminums such as triethoxyaluminum, tripropoxyaluminum, tributoxyaluminum and the like; trialkoxy iron such as triethoxy iron; trialkoxyindium such as trimethoxyindium, triethoxyindium, tripropoxyindium, tributoxyindium and the like; tetraalkoxygermanium such as tetramethoxygermanium, tetraethoxygermanium, tetrapropoxygermanium, tetrabutoxygermanium; hafnium tetraalkoxide such as hafnium tetramethoxide, hafnium tetraethoxide, hafnium tetrapropoxide and hafnium tetrabutoxide; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane; tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium and tetrabutoxytitanium; tetraalkoxytin such as tetramethoxytin, tetraethoxytin, tetrapropoxy tin, tetrabutoxy tin; tetraalkoxyzirconium such as tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxy zirconium, tetrabutoxy zirconium; and pentaalkoxy tantalum such as pentamethoxy tantalum, pentaethoxy tantalum, pentapropoxy tantalum, and pentabutoxy tantalum.

3-2. Metal compound G12

To the metal atom M are bonded 1 hydrocarbon chain-containing group or hydrogen atom and 2 or more hydrolyzable groups A^g1The metal compound G12 of (1) is preferably such that the metal atom M is a 4-valent metal (Ge, Hf, Si, Ti, Sn, Zr, etc.), more preferably such that the metal atom M is Si. Specific examples of the metal atom M as Si include alkyltrialkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, and methyltripropoxysilane; alkenyl trisilanes such as vinyltrimethoxysilane and vinyltriethoxysilaneAn alkoxysilane; trialkoxysilanes such as trimethoxysilane, triethoxysilane, tripropoxysilane and the like; dialkoxyalkylsilanes such as dimethoxymethylsilane and diethoxymethylsilane.

Specifically, the metal compound represented by the formula (G1) is preferably a compound represented by the following formula (G2).

Si(OR^g21)_y(R^g22)_4-y (G2)

[ in the formula (G2), R^g21Represents an alkyl group having 1 to 6 carbon atoms, R^g22Represents a group containing a hydrocarbon chain or a hydrogen atom, y is 3 or 4]

R^g21The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 or 2 carbon atoms.

As R^g21Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

As R^g22Examples of the hydrocarbon chain-containing group represented by the above-mentioned formula^g10The same groups as those described for the hydrocarbon chain-containing group are also applicable, and the preferable ranges are also the same.

The condensate of the metal compound represented by the formula (G1) includes, for example, a compound formed by hydrolysis-condensation reaction between a plurality of metal compounds represented by the formula (G1) via a hydrolyzable group. The plurality of metal compounds represented by the formula (G1) may be the same or different, and preferably the same. The condensation product is preferably a condensation product obtained by condensing 2 to 60 metal compounds represented by the formula (G1), more preferably a condensation product obtained by condensing 2 to 40 metal compounds, still more preferably a condensation product obtained by condensing 2 to 20 metal compounds, and still more preferably a condensation product obtained by condensing 2 to 10 metal compounds. The metal compound represented by the formula (G1) may be hydrolyzed and condensed to obtain a condensate, and commercially available siloxane oligomers and resins may be used as appropriate.

The metal compound (G) is preferably at least 1 selected from the group consisting of the compounds represented by the above formula (G2) and condensates thereof.

The condensate of the compound represented by the formula (G2) is preferably a condensate obtained by passing (OR) between a plurality of metal compounds represented by the formula (G2)^g21) The metal compounds represented by the plural formulae (G2) may be the same or different, and preferably the same, as the compound formed by hydrolysis-condensation of the base. The condensate of the compound represented by the formula (G2) is preferably a condensate obtained by condensing 2 to 60 metal compounds represented by the formula (G2), more preferably a condensate obtained by condensing 2 to 40 metal compounds, still more preferably a condensate obtained by condensing 2 to 20 metal compounds, and still more preferably a condensate obtained by condensing 2 to 10 metal compounds. The condensate of the compound represented by the formula (G2) is preferably a condensate of tetraalkoxysilane, more preferably a condensate of tetramethoxysilane or tetraethoxysilane, and particularly preferably a condensate of tetraethoxysilane. Specific examples of the condensate of the compound represented by formula (G2) include ethyl silicate 40, ethyl silicate 48, methyl silicate 51, and methyl silicate 53A manufactured by COLCOAT co.

In addition, 2 or more kinds of metal compounds (G) may be used.

The amount of the metal compound (G) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more, and further preferably 10% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.8% by mass or less, based on 100% by mass of the entire composition.

The total amount of the polysilazane (F) and the compound (H) having a siloxane chain and the metal compound (G) is preferably 0.3 mass% or more, more preferably 0.4 mass% or more, further preferably 0.5 mass% or more, further preferably 5 mass% or less, more preferably 3 mass% or less, further preferably less than 2.6 mass%, further preferably 1.5 mass% or less, and particularly preferably 1.2 mass% or less, based on 100 mass% of the entire composition.

The mass ratio ((H + G)/(F + H + G)) of the compound (H) having a siloxane chain to the metal compound (G) is preferably 1% or more, more preferably 5% or more, further preferably 8% or more, and further preferably 95% or less, more preferably 85% or less, further preferably 80% or less, further preferably 70% or less, and particularly preferably 60% or less, relative to the total amount of the polysilazane (F), the compound (H) having a siloxane chain, and the metal compound (G). If the mass ratio is too small, appearance defects may occur, and if the mass ratio is too large, excellent curability may not be imparted to the liquid repellent layer.

The mixed composition of the present invention is a composition in which the polysilazane (F), the compound (H) having a siloxane chain, and the metal compound (G) are mixed, and is obtained by mixing these (F) to (H).

4. Solvent (I)

Solvent (I) may be used in the composition of the present invention.

Examples of the solvent (I) include alcohol solvents, ether solvents, ketone solvents, ester solvents, amide solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, and 1-propoxy-2-propanol, and examples of the ether solvent include dimethoxyethane, tetrahydrofuran, and dioxaneExamples of the ketone solvent include acetone and methyl ethyl ketone (2-butanone), examples of the ester solvent include ethyl acetate and butyl acetate, examples of the amide solvent include dimethylformamide, examples of the aliphatic hydrocarbon solvent include pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, cycloheptane, methylcyclohexane and mineral spirits (MineraLspirit), and examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, chlorobenzene and dichlorobenzene. Among these, ketone solvents, ether solvents, ester solvents, and aliphatic hydrocarbon solvents are preferable, and aliphatic hydrocarbon solvents are more preferable. These solvents may be used in a single kind, or 2 or more kinds may be appropriately mixed and used. The solvent (I) is preferably free of water in terms of increased stability of the coating liquid, reduced coating offset, and reduced foreign matter during coating.

The amount of the solvent (I) is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on 100% by mass of the entire composition. The upper limit is set according to the amounts of polysilazane (F), the compound (H) containing a siloxane chain, the metal compound (G), and an additive component other than these (hereinafter referred to as a third component), and may be the solvent (I) other than polysilazane (F), the compound (H) containing a siloxane chain, the metal compound (G), and the third component.

The mixed composition of the present invention is preferably obtained by mixing the polysilazane (F), the compound (H) having a siloxane chain, and the metal compound (G) with the solvent (I).

In preparing the mixed composition of the present invention, a catalyst may coexist. In the present invention, the catalyst is preferably a catalyst capable of curing polysilazane, and examples thereof include 1-methylpiperazine, 1-methylpiperidine, 4 ' -trimethylenedipiperidine, 4 ' -trimethylenebis (1-methylpiperidine), diazabicyclo- [2,2,2] octane, cis-2, 6-dimethylpiperazine, 4- (4-methylpiperidine) pyridine, bipyridine, α -methylpyridine, β -methylpyridine, γ -methylpyridine, piperidine, dimethylpyridine, pyrimidine, pyridazine, 4 ' -trimethylenedipyridine, 2- (methylamino) pyridine, pyrazine, quinoline, quinoxaline, triazine, pyrrole, 3-pyrroline, imidazole, triazole, tetrazole, 1-methylpyrrolidine and other N-heterocyclic compounds, such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, Amines such as triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, dihexylamine, trihexylamine, heptylamine, dihexylamine, octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine, triphenylamine, and the like, for example, 1, 8-diazabicyclo [5,4,0] 7-undecene (DBU), 1, 5-diazabicyclo [4,3,0] 5-nonene (DBN), 1,5, 9-azacyclododecane, 1,4, 7-azacyclononane, and the like.

In addition to the above-mentioned catalysts, the catalyst is preferably a catalyst that functions as a hydrolysis-condensation catalyst of a hydrolyzable group bonded to a silicon atom, and examples of the catalyst include an acidic compound; a basic compound; organometallic compounds, and the like. Examples of the acidic compound include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen peroxide, hydrochloric acid, and hypochlorous acid; and organic acids such as acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, and stearic acid. Examples of the basic compound include ammonia. Examples of the organometallic compound include organometallic compounds containing a metal element such as Al, Fe, Zn, or Sn as a central metal, and organic aluminum compounds such as aluminum carboxylates, aluminum acetylacetonate complexes, and aluminum ethyl acetoacetate complexes; organic iron compounds such as iron carboxylates (e.g., iron octylate); organic zinc compounds such as zinc acetylacetonate monohydrate, zinc naphthenate, and zinc octylate; organotin compounds such as dibutyltin diacetate complex; further, examples of the organic metal compound include metal carboxylates containing Ni, Ti, Pt, Rh, Co, Ru, Os, Pd, Ir, and the like; acetylacetone complexes containing Ni, Pt, Pd, Rh, and the like; fine metal particles of Au, Ag, Pd, Ni, Zn, Ti, etc.; a metal peroxide; a metal chloride; cyclopentadienyl complexes of metals such as ferrocene, zirconocene, etc.

The composition of the present invention may contain various additives such as an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-biofouling agent, a deodorant, a pigment, a flame retardant, and an antistatic agent, in a range where the effects of the present invention are not impaired.

The coating film obtained from the composition of the present invention is usually formed on a substrate, and examples of a method for contacting the coating film with the substrate include a method for applying the composition to the substrate, such as spin coating, dip coating, spray coating, roll coating, bar coating, manual coating (a method for applying a liquid to a substrate by impregnating a cloth or the like with the liquid), flow through (a method for applying a liquid directly to a substrate by using a dropper or the like), and spraying (a method for applying a liquid to a substrate by using spraying), and the like. In particular, from the viewpoint of workability, the spray coating method, the hand coating method, the flow coating method, and the spin coating method are preferable, and the flow coating method and the spin coating method are more preferable.

The composition thus contacted with the substrate is allowed to stand in air at normal temperature, and reacts with moisture in the air to be decomposed and silylized, whereby a coating film containing an Si — O skeleton can be formed on the substrate. The standing time is not particularly limited, but is preferably 1 minute or more, and more preferably 2 minutes or more. From the viewpoint of practicality, the time is preferably 12 hours or less, more preferably 1 hour or less, further preferably 30 minutes or less, and further preferably 10 minutes or less.

The film thickness of the coating film may be, for example, about 0.1 to 200 nm. Preferably 0.2 to 100nm, more preferably 0.3 to 50 nm.

The substrate to be contacted with the composition of the present invention is not particularly limited, and the shape of the substrate may be either a flat surface or a curved surface, or may be a three-dimensional structure in which a plurality of surfaces are combined.

The material of the base material is not limited, and may be made of any of an organic material and an inorganic material. Examples of the organic material include thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, and polyolefin resins; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, and urethane resins. Examples of the inorganic material include ceramics; glass; metals such as iron, silicon, copper, zinc, and aluminum; alloys containing the above metals, and the like.

The above-mentioned base material may be subjected to an easy adhesion treatment in advance. Examples of the easy adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. Further, the undercoat treatment may be performed with a resin, a silane coupling agent, tetraalkoxysilane, or the like, or a glass coating such as polysilazane may be applied to the substrate in advance.

Preferably, a liquid repellent layer is further formed on the surface of the coating film obtained from the composition of the present invention. That is, it is preferable to form an intermediate layer made of the composition of the present invention (hereinafter, sometimes referred to as an intermediate layer-forming composition) on a substrate and further form a liquid repellent layer on a surface (surface on the opposite side of the substrate) of the intermediate layer. Although the detailed mechanism is not clear, when the composition of the present invention is used as the composition for forming an intermediate layer between a liquid-repellent layer and a substrate, the possibility of promoting the dehydration condensation reaction of silanol groups in the liquid-repellent layer is higher than that in the case where only the liquid-repellent layer is formed on the substrate, for example, the composition is affected by a product generated by the hydrolysis condensation reaction of the composition for forming an intermediate layer. In this case, when the composition of the present invention is used as the composition for forming the intermediate layer, the crosslinking density of the liquid repellent layer becomes high, and the abrasion resistance is remarkably improved. In addition, conventionally, heating was required when the liquid repellent layer was formed at a practical speed, but by using the composition of the present invention as the composition for forming the intermediate layer between the liquid repellent layer and the substrate, it was also possible to perform normal temperature curing of the liquid repellent layer at a practical speed.

Hereinafter, the liquid repellent layer (liquid repellent film) will be described.

As a composition for obtaining a liquid repellent film (hereinafter, sometimes referred to as a composition for forming a liquid repellent layer), it is preferable to mix an organosilicon compound (a) in which at least 1 trialkylsilyl-containing molecular chain and at least 1 hydrolyzable group are bonded to a silicon atom (hereinafter, sometimes referred to as a central silicon atom) with a metal compound (B).

1. Organosilicon Compound (A)

As the organosilicon compound (a), a compound in which x is 0 or 1 in the formula (H1) described in the above-mentioned siloxane chain-containing compound (H) is preferably used. By bonding a trialkylsilyl group to the molecular chain, the water/oil repellency, sulfuric acid resistance, and hot water resistance of the film formed from the liquid-repellent layer-forming composition are improved, and the droplets are easily moved. When the alkyl group of the trialkylsilyl group is substituted with a fluoroalkyl group, the liquid repellency (water repellency and/or oil repellency, hereinafter sometimes referred to as "water/oil repellency") of the film interface can be similarly improved.

The preferable range of the organosilicon compound (a) is the same as in the embodiment described above for the compound (H) containing a siloxane chain. Among them, a compound represented by the following formula (H3) is particularly preferable.

[ in the formula (H3), n2 is an integer of 1 to 60 ]

N2 is more preferably an integer of 2 or more, still more preferably an integer of 3 or more, yet more preferably an integer of 45 or less, yet more preferably an integer of 30 or less, and particularly preferably an integer of 25 or less.

The amount of the organosilicon compound (a) is preferably 0.005 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 1% by mass, based on 100% by mass of the entire liquid-repellent layer-forming composition.

2. Metal compound (B)

The metal compound (B) is preferably a metal compound represented by the following formula (B1).

M(R^b10)_r(A^b1)_m-r(b1)

[ In the formula (b1), M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr or Ta, R^b10Represents a group having a siloxane skeleton, a group having a hydrocarbon chain, or a hydrogen atom, and r is 0 or 1. A plurality of A^b1Each independently represents a hydrolyzable group, and M is an integer of 3 to 5 corresponding to the metal atom M]

The metal compound (B) is preferably a compound in which at least a hydrolyzable group A is bonded to a metal atom M as represented by the formula (B1)^b1The compound of (1). In the present specification, "metal" is used to mean a semimetal such as Si or Ge.

As described above, it is considered that the water-and oil-repellent film obtained from the liquid-repellent layer-forming composition has an improved water-and oil-repellent function due to the trialkylsilyl group derived from the organosilicon compound (a), and the structure based on the metal compound (B) acts as a separator in the liquid-repellent film.

M is preferably Al, Si, Ti, Sn or Zr, more preferably Si.

A^b1A hydrolyzable group represented by the formula (I) and R^b10Of the representationThe group having a siloxane skeleton and the group having a hydrocarbon chain can be appropriately selected from the hydrolyzable group, the group having a siloxane skeleton and the group having a hydrocarbon chain described in the above-mentioned compound (H) having a siloxane chain, and the preferable ranges are also the same.

The liquid repellent layer-forming composition may use 2 or more metal compounds (B). Further, a condensate of the metal compound (B) may also be used.

Specifically, the metal compound (B) is preferably a compound represented by the following formula (B2).

Si(OR^b11)_zH_4-z (b2)

[ formula (b2) wherein R^b11Represents an alkyl group having 1 to 6 carbon atoms, and z is 3 or 4]

R^b11The number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 or 2.

As R^b11Examples of the alkyl group include methyl, ethyl, propyl, and butyl.

The amount of the metal compound (B) is preferably 0.01 to 50% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.05 to 1% by mass, based on 100% by mass of the entire liquid repellent layer-forming composition.

The liquid repellent layer-forming composition is a composition obtained by mixing the organosilicon compound (a) and the metal compound (B), and is obtained by mixing these compounds (a) to (B).

3. Catalyst (C)

In the preparation of the liquid repellent layer-forming composition, a catalyst (C) functioning as a hydrolysis-condensation catalyst of a hydrolyzable group bonded to a silicon atom may be allowed to coexist together with the organosilicon compound (a) and the metal compound (B), and an acid, a base, or the like may be used as the catalyst (C), and among these, an acid is preferably used. The acid may be an inorganic acid or an organic acid, and is preferably an organic acid in view of easy control of the hydrolysis-condensation reaction. As described later, by using an acid as the catalyst (C) and suppressing the amount of water used, the reaction at the time of forming the liquid repellent film can be made to progress smoothly, and a good liquid repellent film can be formed.

Specific examples of the acid include nitric acid, hydrochloric acid, maleic acid, phosphoric acid, malonic acid, formic acid, benzoic acid, phenylacetic acid, acetic acid, butyric acid, 2-methylpropionic acid, propionic acid, and 2, 2-dimethylpropionic acid, and organic acids are preferable, and maleic acid (pKa ═ 1.92), formic acid (pKa ═ 3.75), and acetic acid (pKa ═ 4.76) are more preferable.

The catalyst (C) may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

The amount of the catalyst (C) is preferably 0.0001 to 30% by mass, and more preferably 0.00015 to 1% by mass, based on 100% by mass of the entire liquid-repellent layer-forming composition.

4. Water (D)

In the liquid repellent layer-forming composition, water (D) is preferably used, and hydrolysis of the hydrolyzable group is promoted by using water (D). The water (D) may be water in the air, or may be added to the composition to be positively mixed therein.

The amount of the water (D) used in preparing the liquid repellent layer-forming composition is preferably more than 0% by mass and less than 2.20% by mass. By making the amount of the water less than 2.20 mass%, the reaction at the time of forming the liquid repellent film can be smoothly performed, and a good liquid repellent film can be formed.

5. Solvent (E)

The liquid repellent layer-forming composition may further contain a solvent (E). As the solvent (E), the solvents exemplified in the above solvent (I) can be used, and among them, alcohol solvents or ether solvents are preferable, and alcohol solvents are more preferable.

The amount of the solvent (E) is preferably 10 to 99.9% by mass, based on 100% by mass of the entire liquid repellent layer-forming composition.

The liquid repellent layer-forming composition is preferably obtained by mixing a catalyst (C), water (D), a solvent (E), and the like, in addition to the organosilicon compound (a) and the metal compound (B).

The liquid repellent layer-forming composition may contain various additives such as an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-biofouling agent, a deodorant, a pigment, a flame retardant, and an antistatic agent, as long as the effects of the present invention are not impaired.

The liquid repellent film is obtained by curing the liquid repellent layer-forming composition.

The method for bringing the composition for forming a liquid repellent layer into contact with the coating film (intermediate layer) obtained from the composition of the present invention is the same as the method described for bringing the intermediate layer into contact with the substrate.

The liquid-repellent layer can be formed on the intermediate layer by heating the composition for forming a liquid-repellent layer in contact with the intermediate layer for about 1 to 10 times (for example, 80 to 300 ℃) to promote hydrolysis of the hydrolyzable group of the liquid-repellent layer and dehydration condensation reaction of the silanol group, but when the composition of the present invention is used as the composition for forming an intermediate layer, there is a possibility that dehydration condensation reaction of the silanol group of the liquid-repellent layer may be promoted without heating, for example, by being affected by a product generated by the hydrolysis condensation reaction of the composition for forming an intermediate layer. That is, by using the composition of the present invention as an intermediate layer-forming composition, a liquid-repellent film can be formed at a practical rate even when left to stand in air at normal temperature and humidity. The standing time is not particularly limited, but is preferably 1 hour or more, more preferably 3 hours or more, and further preferably 12 hours or more. From the viewpoint of practicality, the time is preferably 48 hours or less, and more preferably 24 hours or less.

The film thickness of the liquid repellent film may be, for example, about 0.5 to 100 nm.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples, and can be carried out by appropriately changing the scope of the present invention and the gist thereof described below, and all of them are included in the technical scope of the present invention.

Production example 1

(preparation of composition for Water repellent layer formation)

Among the compounds represented by the formula (H3), 0.014 parts by mass of a compound (hereinafter referred to as compound 1) having an average value of n2 of 24 and 0.036 parts by mass of triethoxysilane were dissolved in 0.1027 parts by mass of 2-propanol, and the mixture was stirred at room temperature for 10 minutes. To the resulting solution was added dropwise a 0.1M aqueous solution of acetic acid (acetic acid: 7.73X 10)^-5Mass parts, water: 0.013 parts by mass), and stirred at 65 ℃ for 2 hours to obtain a sample solution 1.

The obtained sample solution 1 was diluted with 46.7 parts by mass of 2-propanol to prepare a composition a.

Compositions B and C were obtained in the same manner as composition a except that the kinds and/or amounts of organosilicon compound (a), metal compound (B), catalyst (C), water (D) and solvent (E) were changed as shown in table 5.

[ Table 5]

(preparation of composition for intermediate layer formation)

An intermediate layer-forming composition (composition 1) was obtained by dissolving 0.15 parts by mass of Durazane (registered trademark) 1500Rapid cure (product of MERCK Co., Ltd.), 0.015 parts by mass of the compound (1), and 0.09 parts by mass of tetraethoxysilane in 29.75 parts by mass of isooctane. Durazane (registered trademark) 1500rapid cure has a structural unit represented by the following formula (f 4).

In the formula (f4), R represents a hydrogen atom or a methyl group.

Durazane (registered trademark) 1500rapid cure has 9 to 27 mass% of Si (OC)₂H₅)₃And (f4) the Si-CH group in the structure₃The molar ratio of methyl groups of the radicals to hydrogen atoms of the SiH radicals (methyl groups/hydrogen atoms) being2.39。

The above Si (OC)₂H₅)₃The mass ratio of radicals and the molar ratio of methyl groups to hydrogen atoms being based on¹H-NMR (400MHz, reference: CDCL)₃(-7.24 ppm)) was determined. That is, SiH and SiCH in polysilazane are obtained from the integrated value₃And Si (OCH)₂CH₃)₃The molar ratio of methyl group to hydrogen atom was calculated. Further, Si (OC) contained in polysilazane was calculated by converting each into a mass ratio₂H₅)₃Mass% of the base.

Compositions 2 to 13 were obtained in the same manner as in composition 1 except that the kinds and/or amounts of polysilazane (F), the compound (H) having a siloxane chain, the metal compound (G), and the solvent (I) were changed as shown in table 6.

[ Table 6]

In Table 6, the compounds 1 to 4 are as follows.

Compound 1: of the compounds represented by the above formula (H3), the average value of n2 is 24 (molecular weight calculated from the structural formula; 2212.52)

Compound 2: of the compounds represented by the above formula (H4), the average value of n4 is 24 (molecular weight calculated from the structural formula; 1990.66)

Compound 3: among the compounds represented by the above formula (H4), the average value of n4 is 3 (molecular weight calculated from the structural formula; 432.84)

Compound 4: among the compounds represented by the above formula (H3), the average value of n2 is 3 (molecular weight calculated from the structural formula; 655.3)

[ examples 1 to 15]

(preparation of coating film)

A glass substrate 5X 5cm in size having its surface activated by atmospheric pressure plasma treatment²(EAGLE XG, Corning Inc.) was set at an elevation angle of 45 deg.. 500. mu.L of the composition for forming an intermediate layer was flushed from the upper surface of the glass substrateDrying at normal temperature and humidity for 5 minutes. Further, 500. mu.L of the composition for forming a liquid repellent layer was poured thereon, and the resultant was air-dried at normal temperature and humidity for 1 day to form a coating film on the glass substrate.

Comparative example 1

A glass substrate 5X 5cm in size having its surface activated by atmospheric pressure plasma treatment²(EAGLE XG, Corning Inc.) was set at an elevation angle of 45 deg.. A coating film was formed on the glass substrate by flushing 500 μ L of the liquid repellent layer-forming composition from the upper surface of the glass substrate and air-drying the composition at normal temperature and humidity for 1 day.

The coatings obtained in the above examples and comparative examples were evaluated in the following manner.

(contact Angle)

The amount of water droplets was 3.0 μ L using a contact angle measuring device "DM 700" manufactured by synergetics, inc, and the following analysis method was used: the contact angle of the surface of the coating film with respect to water was measured by the θ/2 method. The contact angle of 95 ° or more was evaluated as excellent water repellency.

(slip speed)

Water was dropped on the surface of the film, and the water repellency was evaluated by the slip speed of the water droplets on the surface of the film. Specifically, 50 μ L of water was dropped onto the surface of the coating film on a glass substrate inclined at 20 ° using a contact angle measuring device "DM 700" manufactured by synergestic interfacial science corporation, and the time from the initial dropping position to the time when the water droplet slipped off by 15mm was measured to calculate the slip-off speed (mm/sec) of the water droplet on the surface of the coating film. The water repellency was evaluated to be excellent when the slip velocity of water droplets was 20 mm/sec or more.

(abrasion resistance)

2.5mL of water was dropped on the film, and a silicon wafer (SR-400, manufactured by Tigers Polymer) was brought into contact therewith. Then, the wafer and the coating film were wiped at a distance of 20mm in 400 times under a condition that a load of 500g was applied from the wafer and a reciprocating speed was 400mm per minute, and the contact angle at the central portion 3 of the abraded portion was measured, and the number of times that 2 out of 3 was decreased to 85 ° or less was measured. The case where the number of times was 400 or more was evaluated as excellent abrasion resistance.

The types of the intermediate layer-forming composition and the liquid repellent layer-forming composition used and the evaluation results of the obtained coating film are shown in table 7.

[ Table 7]

Examples 1 to 15, in which a mixed composition of at least 1 metal compound (G) selected from the group consisting of the metal compounds represented by the formula (G1) and condensates thereof, polysilazane (F), and a compound (H) containing a siloxane chain was used as the composition for forming the intermediate layer, and a liquid-repellent layer was further formed on the intermediate layer, were able to produce a coating film having excellent abrasion resistance and room temperature curability without impairing liquid repellency.

Industrial applicability

When the composition of the present invention is used as a composition for forming an intermediate layer, a coating film obtained by forming a liquid-repellent film on the intermediate layer is excellent in abrasion resistance, preferably excellent in room temperature curability, without impairing liquid repellency (particularly water repellency). Therefore, the polymer is useful as a substrate for display devices such as touch panel displays, optical elements, semiconductor elements, building materials, automobile parts, nanoimprint technology, and the like. Further, the present invention can be suitably used as articles such as bodies, window glasses (front glass, side glass, and rear glass), rearview mirrors, and dampers in transportation equipment such as electric cars, automobiles, ships, and airplanes. In addition, the solar photovoltaic module can be used for outdoor applications such as building outer walls, tents, solar photovoltaic modules, sound insulation boards, and concrete. It can also be used in fish net, insect catching net, water tank, etc. Further, the present invention can be used for various indoor devices such as articles of various members around a kitchen, a bathroom, a washstand, a mirror, and a toilet, a porcelain such as a chandelier and a tile, an artificial marble, and an air conditioner. Further, the resin composition can be used for antifouling treatment of jigs, inner walls, pipes, and the like in factories. It is also suitable for goggles, glasses, protective helmets, pinball machines, fibers, umbrellas, toys, football, etc. Furthermore, the composition can be used as an adhesion preventing agent for various packaging materials such as food packaging materials, cosmetic packaging materials, and can interiors.

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