TW201446895A - Method of producing article with silane-based film - Google Patents

Abstract

An objective of this invention is to provide a method of producing an article comprising a substrate and a silane-based film covering the surface of the substrate, which is capable of forming a silane-based film with higher friction durability. Provided is a method of producing an article comprising a substrate and a silane-based film covering the surface of the substrate, comprising: (a) forming a precursor film including a silane compound on a surface of a substrate, the silane compound having a hydrolyzable group bonding to Si; (b) irradiating the substrate formed with the precursor film with microwave to form a silane-based film originated from the precursor film on the substrate.

Description

Method for producing article having decane film

The present invention relates to a method of producing an article having a decane-based film, and an article produced by the method.

It is known that when a certain decane compound is used for the surface treatment of a substrate, excellent hydrophobicity, oleophobicity, stain resistance, surface smoothness and the like can be provided. The film obtained from the decane compound, that is, the decane-based film, is applied as a so-called functional film to various substrates such as glass, plastic, fiber, and building materials (see Patent Document 1).

The decane-based film is generally formed on the surface of a substrate by a dry coating method such as vacuum deposition or sputtering. Further, the decane-based film may be formed on the surface of the substrate by a wet coating method such as dipping or spraying or a normal piezoelectric method (see Patent Document 1).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2008-534696

As described above, the decane-based film can be formed by a general dry coating method such as vacuum deposition or sputtering, but these methods have a problem of low productivity. On the other hand, although the wet coating method such as immersion or spraying has high productivity, the durability of the obtained decane-based film cannot be said to be sufficient. In particular, since the decane-based film can exhibit the above functions even if it is a film, it is suitably used for optical members such as glasses or touch panels that require light transmittance or transparency, and it is required to further improve the friction durability in such applications.

An object of the present invention is to provide a method for producing an article comprising a substrate and a decane-based film covering the surface of the substrate, which is a method for forming a decane-based film having higher friction durability.

One object of the present invention is to provide a method for producing an article comprising a substrate and a decane-based film coated on the surface of the substrate, comprising: (a) forming a precursor film containing a decane compound on the surface of the substrate, the decane The compound has a group bonded to Si and hydrolyzable; and (b) the substrate on which the precursor film is formed is irradiated with microwaves, and a decane-based film derived from the precursor film is formed on the surface of the substrate.

According to the above production method of the present invention, a decane-based film having high friction durability can be easily formed as compared with the conventional method for forming a decane-based film.

Another object of the present invention is to provide an article obtained by the above production method of the present invention. The decane-based film of the article has high friction durability as described above, compared to the decane-based film of the article obtained by the conventional production method.

According to the present invention, a substrate of a body film before forming a decane compound having a group having a bond capable of being hydrolyzed with Si is irradiated with microwaves, whereby the base can be The surface of the material forms a decane-based film having high friction durability.

Fig. 1 is a graph showing the friction durability of the fluorine-containing decane-based film produced in Examples 1 and 2 of the present invention and Comparative Example 1.

Fig. 2 is a graph showing the friction durability of the fluorine-containing decane-based film produced in Examples 3 and 4 and Comparative Example 2 of the present invention.

Fig. 3 is a graph showing the friction durability of the fluorine-containing decane-based film produced in Examples 5 and 6 and Comparative Example 3 of the present invention.

Hereinafter, the method for producing the article of the present invention and the article obtained by the method of the present invention will be described in detail by way of embodiments of the present invention, but the present invention is not limited thereto.

The method for producing the article of the present invention can be roughly regarded as a method in which a film containing a decane compound is formed on a surface of a substrate as a precursor film, and then the precursor film is post-treated to form a decane-based film. The post-treatment system performs microwave irradiation.

First, prepare a substrate. The substrate which can be used in the present invention may be, for example, glass, resin (natural or synthetic resin, for example, may be a general plastic material, or may be a plate, a film, or the like), or a metal (a metal such as aluminum, copper or iron) or Any combination of materials such as alloys, ceramics, semiconductors, woven fabrics, fabrics, wood, ceramics, stone, etc., as long as at least the forebody is to be formed Before the film, the material constituting the surface of the substrate has a reactive group (a group which can be bonded to a group or a hydroxyl group of the Si after hydrolysis of the decane compound), and is not particularly limited.

For example, when the article having a decane-based film of the present invention is an optical member, a certain layer (or film) can be formed on the surface (outermost layer) of the substrate, and for example, a hard coat layer or an anti-reflection layer can be formed. The antireflection layer may use a single antireflection layer or a multilayer antireflection layer. Examples of the inorganic substance which can be used for the antireflection layer include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO ₃ and the like. These inorganic substances may be used singly or in combination of two or more kinds thereof (for example, a mixture). In the case of a multilayer antireflection layer, it is preferred to use SiO ₂ and/or SiO in its outermost layer. When the article having a decane-based film of the present invention is an optical glass component for a touch panel, a transparent electrode may be provided on a part of the surface of the substrate (glass), and for example, a film of indium tin oxide (ITO) or indium zinc oxide may be used. Further, the substrate may have an antistatic layer, an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film, a hard coat layer, a polarizing film, a retardation film, and the like according to specific specifications thereof. LCD module, etc.

The shape of the substrate is not particularly limited. Further, the surface region of the substrate on which the decane-based film is to be formed may be at least a part of the surface of the substrate, and may be appropriately determined depending on the use of the article to be manufactured, the specific specifications, and the like.

The substrate may be any material as long as at least the surface portion thereof is composed of a material having a hydroxyl group. The material may be glass, and a metal (especially a base metal), a ceramic, a semiconductor, or the like which forms a natural oxide film or a thermal oxide film on the surface may be mentioned. Alternatively, in the case where the resin has a hydroxyl group but is insufficient, or if the hydroxyl group is not originally present, the substrate may be subjected to some pretreatment to introduce and increase a hydroxyl group on the surface of the substrate. Examples of the pretreatment include plasma treatment (for example, corona discharge) and irradiation of ion beams. The plasma treatment is suitable for use by introducing or adding a hydroxyl group to the surface of the substrate and purifying the surface of the substrate (removing foreign matter, etc.). Further, another example of the pretreatment is a method of forming a monomolecular film on the surface of the substrate in advance by the LB method (Langmuir-Blodgett method) or a chemisorption method. An interface adsorbent having a carbon-carbon unsaturated bonding group, followed by a method of breaking an unsaturated bond in an environment containing oxygen or nitrogen.

Further, the substrate may be formed of a material containing at least a surface portion containing a polyoxonium compound or an alkoxysilane, and the polyoxyalkylene compound or alkoxydecane has one or more other reactivity. Other reactive groups such as Si-H groups.

Next, a precursor film containing a decane compound having a group bonded to Si and hydrolyzable is formed on the surface of the substrate.

The decane compound used in the present invention is not particularly limited as long as it has a group which is bonded to Si and is hydrolyzable, and is preferably a fluorine-containing decane compound. Further, as the fluorine-containing decane compound, those having a perfluoropolyether group in addition to the group bonded to Si and hydrolyzable can be used.

The decane compound is one or more selected from the group consisting of chlorosilanes, alkoxy decanes, and decane coupling agents, and examples of the chlorosilanes include methyltrichlorodecane and methyl dichloride. Examples of decane, dimethyldichlorodecane, trimethylchlorodecane, phenyltrichlorodecane, diphenyldichlorodecane, etc., and alkoxydecanes include, for example, tetramethoxydecane and methyltrimethoxydecane. , dimethyl dimethoxy decane, phenyl trimethoxy decane, diphenyl dimethoxy decane, tetraethoxy decane, methyl triethoxy decane, dimethyl diethoxy decane, benzene Alkoxy decane, diphenyldiethoxy decane, isobutyltrimethoxydecane, decyltrimethoxydecane, and the like are particularly preferably used.

Examples of the above decane coupling agent include vinyltrichlorodecane, vinyltrimethoxydecane, vinyltriethoxydecane, vinylstilbene (β-methoxyethoxy)decane, and β-(3,4). -Epoxycyclohexyl)ethyltrimethoxydecane, gamma-glycidoxy Propyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, γ-glycidoxypropyltriethoxydecane, γ-methylpropenyloxypropyl Trimethoxydecane, γ-methylpropenyloxypropyltriethoxydecane, γ-methylpropenylpropylmethyldimethoxydecane, γ-methylpropenylpropylmethylmethyl Ethoxy decane, N-β-(pentylethyl)-γ-aminopropyltrimethoxydecane, γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethyl Oxydecane, γ-chloropropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, and the like.

Examples of the fluorine-containing decane compound having a hydrolyzable group bonded to Si and a perfluoropolyether group include a compound represented by any one of the following formulas (1a) and (1b) (may also be 1) Kind or a mixture of two or more).

In the formula, Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, preferably a carbon number 1 which may be substituted by one or more fluorine atoms. 3 alkyl. The above alkyl group which may be substituted by one or more fluorine atoms is preferably a fluoroalkyl group or a perfluoroalkyl group in which all of the carbon atoms are substituted by fluorine, except that the terminal carbon atom is CF ₂ H-. Preferably, it is a perfluoroalkyl group.

a, b, c and s respectively represent the number of three repeating units of the perfluoropolyether constituting the main skeleton of the polymer, and are independent of each other and are integers of 0 or more and 200 or less, and the sum of a, b, c and s is at least 1, preferably from 1 to 100. The order of existence of each repeating unit with the following a, b, c or s and enclosed in parentheses is in any order in the formula. In the repeating units, -(OC ₄ F ₈ )- may be -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ ) CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF ₃ ) ₂ )-, -(OCF Any of (CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₆ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₆ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- may be any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )-, and -(OCF ₂ CF(CF ₃ ))- Good for - (OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- may be any of -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-, preferably -(OCF ₂ CF ₂ )-.

d and f are 0 or 1.

e and g are integers of 0 or more and 2 or less.

m and l are integers of 1 or more and 10 or less.

X represents a hydrogen atom or a halogen atom. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom.

Y represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms.

Z represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and still more preferably a trifluoromethyl group. base. Representative Z is a fluorine atom, and d and f are 1.

T and R ¹ are bonded to the group of Si.

T represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include -OA, -OCOA, -ON=C(A) ₂ , -N(A) ₂ , -NHA, halogen (in the formula, A represents a substituted or unsubstituted carbon number 1 to 3 alkyl groups) and the like. The hydroxyl group is not particularly limited and may be those produced by hydrolysis of a hydrolyzable group.

R ¹ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

n is an integer of 1 or more and 3 or less.

Other examples of the fluorine-containing decane compound having a hydrolyzable group bonded to Si and a perfluoropolyether group include a compound represented by any one of the following formulas (2a) and (2b) (which may be 1) Kind or a mixture of two or more).

Rf ² -PFPE-X-(SiT _n R ² _3-n ) _α ‧‧‧(2a)

(R ² _3-n T _n Si) _α -X-PFPE-X-(SiT _n R ² _3-n ) _α ‧‧‧(2b)

In the formula, Rf ² represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, preferably a carbon number 1 which may be substituted by one or more fluorine atoms. 3 alkyl. The above alkyl group which may be substituted by one or more fluorine atoms is preferably a fluoroalkyl group or a perfluoroalkyl group in which all carbon atoms are substituted by fluorine except for a terminal carbon atom of CF ₂ H-; It is a perfluoroalkyl group.

PFPE represents -(OC ₄ F ₈ ) _s -(OC ₃ F ₆ ) _b -(OC ₂ F ₄ ) _c -(OCF ₂ ) _d -, a perfluoro(poly)ether group. a, b, c and s respectively represent the number of repeating units of the three perfluoropolyethers constituting the main skeleton of the polymer, which are independent of each other and are integers of 0 or more and 200 or less, and at least the sum of a, b, c and s It is 1, preferably 1 to 100. The order of existence of each repeating unit with the following a, b, c or s and enclosed in parentheses is in any order in the formula. In the repeating units, -(OC ₄ F ₈ )- is -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF _{3 )} CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF ₃ ) ₂ )-, -(OCF( Any of CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₆ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₆ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- is -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )-, and -(OCF ₂ CF(CF ₃ ))-, preferably Is -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- is -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-, preferably -(OCF ₂ CF ₂ )-.

T and R ² are groups bonded to Si.

T represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include -OA, -OCOA, -ON=C(A) ₂ , -N(A) ₂ , -NHA, halogen (in the formula, A represents a substituted or unsubstituted carbon number 1 to 3 alkyl groups) and the like. The hydroxyl group is not particularly limited and may be produced by hydrolysis of a hydrolyzable group.

R ² represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

n is an integer of 1 or more and 3 or less.

X independently represents a 2- to 7-valent organic group. The X group can be understood as a linker connecting the perfluoropolyether portion (PFPE portion) and the decane portion (-SiT _m R ² _3-m ) in the formulae (2a) and (2b). Therefore, as long as the compound represented by the formulae (2a) and (2b) can be stably present, the X group can be any organic group having a valence of 2 to 7. Further, in the valence of the X group, α in the formula is an integer of 1 to 6. For example, when X is a divalent organic group, α is 1, and X is a 7-valent organic group, and α is 6.

In a preferred aspect, X is a 2- to 4-valent organic group and α is 1 to 3, more preferably X is a divalent organic group and α is 1.

The example of the above X is not particularly limited, and examples thereof include a group represented by the following formula: -(R ³¹ ) _p -(X ¹ ) _q -R ³² - wherein R ³¹ represents -(CH ₂ ) _s - Or o-, m- or p-phenyl, preferably -(CH ₂ ) _s -; R ³² represents -(CH ₂ ) _t -, or o-, m- or p-phenylene Preferably, -(CH ₂ ) _t -; X ¹ represents -(X ² ) _r -; each of the X ² systems present is independent, representing -O-, -S-, ortho-, meta- or pair -phenyl, -C(O)O-, -CONR ³⁴ -, -O-CONR ³⁴ -, -NR ³⁴ -, -Si(R ³³ ) ₂ -, -(Si(R ³³ ) ₂ O) _m a group selected from the group consisting of -Si(R ³³ ) ₂ - and -(CH ₂ ) _n -; each of the R ³³ groups present independently represents a phenyl group or a C _1-6 alkyl group, preferably C _{a 1-6} alkyl group, more preferably a methyl group; each of the R ³⁴ groups which are present independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group); Independently, an integer from 1 to 100, preferably an integer from 1 to 20; each of the n-forms present is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably from 1 to 3. An integer; s is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably 1 An integer of up to 3, more preferably 1 or 2; t is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3; r is an integer from 1 to 10, preferably An integer from 1 to 5, more preferably an integer from 1 to 3; p is 0 or 1; q is 0 or 1].

Preferably, the above X is a C _1-20 alkylene group, -R ³¹ -X ³ -R ³² -, or -X ⁴ -R ³² - wherein R ³¹ and R ³² are the same as defined above.

More preferably, the above X is C _1-20 alkyl, -(CH ₂ ) _s -X ³ -(CH ₂ ) _t -, or -X ⁴ -(CH ₂ ) _t - [wherein, s and t are The same as above].

In the above formula, X ³ represents -O-, -S-, -C(O)O-, -CONR ³⁴ -, -O-CONR ³⁴ -, -Si(R ³³ ) ₂ -, -(Si(R ³³ ₂ O) _m -Si(R ³³ ) ₂ -, -O-(CH ₂ ) _u -(Si(R ³³ ) ₂ O) _m -Si(R ³³ ) ₂ -, -CONR ³⁴ -(CH ₂ ) _u -(Si(R ³³ ) ₂ O) _m -Si(R ³³ ) ₂ -, -CONR ³⁴ -(CH ₂ ) _v -N(R ³⁴ )-, or -CONR ³⁴ -(o-, m- or p-Phenyl)-Si(R ³³ ) ₂ -[wherein, R ³³ , R ³⁴ , m and v are the same as above, and u is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably Is an integer from 2 to 3.].

X ^{3 is} preferably -O-.

In the above formula, X ⁴ represents -S-, -C(O)O-, -CONR ³⁴ -, -CONR ³⁴ -(CH ₂ ) _u -(Si(R ³³ ) ₂ O) _m -Si(R ³³ ) ₂ -, -CONR ³⁴ -(CH ₂ ) _v -N(R ³⁴ )-, or -CONR ³⁴ -(o-, m- or p-phenylene)-Si(R ³³ ) ₂ -.

More preferably, the above X is a C _1-20 alkyl group, -(CH ₂ ) _s -X ³ -(CH ₂ ) _t -, or -X ⁴ -(CH ₂ ) _t - [wherein each symbol is as described above the same].

More preferably, the above X is a C _1-20 alkyl group, -(CH ₂ ) _s -O-(CH ₂ ) _t -, -(CH ₂ ) _s -(Si(R ³³ ) ₂ O) _m -Si (R ³³ ) ₂ -(CH ₂ ) _t -, -(CH ₂ ) _s -O-(CH ₂ ) _u -(Si(R ³³ ) ₂ O) _m -Si(R ³³ ) ₂ -(CH ₂ ) _t -, or -(CH ₂ ) _s -O-(CH ₂ ) _t -Si(R ³³ ) ₂ -(CH ₂ ) _u -Si(R ³³ ) ₂ -(C _v H _2v )-[wherein Each symbol is the same as above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.

In the above formula, -(C _v H _2v )- may be a straight or branched chain such as -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH(CH ₃ ) CH ₂ -.

The above X group may be substituted by one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group (preferably a C _1-3 perfluoroalkyl group).

Specific examples of the above X include, for example, -CH ₂ O(CH ₂ ) ₂ -, -CH ₂ O(CH ₂ ) ₃ -, -CH ₂ O(CH ₂ ) ₆ -, -CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -, -CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH _{3 2} (CH ₂ ) ₂ -, -CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -, -CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₃ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -, -CH ₂ O(CH ₂ ) ₃ Si(CH _{3 2} O(Si(CH ₃ ) ₂ O) ₁₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -, -CH ₂ O(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O ₂₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₆ -, -CONH- (CH ₂ ) ₃ -, -CON(CH ₃ )-(CH ₂ ) ₃ -, -CON(Ph)-(CH ₂ ) ₃ - (wherein, Ph represents a phenyl group), -CONH-(CH ₂ ) ₆ -, -CON(CH ₃ )-(CH ₂ ) ₆ -, -CON(Ph)-(CH ₂ ) ₆ - (wherein, Ph represents a phenyl group), -CONH-(CH ₂ ) ₂ NH(CH ₂ ) ₃ -, -CONH-(CH ₂ ) ₆ NH(CH ₂ ) ₃ -, -CH ₂ O-CONH-(CH ₂ ) ₃ -, -CH ₂ O-CONH-(CH ₂ ) ₆ -, - S-(CH ₂ ) ₃ -, -(CH ₂ ) ₂ S(CH ₂ ) ₃ -, -CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ - , -CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ OSi(CH ₃ ) ₂ OSi(CH ₃ ) ₂ (CH ₂ ) ₂ -, -CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O( Si(CH ₃ ) ₂ O) ₂ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -, -CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₃ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -, -CONH-(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₁₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ -, -CONH -(CH ₂ ) ₃ Si(CH ₃ ) ₂ O(Si(CH ₃ ) ₂ O) ₂₀ Si(CH ₃ ) ₂ (CH ₂ ) ₂ - -C(O)O-(CH ₂ ) ₃ -, - C(O)O-(CH ₂ ) ₆ -, -CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -, -CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -CH(CH ₃ )-, -CH ₂ -O-(CH _{2 3} -Si(CH ₃ ) ₂ -(CH ₂ ) ₂ -Si(CH ₃ ) ₂ -(CH ₂ ) ₃ -, -CH ₂ -O-(CH ₂ ) ₃ -Si(CH ₃ ) ₂ -( CH ₂ ) ₂ -Si(CH ₃ ) ₂ -CH(CH ₃ )-CH ₂ -,

Further, examples of other X-based examples include the following:

Wherein D is a group selected from the group consisting of -CH ₂ O(CH ₂ ) ₂ -, -CH ₂ O(CH ₂ ) ₃ -, -CF ₂ O(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -CONH-(CH ₂ ) ₃ -, -CON(CH ₃ )-(CH ₂ ) ₃ -, -CON(Ph) -(CH ₂ ) ₃ - (wherein, Ph represents a phenyl group), and E is -(CH ₂ ) _n - (n is an integer from 2 to 6); D is bonded to the PFPE of the molecular backbone of the formulae (2a) and (2b), and the E is bonded to the Si atom].

Furthermore, examples of other X-based examples include the following:

[wherein, each of the X groups and T is a group bonded to the PFPE of the molecular main chain of the formulae (2a) and (2b): -CH ₂ O(CH ₂ ) ₂ -, - CH ₂ O(CH ₂ ) ₃ -, -CF ₂ O(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -CONH-(CH ₂ ) ₃ -, -CON(CH ₃ )-(CH ₂ ) ₃ -, -CON(Ph)-(CH ₂ ) ₃ - (wherein, Ph represents a phenyl group), or And at least one other T is -(CH ₂ ) _n - (n is an integer of 2 to 6) which is bonded to the Si atom of the molecular chain of the formulae (2a) and (2b), and the remaining T system Separately methyl or phenyl].

Preferred compounds of the formulae (2a) and (2b) are compounds represented by the following formulas (2a') and (2b').

In the above formula, Rf ² , T, R ² , n, s, a, b and c are synonymous with the correlation between the above formulas (2a) and (2b).

d and f are 0 or 1.

h and j are 1 or 2.

i and k are integers of 2 or more and 20 or less.

Z represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group or a pentafluoroethyl group, and still more preferably a trifluoromethyl group. base. Representative Z is a fluorine atom and d and f are 1.

Further, another example of the fluorine-containing decane compound having a hydrolyzable group bonded to Si and a perfluoropolyether group may be a compound represented by the following formula (3) (may be one type or a mixture of two or more types) ).

Rf ³ [-L ³ _p -XR ³¹ -Si(OR ³² ) ₃ ] _q ‧‧‧(3)

In the formula, Rf ³ represents a perfluoropolyether group, preferably a perfluoropolyether group having 1 to 300 carbon atoms: but all or a part of the fluorine atom bonded to the terminal carbon atom may be a hydrogen atom.

p represents 0 or 1.

q means 1 or 2.

R ³¹ represents an alkylene group, preferably an alkylene group having 1 to 3 carbon atoms.

The -OR ³² is bonded to the alkoxy group of Si, and R ³² represents an alkyl group, preferably an alkyl group having 1 to 3 carbon atoms.

L ³ represents -CO-.

X represents a group selected from the group consisting of -O-, -NR ³³ -, -S-, -SO ₂ -, -SO ₂ NR ³³ - and -NR ³³ CO-, preferably -O-. R ³³ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.

Further, the fluorine-containing decane compound used in the present invention may not have a perfluoropolyether group. Other examples of the fluorine-containing decane compound having a group which is bonded to Si and which is hydrolyzable include a compound represented by the following formula (4) (one or a mixture of two or more).

(Rf ⁴ -L ⁴ ) _r SiT _n R ⁴ _4-nr ‧‧‧(4)

In the formula, (Rf ^{4 -} L ⁴ )-, T and R ⁴ are all groups bonded to Si.

Rf ⁴ represents a linear, branched, cyclic fluorine-containing alkyl group having 1 to 20 carbon atoms or a fluorine-containing aromatic group having 6 to 14 carbon atoms.

L ⁴ represents a divalent linking group having a carbon number of 10 or less. The divalent linking group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and the alkylene group may be linear, branched or substituted (for example, a halogen atom, a hydroxyl group, a thiol group, or a carboxyl group). , epoxy, alkyl, aryl, etc. substituted or unsubstituted, and may have a linking group (such as ether, ester, decylamine) inside.

T represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include -OA, -OCOA, -ON=C(A) ₂ , -N(A) ₂ , -NHA, halogen (in the formula, A represents a substituted or unsubstituted carbon number The alkyl group of 1 to 3) is preferably -OA(alkoxy). Examples of A include unsubstituted alkyl groups such as methyl, ethyl, propyl and isopropyl; and substituted alkyl groups such as chloromethyl. Among these, an alkyl group, especially an unsubstituted alkyl group, is preferred, and a methyl group is more preferred. The hydroxyl group is not particularly limited as long as it is hydrolyzed by a hydrolyzable group.

R ⁴ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

n and r are integers of 1 or more and 3 or less, and the sum of n and r is 4 or less.

Further, r may be 0, but in terms of functions such as hydrophobicity, oleophobicity, stain resistance, surface smoothness (or lubricity), r is preferably an integer of 1 or more and 3 or less.

Other examples of the fluorine-containing decane compound having a hydrolyzable group and a perfluoropolyether group bonded to Si include compounds represented by the following formula (5a) or (5b) (one or two or more) a mixture).

Rf ⁵ -PFPE-X-(SiQ _k Y _3-k ) _α ‧‧‧(5a)

(Y _3-k Q _k Si) _α -X-PFPE-X-(SiQ _k Y _3-k ) _α ‧‧‧(5b)

In the formula, Rf ⁵ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, preferably a carbon number 1 which may be substituted by one or more fluorine atoms. 3 alkyl. The above alkyl group which may be substituted by one or more fluorine atoms is preferably a fluoroalkyl group or a perfluoroalkyl group in which all carbon atoms are substituted by fluorine except for a terminal carbon atom of CF ₂ H-. Preferably, it is a perfluoroalkyl group.

PFPE independently represents -(OC ₄ F ₈ ) _a -(OC ₃ F ₆ ) _b -(OC ₂ F ₄ ) _c -(OCF ₂ ) _d -, where a, b, c and d are independent An integer of 0 or more and 200 or less, and a sum of a, b, c and d is at least 1, preferably 1 to 100. The order of existence of each repeating unit with the following a, b, c or d and enclosed in parentheses is in any order in the formula. In the repeating units, -(OC ₄ F ₈ )- is -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF _{3 )} CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF ₃ ) ₂ )-, -(OCF( Any of CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₆ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₆ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- may be any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )-, and -(OCF ₂ CF(CF ₃ ))- Good for - (OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- is -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-, preferably -(OCF ₂ CF ₂ )-.

The X and α systems are the same as those described in the above formulas (2a) and (2b).

In a preferred embodiment, X is a 2- to 4-valent organic group and α is 1 to 3, more preferably X is a divalent organic group and α is 1.

Each of the Y lines present is independent of each other and represents a hydrogen atom, a hydroxyl group, a hydrolyzable group or a hydrocarbon group. The hydrolyzable group is the same as that described in the above R ¹² . The hydroxyl group is not particularly limited and may be those produced by hydrolysis of a hydrolyzable group.

The above Y is preferably a hydroxyl group, -OR (wherein R represents a C _1-12 alkyl group, preferably a C _1-6 alkyl group, more preferably a C _1-3 alkyl group), a C _1-12 alkyl group, C _2-12 alkenyl, C _2-12 alkynyl or phenyl, more preferably -OCH ₃ , -OCH ₂ CH ₃ , -OCH(CH ₃ ) ₂ . These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group and a C _2-6 alkynyl group.

Each of the Q systems appearing above independently represents -Z-SiR ¹³ _p R ¹⁴ _3-p .

Each of the Z systems appearing above independently represents a divalent organic group. Preferably, Z is C _1-6 alkyl, -(CH ₂ ) _s' -O-(CH ₂ ) _t' - (wherein s' is an integer from 1 to 6, and t' is from 1 to 6 Integer) or -phenyl-(CH ₂ ) _u' - (wherein u' is an integer from 0 to 6), more preferably C _1-3 alkyl. These groups may be substituted, for example, by one or more substituents selected from a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group and a C _2-6 alkynyl group.

Each of the R ¹³ groups which appear above independently represents a hydroxyl group or a hydrolyzable group. R ^{13 is} preferably -OR (wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

Each of the R ¹⁴ groups appearing above independently represents an alkyl group or Q' having a carbon number of 1 to 22.

The above Q' is synonymous with Q,

In each of Q and Q', the above p is independently an integer of 0 to 3, and the sum of p is 1 or more. In each of Q or Q', when the above p is 0, the Si in Q or Q' does not have a hydroxyl group or a hydrolyzable group. In the case where a hydroxyl group and a hydrolyzable group are not present, the adhesion to the substrate is lowered and the durability is lowered. Therefore, at least one of Si or Q' must have at least one hydroxyl group or hydrolyzable group. In other words, the sum of the above p is at least 1 or more.

In the Q-Q' _0-5 chain of the Si atom bonded to the end of the main chain of the molecule having a perfluoropolyether group, the terminal Q' (Q in the absence of Q') is preferably 2 The above is, for example, 2 or 3, more preferably 3. Here, the terminus refers not only to the end of the main chain of the -Q- _Q'0-5 chain but also to the end of the branched chain. That is, when the -Q-Q' _0-5 chain forms a branched chain, there are multiple ends.

In the above Q, when at least one of R ¹⁴ is Q', two or more Si atoms which are linearly linked by the Z group are present in Q. The number of atoms of Si linearly connected through the Z group is at most five. Further, "Si atoms which are linearly connected by a Z group in Q" are equal to the number of repetitions of -Z-Si- which are linearly linked in Q.

The above k is an integer selected from 1 to 3, preferably 2 or more. More preferably 3. By making k 3, the bonding to the substrate can be made stronger, resulting in high friction durability.

The decane compound used can function according to the function of the decane film. The body is suitably selected for its hydrophobicity, oleophobicity, stain resistance, surface smoothness (or lubricity), and the like.

For specific decane compounds, for example, Daikin Industries Co., Ltd. can be used. OPTOOL (registered trademark) series (such as OPTOOL DSX-E, OPTOOL AES, OFTOOL UD500, etc.), or KY-130, KY-178, KY-185 of Shin-Etsu Chemical Co., Ltd., or DC2634 of Dow Corning Corporation .

The formation of the precursor film can be applied to the following embodiments: The decane compound having a group which is bonded to Si and hydrolyzable is coated on the surface of the substrate either alone or as a film-forming composition containing the compound.

The above film-forming composition can be regarded as a fluorine-containing polyether compound of a fluorine-containing oil. Preferably, the substance may contain a perfluoropolyether compound (hereinafter referred to as "fluorine-containing oil"). The fluorine-containing oil contributes to an increase in the surface smoothness of the decane-based film.

In the film forming composition, the above decane-based compound is combined The fluorine-containing oil is, for example, contained in an amount of from 0 to 80 parts by mass, preferably from 0 to 40 parts by mass, based on 100 parts by mass.

The fluorine-containing oil may, for example, be a compound represented by the following formula (6) (perfluoropolyether compound).

R ²¹ -(OC ₄ F ₈ ) _s' -(OC ₃ F ₆ ) _a' -(OC ₂ F ₄ ) _b' -(OCF ₂ ) _c' -R ²² ‧‧‧(6)

In the formula, R ²¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, preferably a carbon number of 1 to 3 which may be substituted by one or more fluorine atoms. alkyl. The above alkyl group which may be substituted by one or more fluorine atoms is preferably a fluoroalkyl group or a perfluoroalkyl group in which all carbon atoms are substituted by fluorine except for a terminal carbon atom of CF ₂ H-. It is a perfluoroalkyl group.

R ²² represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, preferably a carbon number which may be substituted by one or more fluorine atoms. Alkyl groups of 1 to 3. The above alkyl group which may be substituted by one or more fluorine atoms is preferably a fluoroalkyl group or a perfluoroalkyl group in which all carbon atoms are substituted by fluorine except for a terminal carbon atom of CF ₂ H-. It is a perfluoroalkyl group.

a', b', c', and s' respectively represent the number of three repeating units of the perfluoropolyether constituting the main skeleton of the polymer, and are independent of each other and are integers of 0 or more and 300 or less, a', b', and c. The sum of 'and s' is at least 1, preferably from 1 to 100. The order of existence of each repeating unit with the following a', b', c' or s' and enclosed in parentheses is in any order in the formula. In the repeating units, -(OC ₄ F ₈ )- is -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF _{3 )} CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF ₃ ) ₂ )-, -(OCF( Any of CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₆ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₆ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- is -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )-, and -(OCF ₂ CF(CF ₃ ))-, preferably Is -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- is -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-, preferably -(OCF ₂ CF ₂ )-.

Examples of the perfluoropolyether compound represented by the above formula (6) include a compound represented by any one of the following formula (6a) or (6b) (may be one type or a mixture of two or more types).

R ²¹ -(OCF ₂ CF ₂ CF ₂ ) _a" -R ²² ‧‧‧(6a), R ²¹ -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _s" -(OCF ₂ CF ₂ CF ₂ ) _a" - (OCF ₂ CF ₂ ) _b" -(OCF ₂ ) _c" -R ²² ‧‧‧(6b)

In the equation, R ²¹ and R ²² are as defined above; in the formula (6a), a" is an integer of 1 or more and 100 or less; in the formula (6b), a" and s" are independently 0 or more and 30. The following integers, b" and c", are each independently an integer of 1 or more and 300 or less. In the equation, the following a", b", c" or s" is attached and the existence of each repeating unit enclosed in parentheses The order is in any order in the formula.

The compound represented by the formula (6a) and the compound represented by the formula (6b) may be used singly or in combination. It is preferred to use a compound represented by the formula (6b) to obtain a higher surface smoothness than the compound represented by the formula (6a). When such a combination is used, it is preferred to use a compound represented by the formula (6a) and a compound of the formula (6b) at a mass ratio of 1:1 to 1:30. According to this mass ratio, a decane-based film excellent in the balance between surface smoothness and friction durability can be obtained.

Further, from another viewpoint, the fluorine-containing oil may be a compound represented by the formula: Rf ¹ -F (wherein Rf ¹ is as defined above). The point of obtaining high affinity with the compound represented by any one of the above formulas (1a), (1b), (2a), (2b), (3), and (4) is based on Rf. ^The compound represented by ^1- F is preferred.

The fluorine-containing oil may have an average molecular weight of from 1,000 to 30,000. Thereby, high surface smoothness can be obtained. In the case of the compound of the formula (6a), it is preferably a compound of the formula (6b), preferably having an average molecular weight of from 2,000 to 6,000. In the case, it is preferred to have an average molecular weight of 8,000 to 30,000. In the range of these average molecular weights, high surface smoothness can be obtained.

Moreover, the film formation composition may further contain a polyfluorene oxide compound (hereinafter referred to as "polyoxyxane oil") which can be regarded as a polyoxygenated oil. Polyoxygenated oil can improve the surface smoothness of the decane film.

The film-forming composition may contain, for example, from 0 to 300 parts by mass, preferably from 50 to 200 parts by mass, per 100 parts by mass of the total of the decane compound.

The polyoxyxene oil can be, for example, a linear or cyclic polyoxyxene oil bonded to 2,000 or less using a decane. The linear polyoxygenated oil may be a so-called pure polyoxygenated oil or a modified polyoxygenated oil. The pure polyoxygenated oil may, for example, be dimethylpolyphthalic acid oil, methylphenylpolyphosphonium oil or methylhydrogenpolyoxygenated oil. The modified polyoxyxene oil can be exemplified by the modification of pure polyoxygenated oil via alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amine, epoxy, carboxyl, alcohol, etc. . Examples of the cyclic polysiloxane oil include cyclic dimethyl siloxane oil and the like.

The method of coating the precursor film is not particularly limited. For example, a wet coating method and a dry coating method can be used, but in terms of high productivity, a wet coating method is preferred.

Examples of the wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like.

Examples of the dry coating method include vacuum evaporation, sputtering, CVD (Chemical Vapor Deposition), and the like. Specific examples of the vacuum vapor deposition method include resistance heating, electron beam, high frequency heating, ion beam, and the like. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and the like.

Furthermore, it can also be covered by a normal piezoelectric slurry method.

When the wet coating method is used, the decane compound (which may be used alone or in the form of a composition containing the compound) is first diluted with a solvent and applied to the surface of the substrate. From the standpoint of the stability of the decane compound or composition and the volatility of the solvent. Preferably, the following solvent is used: a perfluoroaliphatic hydrocarbon having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane, and perfluoro-1,3-dimethylcyclohexane); Fluorinated aromatic hydrocarbons (eg bis(trifluoromethyl)benzene); polyfluoroaliphatic hydrocarbons; hydrofluoroethers (HFE) (eg perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ), perfluorobutyl methyl) Ether (C ₄ F ₉ OCH ₃ ), perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ), perfluorohexyl methyl ether (C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ ), etc. The alkyl perfluoroalkyl ether (perfluoroalkyl group and alkyl group may be linear or branched) and the like. These solvents may be used singly or as a mixture of two or more kinds. Among them, preferred are hydrofluoroethers, particularly preferably perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and/or perfluorobutyl ethyl ether (C ₄ F ₉ OC ₂ H ₅ ).

The formation of the precursor film can be carried out in such a manner that the decane compound is present together with the catalyst for hydrolysis and dehydration condensation in the precursor film. Conveniently, in the wet coating method, a decane compound (which may be in the form of a composition alone or in a form containing the compound) may be diluted with a solvent, and a catalyst may be added to the diluent of the decane compound before being applied to the surface of the substrate. . In the dry coating method, the catalyst-added decane compound may be directly subjected to vacuum evaporation treatment, or may be vacuum-deposited by impregnating a porous metal body such as iron or copper with a catalyst-added decane compound. deal with.

Any suitable acid or base can be used as the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid or the like can be used. Further, as the base catalyst, for example, ammonia, an organic amine or the like can be used.

After the precursor film is formed on the surface of the substrate in the above manner, the substrate on which the precursor film is formed is irradiated with microwaves.

The frequency of the microwave to be irradiated by the present invention is not particularly limited, but is preferably 300 MHz to 300 GHz. For example, the center frequency specified by the ITU (International Telecommunication Union) is 433.92 MHz, 915 MHz, 2.45 GHz, 5.8 GHz, 24.125 GHz, and 61.25 GHz. For microwaves of 122.5 GHz or 245 GHz, a representative microwave can be used with a center frequency of 2.45 GHz. By using this frequency, the base material forming the precursor film and the water molecules acting on the hydrolyzable group can be efficiently heated to promote the formation of the decane film.

The output of the microwave irradiated by the present invention is not particularly limited, but is preferably 100 W to 20 kW, more preferably 5 to 15 kW, and particularly preferably 10 kW. By making the output 100 W or more, the precursor film is efficiently heated and the formation of a decane film is promoted. Moreover, by making the output 20 kW or less, damage to the substrate can be suppressed.

The irradiation time of the irradiated microwave of the present invention may be changed depending on the microwave output, the composition of the precursor film, the presence or absence of moisture (as will be described later), and the like, and is generally 0.1 to 10 minutes, preferably 1 to 3 minutes. The method of the present invention is industrially advantageous in that a decane-based film can be formed in such a short period of time.

Further, before the precursor film is irradiated with microwaves or during irradiation, water may be supplied to the precursor film. By supplying water to the precursor film, hydrolysis of the hydrolyzable group of the precursor film is promoted, and a decane film having high friction durability can be obtained.

The method of supplying moisture to the precursor film is not particularly limited, and examples thereof include a spray of water and a method of blowing steam or superheated steam.

Further, the system is maintained at, for example, 80 ° C to 250 ° C, preferably 80 ° C to 180 ° C, more preferably 100 ° C to 150 ° C, thereby preventing the substrate and the formed The decane-based film is attached with water droplets, whereby the drying step after the formation of the decane-based film can be omitted.

By the above manner, a precursor film can be formed on the surface of the substrate. A decane film. The decane-based film thus obtained has high friction durability. Further, in addition to high friction durability, the decane-based film can also obtain hydrophobicity, oleophobicity, stain resistance (for example, prevention of adhesion such as fingerprints) and surface smoothness (or lubricity) depending on the decane-based compound to be used. For example, such as fingerprints and the like, it is suitable for use as a functional film.

The invention is not limited by any theory, but is believed to be by the method of the invention The reason for improving the friction durability of the decane-based film is as follows. In the formation of a decane film, film formation can be promoted by heating the precursor film. However, in general heating with dry air as a medium, heat transfer efficiency is not good, or temperature unevenness is likely to occur. On the other hand, in the method of the present invention, the substrate on which the precursor film is formed is directly and uniformly heated by irradiating the microwave, so that the film formation reaction is carried out very efficiently. Further, by supplying water to the precursor film, water acts on the Si and hydrolyzable groups of the precursor film, and hydrolysis rapidly occurs. Then, the substrate on which the precursor film is formed is heated by microwaves, so that dehydration condensation of the decane compounds and the reactive groups (for example, hydroxyl groups) existing on the surface of the substrate are rapidly formed. Reaction (eg dehydration condensation). As a result, the film strength of the decane-based film itself and the adhesion strength between the decane-based film and the surface of the substrate are increased. Therefore, it is considered that a decane-based film having high friction durability can be obtained.

Therefore, the obtained article having a decane-based film is not particularly limited. But it can be an optical member. Examples of the optical member can be exemplified by lenses such as glasses, PDP, LCD, etc., front protection plates, anti-reflection plates, polarizing plates, anti-glare plates, and touch panel sheets of mobile phones, personal digital assistants (PDAs), and the like. Blue light (Blu-ray) (registered trademark) Optical disc, DVD, CD-R, MO, etc.

The thickness of the decane-based film is not particularly limited. In the case of an optical member, the thickness of the decane-based film is from 1 to 30 nm, preferably from 1 to 15 nm, in terms of optical properties, friction durability, and stain resistance.

The article having a decane-based film obtained by the production method of the present invention has been described above, but the present invention is not limited to the above-exemplified ones.

(Example)

Hereinafter, the method for producing the article of the present invention will be further specifically described by way of examples, but the present invention is not limited to the examples.

(Example 1) . Modulation of film forming composition

0.1 parts by weight of a compound represented by the following formula (molecular weight: about 4,000) as a main component, and 90 parts by weight of hydrofluoroether (Novec HFE 7200 (perfluorobutyl ether) manufactured by 3M Company) were mixed to prepare a composition for forming a film. Things.

(wherein, the average value of n is 20, and the average value of m is 3).

. Substrate and pretreatment

As the substrate, chemically strengthened glass ("GORILLA" glass, thickness: 0.55 mm, plane size: 55 mm × 100 mm) manufactured by Corning Corporation was used. The base material (chemically strengthened glass) was cleaned and activated by plasma treatment using an atmospheric piezoelectric slurry generator (Dyne-A-Mite IT, a plasma processing apparatus manufactured by Enercon Co., Ltd.).

. Formation of precursor film

The film formation composition prepared above was uniformly sprayed onto the surface of the substrate by using a spray coating device (manufactured by Toho Chemical Co., Ltd.) equipped with a two-fluid nozzle. The amount of coating for the film-forming composition was 0.2 ml for one substrate (coating liquid flow rate: 3.0 ml/min). Thereby, a precursor film is formed on the surface of the substrate.

. Post processing

Next, the substrate on which the precursor film was formed was placed in a microwave generator (manufactured by Micro Denshi Co., Ltd.). Next, the microwave was irradiated at a frequency of 2.45 GHz and output at 10 Kw for 1 minute, after which the substrate was taken out by the apparatus. In this manner, a fluorine-containing decane-based film derived from the precursor film is formed on the surface of the substrate.

(Example 2)

In the same manner as in Example 1, except that water vapor (flow rate: 40 liters/hour) and hot air (120 ° C) were introduced during the post-treatment, a precursor film was formed on the surface of the substrate in the same manner as in Example 1. A fluorine-containing decane-based film.

(Example 3)

A fluorine-containing decane-based film derived from a precursor film was formed on the surface of the substrate in the same manner as in Example 1 except that the compound represented by the following formula was used as the fluorine-containing decane compound used for the composition for forming a film. But the average value of n is 20.

CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si[CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ] ₃

(Example 4)

In the same manner as in Example 3, a fluorine-derived film derived from the precursor film was formed on the surface of the substrate, except that the microwave was irradiated while introducing steam (flow rate: 40 liter/hour) and hot air (120 ° C). A decane film.

(Example 5)

A fluorine-containing decane-based film derived from a precursor film was formed on the surface of the substrate in the same manner as in Example 1 except that the compound represented by the following formula was used as the fluorine-containing decane compound used for the composition for forming a film. However, the average value of n is 15, and the average value of m is 16.

CF ₃ O(CF ₂ CF ₂ O) _n (CF ₂ O) _m CF ₂ CH ₂ OCH ₂ CH ₂ CH ₂ Si[CH ₂ CH ₂ CH ₂ Si(OCH ₃ ) ₃ ] ₃

(Example 6)

In the same manner as in Example 5, a fluorine-derived film derived from the precursor film was formed on the surface of the substrate, except that the microwave was irradiated with water vapor (flow rate: 40 liter/hour) and hot air (120 ° C). A decane film.

(Comparative Example 1)

The source was formed on the surface of the substrate in the same manner as in Example 1 except that the post-treatment was usually dried in a conventional manner, that is, the substrate on which the precursor film was formed was heated at 120 ° C for 1 hour in an electric furnace. A fluorine-containing decane film derived from a precursor film.

(Comparative Example 2)

The source was formed on the surface of the substrate in the same manner as in Example 3 except that the post-treatment was usually dried in a conventional manner, that is, the substrate on which the precursor film was formed was heated at 120 ° C for 1 hour in an electric furnace. A fluorine-containing decane film derived from a precursor film.

(Comparative Example 3)

The formation of the substrate surface was carried out in the same manner as in Example 5 except that the post-treatment was usually dried in a conventional manner, that is, the substrate on which the precursor film was formed was heated at 120 ° C for 1 hour in an electric furnace. A fluorine-containing decane film of the precursor film.

The processing conditions after the examples and comparative examples were summarized in Table 1 below.

(assessment)

The static contact angle of water was measured for the fluorine-containing decane-based film formed on the surface of the substrate in the above Examples and Comparative Examples. The static contact angle of water was carried out using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) and using 1 μL of water.

First, as an initial evaluation, after the formation of the fluorine-containing decane-based film, the static contact angle of water (the number of times of rubbing) was measured without any contact on the surface of the film.

Thereafter, a steel wool friction durability evaluation was performed to evaluate the friction durability. Specifically, the substrate on which the fluorine-containing decane-based film is formed is horizontally disposed, and the steel wool (count # 0000, size 10 mm × 10 mm × 5 mm) is brought into contact with the fluorine-containing decane-based film to expose the upper surface, and A load of 1000 gf was applied thereto, and then the steel wool was moved back and forth at a speed of 140 mm/sec under application of a load. The static contact angle (degrees) of water was measured every 2000 times. The evaluation is stopped when the measured value of the contact angle is less than 100 degrees. The results are shown in Table 2. Further, the results of Examples 1 and 2 and Comparative Example 1 using the same fluorine-containing decane compound are shown in Fig. 1, and the results of Examples 3 and 4 and Comparative Example 2 are shown in Fig. 2, and Example 5, The results of 6 and Comparative Example 3 are shown in Fig. 3.

As can be seen from Table 2 and Figs. 1 to 3, it was confirmed that the post-treatment by using microwaves can greatly enhance the fluorine-containing decane-based film as compared with the case of post-treatment by drying in a dry air at 150 °C. Friction durability.

It is considered that the substrate is heated by drying with dry air as a medium, and the microwave itself directly heats the substrate itself, so that the reaction can be efficiently carried out.

Further, in Examples 2, 4 and 6 in which microwaves and water vapor were combined, the friction durability of the fluorine-containing decane-based film was further improved as compared with Examples 1, 3 and 5 in which no water vapor was used.

This is considered to be that the water is allowed to act on the hydrolyzable group of the precursor film by using water vapor, and the hydrolysis is rapidly carried out to form a solid fluorine-containing decane-based film.

(industrial availability)

The present invention is suitable for use in forming a decane-based film on the surface of a wide variety of substrates, particularly on the surface of optical members requiring penetration.

The illustrations in this case are graphs showing the friction durability data of the examples and comparative examples of the present case, which are not sufficient to represent the technical features of the present case, so there is no representative representative figure in this case.

Claims (22)

A method for producing an article comprising a substrate and a decane-based film coated on the surface of the substrate, comprising: (a) forming a body film before the formation of a decane compound on the surface of the substrate, the decane compound having a bond to Si and a substrate to be hydrolyzed; (b) a substrate on which the precursor film is formed is irradiated with microwaves, and a decane film derived from the precursor film is formed on the surface of the substrate. The manufacturing method according to claim 1, wherein the (b) includes supplying moisture to the front film while irradiating the microwave. The manufacturing method according to claim 1, wherein the water is supplied as water vapor. The manufacturing method according to any one of claims 1 to 3, wherein the frequency of the microwave is selected from the group consisting of 300 MHz to 300 GHz. The manufacturing method according to any one of claims 1 to 4, wherein the microwave output is 100 W to 20 kW. The production method according to any one of claims 1 to 5, wherein the decane compound is a fluorine-containing decane compound. The production method according to any one of claims 1 to 6, wherein the decane compound further has a perfluoropolyether group. The production method according to claim 6 or 7, wherein the fluorine-containing decane compound contains at least one compound represented by any one of the following formulas (1a) and (1b). In the formula, Rf ¹ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, and a, b, c and s each independently represent an integer of 0 or more and 200 or less, a. The sum of b, c and s is at least 1, and the order of existence of each repeating unit enclosed by a, b, c or s and enclosed in parentheses is in any order in the formula, d and f are 0 or 1, e and g is an integer of 0 or more and 2 or less, m and l are integers of 1 or more and 10 or less, X represents a hydrogen atom or a halogen atom, Y represents a hydrogen atom or a lower alkyl group, and Z represents a fluorine atom or a lower fluoroalkyl group, T A hydroxyl group or a hydrolyzable group, R ¹ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 or more and 3 or less. The production method according to claim 8, wherein Rf ¹ is a perfluoroalkyl group having 1 to 16 carbon atoms. The production method according to claim 6 or 7, wherein the fluorine-containing decane compound contains at least one compound represented by any one of the following formulas (2a) and (2b), Rf ² -PFPE -X-(SiT _n R ² _3-n ) _α ‧‧‧(2a) (R ² _3-n T _n Si) _α -X-PFPE-X-(SiT _n R ² _3-n ) _α ‧‧‧ (2b) In the equation, Rf ² represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, and PFPE represents -(OC ₄ F ₈ ) _s -(OC ₃ F ₆ ) _b -(OC ₂ F ₄ ) _c -(OCF ₂ ) _d -, a, b, c and s each independently represent an integer of 0 or more and 200 or less, and the sum of a, b, c and s is at least 1, attached The order of existence of each repeating unit in a, b, c or s and enclosed in parentheses is in any order in the formula, X independently represents a 2- to 7-valent organic group, and T represents a hydroxyl group or a hydrolyzable group, R ² represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and n is an integer of 1 or more and 3 or less, and α is independently an integer of 1 to 6. The production method according to claim 10, wherein Rf ² is a perfluoroalkyl group having 1 to 16 carbon atoms. The manufacturing method according to claim 10, wherein X is a divalent organic group and α is 1. The production method according to claim 6 or 7, wherein the fluorine-containing decane compound contains at least one compound represented by the following formula (3), Rf ³ [-L ³ _p -XR ³¹ -Si (OR ³² ) ₃ ] _q ‧‧‧(3), wherein Rf ³ represents a perfluoropolyether group; but all or a part of the fluorine atom bonded to the terminal carbon atom may be a hydrogen atom, and p represents 0 or 1, q represents 1 or 2, R ³¹ represents an alkylene group, R ³² represents an alkyl group, L ³ represents -CO-, and X represents -O-, -NR ³³ -, -S-, -SO ₂ -, -SO ₂ NR ³³ - and -NR ³³ CO- are selected as a group selected, and R ³³ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms. The production method according to claim 6 or 7, wherein the fluorine-containing decane compound contains at least one compound represented by the following formula (4), (Rf ^{4 -} L ⁴ ) _r SiT _n R ⁴ _{In the} formula _4-nr ‧‧‧(4), Rf ⁴ represents a linear, branched or cyclic fluoroalkyl group having 1 to 20 carbon atoms or a fluorine-containing aromatic group having 6 to 14 carbon atoms, L ⁴ represents a divalent linking group having 10 or less carbon atoms, T represents a hydroxyl group or a hydrolyzable group, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and n and r are integers of 1 or more and 3 or less, n and r. The sum is 4 or less. The production method according to claim 6 or 7, wherein the fluorine-containing decane compound contains at least one compound represented by any one of the following formulas (5a) and (5b), Rf ⁵ -PFPE -X-(SiQ _k Y _3-k ) _α ‧‧‧(5a) (Y _3-k Q _k Si) _α -X-PFPE-X-(SiQ _k Y _3-k ) _α ‧‧‧(5b) Wherein Rf ⁵ represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, and PFPE independently represents -(OC ₄ F ₈ ) _a -(OC ₃ F ₆ ) _b - (OC ₂ F ₄ ) _c -(OCF ₂ ) _d - Here, a, b, c, and d are each independently an integer of 0 or more and 200 or less, and the sum of a, b, c, and d is at least 1. The order of existence of each repeating unit enclosed by a, b, c or d and enclosed in parentheses is in any order in the formula, and X independently represents an organic group of 2 to 7 valence, and each Y line appearing is independent The ground represents a hydrogen atom, a hydroxyl group, a hydrolyzable group, or a hydrocarbon group, and each of the Q systems present independently represents -Z-SiR ¹³ _p R ¹⁴ _3-p , and each of the Z systems appearing independently represents a divalent an organic group; each occurrence of R ¹³ Department independently represents a hydroxyl group or a hydrolyzable group, are out Each of R ¹⁴ each independently represent a carbon-based alkyl group of 1 to 22, or the Q ', Q' is synonymous with Q, and Q in each of the Q ', p lines each independently an integer of 0 to 3, the P The sum is 1 or more. In Q, the number of Si which is linearly bonded through the Z-group is at most 5, k is an integer of 1 to 3, and α is independently an integer of 1 to 6, respectively. The production method according to claim 15, wherein Rf ⁵ is a perfluoroalkyl group having 1 to 16 carbon atoms. The production method according to Item 15 or Item 16, wherein X is a divalent organic group and α is 1. An article obtained by the method of manufacturing according to any one of claims 1 to 17. The article of claim 18, wherein the decane-based film is an antifouling coating. The article of claim 18, wherein the material constituting the surface of the substrate has a hydroxyl group. The article according to any one of claims 18 to 20, wherein the material constituting the surface of the substrate is selected from the group consisting of glass, resin, metal, and ceramic. The article of any one of claims 18 to 21, wherein the article is an optical member.