JP6903903B2 - Laminate - Google Patents

Description

The present invention relates to a laminate including a decorative layer.

A technique for improving the design of an article by providing a decorative layer on the surface of the article is known. Further, a technique of not only providing a decorative layer but also providing a surface protective layer and an antireflection layer on the decorative layer is also known.

For example, Patent Document 1 has a film body and a cured resin film having a fine concavo-convex structure formed on the surface of the film body, and the film body has a thermoplastic resin layer and a surface of the thermoplastic resin layer. Described is a laminating film that is a film or sheet having a decorative layer formed on the surface of the decorative layer and a protective layer formed on the surface of the decorative layer. This laminated film has a fine concavo-convex structure having a plurality of convex portions on the surface, and the average distance between the convex portions is 400 nm or less. Therefore, the reflectance on the surface is low and the wavelength dependence of the reflectance is high. Few. Therefore, it is said that the original patterns and colors of the decorative layer and the base material are sufficiently reproduced and the design is high.

In Patent Document 2, when a polyester resin is used as the transparent resin layer on the decorative layer in the film described in Patent Document 1, it is assumed that the hard coat surface of the decorative sheet is finely embossed with exactly the same shape. However, it has been pointed out that there are times when the effect of improving sharpness can be obtained and times when it cannot be obtained.

Further, in Patent Document 2, it is a decorative sheet having a transparent hard coat (A), a transparent polyester resin layer (B), and a decorative layer (C) in this order from the surface layer side.
(1) The transparent hard coat (A) and the transparent polyester resin layer (B) are directly laminated;
(2) The transparent polyester resin layer (B) and the decorative layer (C) are laminated directly or via a transparent adhesive (E);
(3) The transparent hard coat (A) is the outermost layer;
(4) The surface of the transparent hard coat (A) is finely embossed;
(5) The shape of the fine embossing has a plurality of convex portions, the average distance between the convex portions is 100 to 500 nm, and the average height of the convex portions is 80 to 500 nm;
(6) The 60 ° gloss (Ga) on the fine embossed surface of the transparent hard coat (A) and the 60 ° gloss (Gb) on the hard coat laminated surface of the transparent polyester resin layer (B) satisfy the following formula (α). thing;
A decorative sheet featuring the above was proposed.
Gb-Ga ≧ 35 ・ ・ ・ (α)

Further, in Patent Document 3, it is a decorative sheet having a transparent hard coat (A), a transparent resin layer (B), and a decorative layer (C) in this order from the surface layer side.
(1) The transparent hard coat (A) and the transparent resin layer (B) are laminated directly or via the transparent anchor coat (D);
(2) The transparent resin layer (B) and the decorative layer (C) are laminated directly or via a transparent adhesive (E);
(3) The transparent hard coat (A) is the outermost layer;
(4) The surface of the transparent hard coat (A) is finely embossed;
(5) The shape of the fine embossing has a plurality of convex portions, the average distance between the convex portions is 100 to 500 nm, and the height of the convex portions is 80 to 500 nm;
(6) The transparent resin layer (B) is a transparent polyvinyl chloride-based resin layer (B1) or a transparent polyolefin-based resin layer (B2);
(7) The 60 ° gloss (Ga) on the fine embossed surface of the transparent hard coat (A) and the 60 ° gloss (Gb) on the hard coat laminated surface side of the transparent resin layer (B) satisfy the following formula (α). ;
A decorative sheet featuring the above was proposed.
Gb-Ga ≧ 0 ・ ・ ・ (α)

Japanese Unexamined Patent Publication No. 2009-269237 Japanese Unexamined Patent Publication No. 2014-210368 Japanese Unexamined Patent Publication No. 2014-213578

However, with the conventional technique, stains such as fingerprints are easily attached, and it is difficult to maintain high designability.

The present invention has been made in view of the above situation, and provides a laminate including a decorative layer, which is excellent in antifouling property, water repellency and oil repellency, and can maintain high designability for a long period of time. The purpose is.

The present invention is a laminate including a decorative layer and a transparent layer, wherein the transparent layer contains a compound having a perfluoro (poly) ether group.

It is preferable that the transparent layer has a fine uneven pattern.

The perfluoro (poly) ether group is
Formula:-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(In the formula, a, b, c and d are independently integers of 0 or 1 or more, the sum of a, b, c and d is 1 or more, and a, b, c or d The order of existence of each repeating unit attached and enclosed in parentheses is arbitrary in the formula.) It is preferable that the group is represented by ().

The compound contained in the transparent layer comprises a compound obtained by curing a perfluoro (poly) ether group and a compound (F) having a curable moiety, a perfluoro (poly) ether group, and a hydrolyzable group. Compound (G) and
Formula: R ^111- PFPE-R ¹¹³
(In the formula, PFPE is a perfluoro (poly) ether group, R ¹¹¹ and R ¹¹³ are independently F, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, and 1 to 16 carbon atoms. Alkyl fluorinated group, alkoxy group fluorinated with 1 to 16 carbon atoms, -R ^114- X ¹¹¹ (R ¹¹⁴ is a single-bonded or divalent organic group, X ¹¹¹ is -NH ₂ , -OH, -COOH, -CH = CH ₂ , -OCH ₂ CH = CH ₂ , halogen, phosphoric acid, phosphate ester, carboxylic acid ester, thiol, thioether, alkyl ether (which may be substituted with fluorine), aryl, aryl ether or amide)) It is preferable that it is at least one selected from the group consisting of the compound (H) represented by.

The transparent layer is further composed of a resin obtained by curing a curable resin, a resin obtained by curing a curable monomer, and a resin containing a polysiloxane structure formed by using a silicon-containing compound. It preferably contains at least one resin selected from the group.

The laminate further comprises a resin obtained by curing a curable resin, a resin obtained by curing a curable monomer, and a resin containing a polysiloxane structure formed by using a silicon-containing compound. It is also preferable to include a resin layer containing at least one resin selected from the group.

It is also preferable that the laminate further contains an adhesive layer.

The laminate of the present invention is a laminate including a decorative layer, and is excellent in antifouling property, water repellency and oil repellency, and can maintain high designability for a long period of time.

It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is sectional drawing which shows one Embodiment of the laminated body of this invention. It is sectional drawing which shows one Embodiment of the laminated body of this invention.

Hereinafter, the present invention will be specifically described.

The laminate of the present invention includes a decorative layer and a transparent layer.

The material of the decorative layer is not particularly limited, and examples thereof include wood, metal, leather, and thermoplastic resin. Further, the decorative layer may contain a colorant, a pigment and the like.

The pattern of the decorative layer is not particularly limited, and may be the pattern of the material of the decorative layer itself, or may be a pattern, characters, or the like. The above patterns include wood grain, stone grain, cloth grain, sand grain, texture, leather grain, geometric pattern, letters, tiled pattern, brickwork pattern, parquet pattern, patchwork pattern, hairline pattern, solid, pattern pattern, Japanese paper patterns and the like can be mentioned.

The color of the decorative layer is not particularly limited, and may be the color of the material of the decorative layer itself or the color of the colorant. Examples of the above colors include black, white, red, blue, green, yellow and the like, as well as metallic colors, polarized colors, structural colors and the like. Further, the decorative layer may have gloss or luster, or may be matte, and may be, for example, metallic, piano black, carbon, satin, pearl, or the like. ..

The film thickness of the decorative layer may be 0.5 to 30 μm. The film thickness may be the film thickness when the decorative layer is formed by printing or thin film deposition. When the pattern of the material of the decorative layer itself is adopted as the pattern of the decorative layer, the article itself can be used as the decorative layer, so that the film thickness (size) of the decorative layer is not limited at all. ..

The decorative layer can be formed by, for example, printing, coating, plating, vapor deposition, sputtering, ion plating, molding, polishing, etching, or the like.

Examples of the printing method include an offset printing method, a gravure rotary printing method, a screen printing method, a roll coating method, a spray coating method, a flexographic printing method, and the like. As the printing ink used for the above printing, a binder mixed with a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent and the like can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, and polyamides. Resins such as based resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, and resin compositions thereof can be used.

The decorative layer may be formed on one side of the transparent layer, on one side of the resin layer described later, or on one side of the transparent base material layer described later, or may be formed on one side of the transparent base material layer described above. It may be formed on the surface of the component on which the transparent layer or the resin layer is arranged.

In the laminated body of the present invention, it is preferable that the transparent layer has a fine uneven pattern. By having the fine concavo-convex pattern, it is possible to impart antireflection property to the laminated body, and it is possible to obtain an effect that the decoration of the decorative layer can be visually recognized more vividly. Further, it can be expected that the antifouling property, water repellency and oil repellency of the laminated body are further improved.

Further, when the laminated body includes the decorative layer having gloss or luster, or when the laminated body includes the decorative layer having a bright color, when the laminated body is installed near the windshield of the vehicle, the laminated body becomes Light may be reflected or the laminate may be reflected on the windshield, obstructing the driver's view. When the transparent layer has a fine concavo-convex pattern, gloss, luster, brightness and the like can be appropriately lowered, and both designability and safety can be achieved.

The fine concavo-convex pattern may be provided on the surface of the transparent layer as long as it is provided on the surface of the laminated body, or may be provided on both the transparent layer and the resin layer described later. When the fine concavo-convex pattern is provided on the surface of the transparent layer, the fine concavo-convex pattern is provided on the surface of the two surfaces of the transparent layer opposite to the decorative layer.

The term "fine" preferably means nanometer size, and more preferably means that the pattern pitch is equal to or less than the wavelength of visible light. The wavelength of the visible light is about 780 nm. When having such a fine structure, the laminated body can be used as an optical film such as a light reflection antireflection film.

As the fine uneven pattern, a pattern having a pattern pitch of 1000 to 1 nm is preferable, a pattern having a pattern pitch of 780 to 2 nm is more preferable, and a pattern having a pattern pitch of 500 to 2 nm is further preferable. The pattern pitch is the distance between the tops of adjacent convex portions. The pattern pitch can be measured by observation with a scanning electron microscope.

The depth of the fine concavo-convex pattern is not particularly limited, but is preferably nanometer-sized, and more preferably equal to or less than the wavelength of visible light. When having such a fine structure, the laminated body can be used as an optical film such as a light reflection antireflection film.

As the fine uneven pattern, a pattern having a pattern depth of 3000 to 3 nm is preferable, and a pattern having a pattern depth of 1000 to 3 nm is more preferable. The pattern depth is the difference between the height of the top of the convex portion and the height of the bottom of the concave portion. The pattern depth can be measured by observation with a scanning electron microscope.

The shape of the convex portion is not particularly limited, and examples thereof include a substantially conical shape and a substantially pyramidal shape. The fine uneven pattern may be a moth-eye pattern, a pillar pattern, or the like.

The transparent layer is preferably arranged as the outermost layer of the laminated body.

The laminate of the present invention is characterized in that the transparent layer contains a compound having a perfluoro (poly) ether group.

As the above-mentioned perfluoro (poly) ether group (PFPE),
Formula:-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(In the equation, a, b, c and d are independently integers of 0 or 1 or more, the sum of a, b, c and d is at least 1, and a, b, c or d The order of existence of each repeating unit attached and enclosed in parentheses is arbitrary in the formula.) The group represented by) is preferable.

Preferably, a, b, c and d are each independently an integer of 0 or more and 200 or less, for example, an integer of 1 to 200, and more preferably each independently of an integer of 0 or more and 100 or less. Further, the sum of a, b, c and d is preferably 5 or more, and more preferably 10 or more, for example, 10 or more and 100 or less. Of these 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) It may be any of (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-, but it is preferable. -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )-is either-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))- It is good, but preferably − (OCF ₂ CF ₂ CF ₂ ) −. Further, − (OC ₂ F ₄ ) − may be any of − (OCF ₂ CF ₂ ) − and − (OCF (CF ₃ )) −, but − (OCF ₂ CF ₂ ) − is preferable. is there.

In one embodiment, the PFPE is − (OC ₃ F ₆ ) _b − (in the formula, b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less). Preferably, − (OCF ₂ CF ₂ CF ₂ ) _b − (in the formula, b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or − (OCF (CF). ₃ ) CF ₂ ) _b − (In the formula, b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less), and more preferably − (OCF ₂ CF ₂ CF. ₂ ) _b − (in the formula, b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less).

In another embodiment, the PFPE is − (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d − (in the equation, a and b are independent of each other. C and d are independently integers of 0 or more and 30 or less, preferably 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less, and the subscripts a, b, and c. The order of existence of each repeating unit enclosed in parentheses with or d is arbitrary in the formula), preferably − (OCF ₂ CF ₂ CF ₂ CF ₂ ) _a − (OCF ₂ CF ₂ CF). ₂ ) _b − (OCF ₂ CF ₂ ) _c − (OCF ₂ ) _d −. In one embodiment, the PFPE is − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d − (in the formula, c and d are independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably. Is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with a subscript c or d may be arbitrary in the formula).

In yet another embodiment, PFPE is a group represented by- ^{(R 19- R 18} ) _{n "} -. In the formula, R ¹⁹ is OCF ₂ or OC ₂ F ₄ , preferably OC ₂ F. _{In the} equation, R ¹⁸ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or from these groups. It is a combination of two or three groups that are independently selected. Preferably, R ¹⁸ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ and OC ₄ F ₈ or a combination of these. A combination of two or three groups selected independently of the groups. N "is an integer of 2-100. Preferably, such PFPE ^{_{is, - (OC 2 F 4 -R}} 8) f - is a group represented by. In the formula, R ⁸ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of 2 or 3 groups selected independently of these groups. is there. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but is, for example, -OC ₂ F ₄ OC ₃ F _6- , -OC. _{2 F 4 OC 4 F 8 -} , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC _{4 F 8 -, - OC 2} F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 -, - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, - OC 4 F 8 OC ₂ F ₄ OC ₂ F ₄ -etc. The above f is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either straight chain or branched chain, and are preferably straight chain. In this embodiment, the PFPE is preferably − (OC ₂ F ₄ −OC ₃ F ₆ ) _f − or − (OC ₂ F ₄ −OC ₄ F ₈ ) _f −.

As the above compound,
A compound obtained by curing a compound (F) having a perfluoro (poly) ether group and a curable moiety,
Compound (G) having a perfluoro (poly) ether group and a hydrolyzable group, and
Formula: R ^111- PFPE-R ¹¹³
(In the formula, PFPE is a perfluoro (poly) ether group, R ¹¹¹ and R ¹¹³ are independently F, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, and 1 to 16 carbon atoms. Alkyl fluorinated group, alkoxy group fluorinated with 1 to 16 carbon atoms, -R ^114- X ¹¹¹ (R ¹¹⁴ is a single-bonded or divalent organic group, X ¹¹¹ is -NH ₂ , -OH, -COOH, -CH = CH ₂ , -OCH ₂ CH = CH ₂ , halogen, phosphoric acid, phosphate ester, carboxylic acid ester, thiol, thioether, alkyl ether (which may be substituted with fluorine), aryl, aryl ether or amide)) Compound (H) represented by
It is preferable that it is at least one selected from the group consisting of.

As the above-mentioned compound, at least one selected from the group consisting of the compound obtained by curing the compound (F) and the compound (G) is more suitable because a laminated body having excellent durability can be realized. Preferably, a compound obtained by curing the compound (F) having a perfluoro (poly) ether group and a curable moiety is more preferable.

Compound (F) has a perfluoro (poly) ether group and a curable site.

The curable site is not particularly limited, and examples thereof include an allyl group, a cinnamon acid group, a sorbic acid group, an acryloyl group, and a methacryloyl group.

As the compound (F), the component (A): polyisocyanate, which is a trimer of diisocyanate, and the component (B): carbon-carbon, which is a reaction product of a compound having active hydrogen and a perfluoro (poly) ether group. A double bond-containing compound (perfluoro (poly) ether-based compound) is preferable.

As used herein, the term "active hydrogen" means a hydrogen atom that can be donated as a proton to an isocyanate group.

Component (B) can have an active hydrogen-containing group. In the present specification, the "active hydrogen-containing group" refers to a group containing the active hydrogen, for example, -OH groups, -C (= O) H group, -SH group, -SO ₃ H group, - SO ₂ H group, -SOH group, -NH ₂ group, -NH- group, -SiH group and the like.

The component (A) is a polyisocyanate that can be obtained by trimerizing the diisocyanate. Polyisocyanate, which is a trimer of diisocyanate, may exist as a polymer obtained by polymerizing them.

The polyisocyanate, which is a trimer of the diisocyanate of the component (A), may preferably be an isocyanurate-type polyisocyanate. The isocyanurate-type polyisocyanate may exist as a polymer obtained by polymerizing them. That is, the isocyanurate-type polyisocyanate may be a monocyclic compound having only one isocyanurate ring, or may be a polycyclic compound obtained by polymerizing this monocyclic compound. It may be a mixture. As a known isocyanurate-type polyisocyanate, for example, "Sumijour (registered trademark) N3300" manufactured by Sumitomo Bayer Urethane Co., Ltd. can be mentioned.

The diisocyanate used to obtain the polyisocyanate which is a trimeric of the diisocyanate of the component (A) is not particularly limited, but is a diisocyanate in which an isocyanate group is bonded to an aliphatic group, for example, hexamethylene diisocyanate, isophorone diisocyanate, or xylyl. Range isocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate; diisocyanates in which an isocyanate group is bonded to an aromatic group, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, trizine diisocyanate, naphthalene diisocyanate can be mentioned.

The polyisocyanate, which is a trimer of the component (A) diisocyanate, is not particularly limited, and examples thereof include compounds having the following structures.

As described above, these polyisocyanates may exist as a polymer. For example, in the case of an isocyanurate type polyisocyanate of hexamethylene diisocyanate, they may exist as a polymer having the following structure.

The component (B) includes a component (B1): a perfluoro (poly) ether having an active hydrogen, and a component (B2): a monomer having a group having a carbon-carbon double bond and an active hydrogen.

The component (B1) is at least one compound represented by one of the following formulas (B1-i) and (B1-ii).
Rf-PFPE-Z-X (B1-i)
XZ-PFPE-Z-X (B1-ii)

In the above formulas (B1-i) and (B1-ii), Rf has 1 to 16 carbon atoms (for example, linear or branched chain) which may be substituted with one or more fluorine atoms. It is an alkyl group, preferably a linear or branched chain alkyl group having 1 to 3 carbon atoms which may be substituted with one or more fluorine atoms. Rf is preferably linear. Further, the alkyl group which may be substituted with one or more fluorine atoms preferably has a terminal carbon atom of CF ₂ H− and all other carbon atoms are wholly substituted with a fluorine atom. It is a fluoroalkyl group or a perfluoroalkyl group, more preferably a perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ .

In the above formulas (B1-i) and (B1-ii), PFPE is the above-mentioned perfluoro (poly) ether group, and the formula:-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- ( OC ₂ F ₄ ) A group represented by _c − (OCF ₂ ) _{d −.}

In the above formulas (B1-i) and (B1-ii), Z is an independently divalent organic group. Z is preferably ^{R 1.} R ¹ is independently expressed by the following equation:
_{^{- (Y) f - (CR}} 3 2) j -
It is a group represented by.

As used herein, the term "divalent organic group" means a carbon-containing divalent group. The divalent organic group is not particularly limited, and examples thereof include a divalent group obtained by desorbing one hydrogen atom from a hydrocarbon group.

In the present specification, the hydrocarbon group means a group containing carbon and hydrogen. The hydrocarbon group is not particularly limited, but may be substituted with one or more substituents, such as a hydrocarbon group having 1 to 20 carbon atoms, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon. Examples include hydrocarbon groups. The aliphatic hydrocarbon group may be linear, branched, cyclic, or saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. The hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or in the molecular chain.

In the present specification, the substituent of the hydrocarbon group is not particularly limited, but may be, for example, an alkyl group having 1 to 6 carbon atoms and the number of carbon atoms which may be substituted by one or more halogen atoms. 2 to 6 alkenyl groups, 2 to 6 carbon alkynyl groups, 3 to 10 carbon cycloalkyl groups, 3 to 10 carbon unsaturated cycloalkyl groups, 5 to 10 member heterocyclyl groups, 5 to 10 member Examples thereof include an unsaturated heterocyclyl group of the above, an aryl group having 6 to 10 carbon atoms, and a heteroaryl group having 5 to 10 members.

In the above formula, Y is preferably a divalent polar group. The divalent polar group is not particularly limited, but for example, -COO-, -OCO-, -CONH-, -OCH ₂ CH (OH) CH _2- , -CH ₂ CH (OH) CH ₂ O-, -COS-, -SCO-, -O- and the like can be mentioned, preferably -COO-, -CONH-, -CH ₂ CH (OH) CH ₂ O-, or -O-.

In the above formula, R ³ is a hydrogen atom or a fluorine atom independently at each appearance.

In the above formula, f is an integer of 0 to 50, preferably an integer of 0 to 20 (for example, an integer of 1 to 20). j is an integer of 0 to 100, preferably an integer of 0 to 40 (for example, an integer of 1 to 40). The sum of f and j is 1 or more. The order of existence of each repeating unit in parentheses with f and j is arbitrary in the above equation.

^{R 1} represented by the above formula is preferably a group represented by the following formula independently of each other.
− (Y) _f − (CF ₂ ) _g − (CH ₂ ) _h −

In the above formula, Y and f are as described above. g and h are each independently an integer of 0 to 50, preferably an integer of 0 to 20 (for example, an integer of 1 to 20). The sum of f, g, and h is 1 or more, preferably 1 to 10. f, g, and h are more preferably integers of 0 to 2, and further preferably f = 0 or 1, g = 2, h = 0 or 1. Further, the order of existence of each repeating unit in parentheses with f, g, and h is arbitrary in the above formula.

In the above formulas (B1-i) and (B1-ii), X is an active hydrogen-containing group. X is preferably independently of -OH group, -C (= O) H group, -SH group, -SO ₃ H group, -SO ₂ H group, -SOH group, -NH ₂ group, -. It is an NH-group or -SiH group, more preferably an -OH group or -NH ₂ group, and even more preferably a -OH group.

The component (B1) is preferably at least one compound represented by one of the following formulas (B1-i') and (B1-ii'), and more preferably the following formula (B1-i'). It is at least one compound represented by'). When the component (B1) is at least one compound represented by the following formula (B1-i'), PFPE is preferably a group represented by the following formula (D1).
Rf-PFPE-R-CH ₂ OH (B1-i')
HOCH _2- R ^1- PFPE-R ^1- CH ₂ OH (B1-ii')

In the above formula, Rf, PFPE, and R ¹ are as described above.

The perfluoro (poly) ether having the active hydrogen of the component (B1) has one active hydrogen-containing group (for example, a hydroxyl group) at the end of one molecule in addition to the perfluoro (poly) ether group, or 2 It is a compound having one active hydrogen-containing group hydroxyl group at each of one molecular end.

The number average molecular weight of the perfluoro (poly) ether having the active hydrogen of the component (B1) is not particularly limited, but is preferably 500 to 12000, more preferably 1000 to 10000, and further preferably 1500 to 8000. is there.

The above number average molecular weight is ^{measured by 19} F-NMR.

The group having a carbon-carbon double bond and the monomer having active hydrogen of the component (B2) have at least one (preferably one) active hydrogen-containing group (preferably a hydroxyl group) at the molecular terminal thereof.

The group having a carbon-carbon double bond and the monomer having active hydrogen of the component (B2) preferably have a group represented by the following formula as a group having a carbon-carbon double bond.
-OC (O) -CR ² = CH ₂

In the above formula, R ² is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom, and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is an alkyl group, more preferably a hydrogen atom or a methyl group. Here, the ^{group in which R 2} is a hydrogen atom or a methyl group, that is, -OC (O) -CH = CH ₂ , or -OC (O) -CCH ₃ = CH _2, is collectively referred to as "(meth)". Also called "acrylate group".

The component (B2) is not particularly limited, but for example, the following compounds:
HO (CH ₂ CH ₂ ) _i OCO (R) C = CH ₂
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom. I is an integer of 2 to 10. ), For example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate;
CH ₃ CH (OH) CH ₂ OCO (R) C = CH ₂
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom.), For example, 2-hydroxypropyl (meth). Acrylic;
CH ₃ CH ₂ CH (OH) CH ₂ OCO (R) C = CH ₂
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom.), For example, 2-hydroxybutyl (meth). Acrylic;
C ₆ H ₅ OCH ₂ CH (OH) CH ₂ OCO (R) C = CH ₂
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom.), For example, 2-hydroxy-3-phenoxy. Propyl (meth) acrylate;
HOCH ₂ C (CH ₂ OCO (R) C = CH ₂ ) ₃
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom.) For example, pentaerythritol triacrylate;
C (CH ₂ OCO (R) C = CH ₂ ) ₃ CH ₂ OCH ₂ C (CH ₂ OCO (R) C = CH ₂ ) ₂ CH ₂ OH
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom.) For example, dipentaerythritol polyacrylate;
HOCH ₂ CH ₂ OCOC ₆ H ₅ OCOCH ₂ CH ₂ OCO (R) C = CH ₂
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom.), For example, 2-acryloyloxyethyl-. 2-Hydroxyethyl phthalic acid;
H (OCH ₂ CH ₂ ) _n OCO (R) C = CH ₂
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom. N is an integer of 1 to 30. ), For example, poly (ethylene glycol) acrylate;
H (OCH (CH ₃ ) CH ₂ ) _n OCO (R) C = CH ₂
(In the above formula, R is an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydrogen atom, a chlorine atom, a fluorine atom, or a fluorine atom. N is an integer of 1 to 30. ), For example, poly (propylene glycol) acrylate;
Allyl alcohol;
HO (CH ₂ ) _k CH = CH ₂
(In the above formula, k is an integer of 2 to 20.);
(CH ₃ ) ₃ SiCH (OH) CH = CH ₂ ; and
Styrylphenol can be mentioned.

In one embodiment, the component (B) may consist of a component (B1) and a component (B2).

The carbon-carbon double bond-containing compound contained in the compound (F) may have a group derived from a different type of component (B1) in one molecule of triisocyanate. Further, one molecule of triisocyanate may have a group derived from a component (B2) of a different type (for example, having a different number of carbon-carbon double bonds).

Compound (F) may contain one or more carbon-carbon double bond-containing compounds. For example, the compound (F) is a compound obtained by reacting the component (A) with the compound B1 as the component (B1) and the compound B2 as the component (B2), and the component (A) and the component (B1). It may be a mixture of a compound obtained by reacting compound B1'as a compound with compound B1'and compound B2'as a component (B2). These compounds may be synthesized simultaneously or separately and then mixed.

Known compounds (F) include, for example, "Optur (registered trademark) DAC" and "Optur DAC-HP" manufactured by Daikin Industries, Ltd., and "KY-1203" and "KNS5300" manufactured by Shinetsu Chemical Industries, Ltd. , DIC's "Mega Fvck (registered trademark) RS-75", "Mega Fvck RS-72-K", "Mega Fvck RS-76-E", "Mega Fvck RS-76-NS", "Mega Fvck" RS-90 ”,“ Defenser® TF3028 ”,“ Defensa TF3001 ”, and“ Defensa TF3000 ”,“ SUA1900L10 ”and“ SUA1900L6 ”manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Trademarks) P56 ”,“ Fluorolink P54 ”,“ Fluorolink F10 ”,“ Fluorolink A10P ”,“ Fluorolink AD1700 ”,“ Fluorolink MD700 ”,“ Fluorolink E10H ”and the like.

Compound (G) has a perfluoro (poly) ether group and a hydrolyzable group.

As used herein, the "hydrolyzable group" means a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups are -OR, -OCOR, -ON = CR ₂ , -NR ₂ , -NHR, halogen (in these formulas, R is substituted or unsubstituted carbon number 1 to 4). (Indicating an alkyl group of) and the like, preferably −OR (that is, an alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.

Compound (G) has the following formula:
−SiR ¹ _n1 R ² _3-n1
(In the formula, R ¹ represents a hydrolyzable group;
R ² represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms;
n1 is an integer of 1 to 3. )
It is preferable to have a group represented by.

Compound (G) is represented by the following formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):

[During the ceremony:
PFPE is independent of each appearance and formula:
− (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d −
(In the equation, a, b, c and d are independently integers from 0 to 200, the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d. The order of existence of each repeating unit enclosed in parentheses with a mark is arbitrary in the formula.)
It is a group represented by;
Rf represents an alkyl group having 1 to 16 carbon atoms which may be independently substituted with one or more fluorine atoms at each appearance;
R ¹ represents a hydrolyzable group independently at each appearance;
R ² independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each appearance;
R ¹¹ independently represents a hydrogen or halogen atom at each appearance;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each appearance;
n1 is an integer of 0 to 3 independently for each unit ^{(-SiR 1} _n1 R ² _3-n1);
However, in equations (A1), (A2), (B1) and (B2), at least one n1 is an integer of 1-3;
X ¹ independently represents a single bond or a 2-10 valent organic group;
X ² independently represents a single bond or divalent organic group at each appearance;
t is an integer from 1 to 10 independently for each occurrence;
α is an integer of 1 to 9 independently of each other;
α'is an integer from 1 to 9 independently of each other;
X ⁵ each independently represents a single bond or a 2-10 valent organic group;
β are each independently an integer of 1-9;
β'is an integer from 1 to 9 independently of each other;
X ⁷ each independently represents a single bond or a 2-10 valent organic group;
γ is an integer of 1 to 9 independently of each other;
γ'is an integer from 1 to 9 independently of each other;
R ^a independently represents ^{−Z 1 −} SiR ⁷¹ _p1 R ⁷² _q1 R ⁷³ _r1 at each appearance;
Z ¹ independently represents an oxygen atom or a divalent organic group at each appearance;
R ⁷¹ is independently at each occurrence, represents a R ^{a ';}
R ^{a 'is} located in the same meaning as ^{R a;}
During R ^a, Si is connected to the linear via Z ¹ group is five at the maximum;
R ⁷² represents a hydrolyzable group independently at each appearance;
R ⁷³ independently represents a hydrogen atom or lower alkyl group at each appearance;
p1 is an integer from 0 to 3 independently for each occurrence;
q1 is an integer from 0 to 3 independently for each occurrence;
r1 is an integer from 0 to 3 independently for each occurrence;
However, in equations (C1) and (C2), at least one q1 is an integer of 1-3;
R ^b represents a hydrolyzable group independently at each appearance;
R ^c independently represents a hydrogen atom or a lower alkyl group at each appearance;
k1 is an integer of 1-3 independently for each occurrence;
l1 is an integer from 0 to 2 independently for each occurrence;
m1 is an integer from 0 to 2 independently for each occurrence;
However, the sum of k1, l1 and m1 is 3 in the unit enclosed in parentheses with γ;
X ⁹ each independently represents a single bond or a 2-10 valent organic group;
δ is an integer from 1 to 9 independently of each other;
δ'is an integer from 1 to 9 independently of each other;
R ^d is, independently at each ^occurrence, represents a ^{_{-Z 2 -CR 81 p2 R 82 q2}} R 83 r2;
Z ² independently represents an oxygen atom or a divalent organic group at each appearance;
R ⁸¹ independently represents ^{R d'} in each appearance;
R ^d' is synonymous with ^{R d;}
In R ^d , the maximum number of Cs that are linearly connected via ^{two Z groups is five;}
R ⁸² independently represents −Y—SiR ⁸⁵ _n2 R ⁸⁶ _{3-n2 at each appearance;}
Y independently represents a divalent organic group at each appearance;
R ⁸⁵ represents a hydrolyzable group independently at each appearance;
R ⁸⁶ independently represents a hydrogen atom or lower alkyl group at each appearance;
n2 represents an integer of 1 to 3 independently for each unit (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2);
However, in equations (C1) and (C2), at least one n2 is an integer of 1-3;
R ⁸³ independently represents a hydrogen atom or lower alkyl group at each appearance;
p2 is an integer from 0 to 3 independently for each occurrence;
q2 is an integer from 0 to 3 independently for each occurrence;
r2 is an integer from 0 to 3 independently for each occurrence;
R ^e is, independently at each ^occurrence, represents ^{_{-Y-SiR 85 n2 R 86 3}} -n2;
R ^f independently represents a hydrogen atom or a lower alkyl group at each appearance;
k2 is an integer from 0 to 3 independently for each occurrence;
l2 is an integer from 0 to 3 independently for each occurrence;
m2 is an integer from 0 to 3 independently for each occurrence;
However, in equations (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3. However, the sum of k2, l2 and m2 is 3. ]
At least one perfluoro (poly) ether group-containing silane compound represented by any of the above is preferable.

Hereinafter, regarding the perfluoro (poly) ether group-containing silane compound represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2). explain.

Equations (A1) and (A2):

In the above formula, PFPE is − (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d −, which corresponds to a perfluoro (poly) ether group. To do. Here, a, b, c and d are independently integers of 0 or 1 or more, and the sum of a, b, c and d is at least 1. Preferably, a, b, c and d are each independently an integer of 0 or more and 200 or less, for example, an integer of 1 to 200, and more preferably each independently of an integer of 0 or more and 100 or less. Further, the sum of a, b, c and d is preferably 5 or more, and more preferably 10 or more, for example, 10 or more and 100 or less. In addition, the order of existence of each repeating unit with the subscripts a, b, c or d and enclosed in parentheses is arbitrary in the formula. Of these 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) It may be any of (CF ₃ ) CF (CF ₃ ))-,-(OCF (C ₂ F ₅ ) CF ₂ )-and-(OCF ₂ CF (C ₂ F ₅ ))-, but it is preferable. -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )-is either-(OCF ₂ CF ₂ CF ₂ )-,-(OCF (CF ₃ ) CF ₂ )-and-(OCF ₂ CF (CF ₃ ))- It is good, but preferably − (OCF ₂ CF ₂ CF ₂ ) −. Further, − (OC ₂ F ₄ ) − may be any of − (OCF ₂ CF ₂ ) − and − (OCF (CF ₃ )) −, but − (OCF ₂ CF ₂ ) − is preferable. is there.

In one embodiment, the PFPE is − (OC ₃ F ₆ ) _b − (in the formula, b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less). Preferably, − (OCF ₂ CF ₂ CF ₂ ) _b − (in the formula, b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less) or − (OCF (CF). ₃ ) CF ₂ ) _b − (In the formula, b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less), and more preferably − (OCF ₂ CF ₂ CF. ₂ ) _b − (in the formula, b is an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less).

In another embodiment, the PFPE is − (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d − (in the equation, a and b are independent of each other. C and d are independently integers of 0 or more and 30 or less, preferably 1 or more and 200 or less, preferably 5 or more and 200 or less, and more preferably 10 or more and 200 or less, and the subscripts a, b, and c. The order of existence of each repeating unit enclosed in parentheses with or d is arbitrary in the formula), preferably − (OCF ₂ CF ₂ CF ₂ CF ₂ ) _a − (OCF ₂ CF ₂ CF). ₂ ) _b − (OCF ₂ CF ₂ ) _c − (OCF ₂ ) _d −. In one embodiment, the PFPE is − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d − (in the formula, c and d are independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably. Is an integer of 10 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with a subscript c or d may be arbitrary in the formula).

In yet another embodiment, PFPE ^{_{is, - (OC 2 F 4 -R}} 8) f - is a group represented by. In the formula, R ⁸ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of 2 or 3 groups selected independently of these groups. is there. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but is, for example, -OC ₂ F ₄ OC ₃ F _6- , -OC. _{2 F 4 OC 4 F 8 -} , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC _{4 F 8 -, - OC 2} F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 -, - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and _-OC 4 F ₈ OC ₂ F ₄ OC ₂ F ₄ -etc. The above f is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either straight chain or branched chain, and are preferably straight chain. In this embodiment, the PFPE is preferably − (OC ₂ F ₄ −OC ₃ F ₆ ) _f − or − (OC ₂ F ₄ −OC ₄ F ₈ ) _f −.

In the above formula, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.

The "alkyl group having 1 to 16 carbon atoms" in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms is a straight chain or a branched chain. It is also preferable, preferably an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain, particularly an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms in a straight chain.

The Rf is preferably a one or more alkyl groups of 1 to 16 carbon atoms which is substituted by fluorine atoms, more preferably CF 2 _{H-C 1-15} fluoroalkylene group, more preferably Is a perfluoroalkyl group having 1 to 16 carbon atoms.

The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably the linear or branched chain having 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. It is a perfluoroalkyl group of 3, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ . ..

In the above formula, R ¹ represents a hydrolyzable group independently at each appearance.

In the above formula, R ² independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms at each appearance.

As used herein, the "hydrolyzable group" means a group that can be eliminated from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups are -OR, -OCOR, -ON = CR ₂ , -NR ₂ , -NHR, halogen (in these formulas, R is substituted or unsubstituted carbon number 1 to 4). (Indicating an alkyl group of) and the like, preferably −OR (that is, an alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.

In the above formula, R ¹¹ independently represents a hydrogen atom or a halogen atom at each appearance. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, and more preferably a fluorine atom.

In the above formula, R ¹² independently represents a hydrogen atom or a lower alkyl group at each appearance. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.

In the above formulas, n1 ^{_{is, (- SiR 1 n1 R 2}} 3-n1) independently for each unit, an integer of 0 to 3, preferably 1 to 3, more preferably 3. However, in the equation, not all n1s become 0 at the same time. In other words, at least one R ¹ is present in the equation.

In the above formula, X ¹ independently represents a single bond or a 2- to 10-valent organic group. The X ¹ is a perfluoro (poly) ether portion (that is, Rf-PFPE portion or -PFPE-) that mainly provides water repellency, surface slipperiness, etc. in the compounds represented by the formulas (A1) and (A2). A part) and a silane part (that is, a group enclosed in parentheses with α) that provides a binding ability to a base material are understood as a linker. Therefore, the X ¹ may be any organic group as long as the compounds represented by the formulas (A1) and (A2) can be stably present.

In the above equation, α is an integer of 1 to 9 independently, and α'is an integer of 1 to 9 independently of each other. These α and α'can change depending on the valence of ^{X 1.} In formula (A1), the sum of α and α'is the same as the valence of ^{X 1.} For example, if X ¹ is a 10-valent organic group, the sum of α and α'is 10, for example α is 9 and α'is 1, α is 5 and α'is 5, or α is 1 and α. 'Can be 9. When X ¹ is a divalent organic group, α and α'are 1. In the formula (A2), α is a value obtained by subtracting 1 from the valence ^{of X 1.}

The X ¹ is preferably 2 to 7 valent, more preferably 2 to 4 valent, and even more preferably a divalent organic group.

In one embodiment, X ¹ is a 2-4 valent organic group, α is 1-3 and α'is 1.

In another embodiment, X ¹ is a divalent organic group, α is 1, and α'is 1. In this case, the formulas (A1) and (A2) are represented by the following formulas (A1') and (A2').

The ^{example of X 1} is not particularly limited, but for example, the following equation:
-(R ³¹ ) _p' -(X ^a ) _q'-
[During the ceremony:
R ³¹ represents a single bond, − (CH ₂ ) _s'− or o−, m − or p-phenylene group, preferably − (CH ₂ ) _s'− .
s'is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
X ^a represents − (X ^b ) _l'− ,
X ^b is an independent -O-, -S-, o-, m- or p-phenylene group, -C (O) O-, -Si (R ³³ ) ₂ -,-( _{^{Si (R 33) 2 O)}} m '-Si (R 33) 2 -, - CONR 34 -, - O-CONR 34 -, - NR 34 - and - _(CH 2) _n' - is selected from the group consisting of Represents a group
R ³³ independently represents a phenyl group, a C _1-6 alkyl group or a C _1-6 alkoxy group at each appearance, preferably a phenyl group or a C _1-6 alkyl group, more preferably a methyl group. And
R ³⁴ independently represents a hydrogen atom, a phenyl group or a C _1-6 alkyl group (preferably a methyl group) at each appearance.
m'is an integer of 1 to 100, preferably an integer of 1 to 20, independently of each occurrence.
n'is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, independently of each occurrence.
l'is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3.
p'is 0, 1 or 2,
q'is 0 or 1 and
Here, at least one of p'and q'is 1, and the order of existence of each repeating unit in parentheses with p'or q'is arbitrary].
The divalent group represented by is mentioned. Here, R ³¹ and X ^a (typically ^{hydrogen atoms of R 31} and X ^a ) are one or more selected from fluorine atoms, C _1-3 alkyl groups and C _{1-3 fluoroalkyl groups.} It may be substituted with a substituent of.

Preferably, X ¹ is − (R ³¹ ) _{p ′} − (X ^a ) _{q ′} − R ³² −. R ³² represents a single bond, − (CH ₂ ) _t'− or o−, m − or p-phenylene group, preferably − (CH ₂ ) _{t ′} −. t'is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. Here, R ³² (typically ^{the hydrogen atom of R 32} ) is substituted with one or more substituents selected from fluorine atoms, C _1-3 alkyl groups and C _{1-3 fluoroalkyl groups.} May be.

Preferably, the above X ¹ is
C _1-20 alkylene group,
−R ³¹ −X ^c −R ^32- , or −X ^d −R ^32-
[In the formula, R ³¹ and R ³² have the same meaning as above. ]
Can be.

More preferably, the above X ¹ is
C _1-20 alkylene group,
_{- (CH 2) s' -X} c -,
_{- (CH 2) s '-X} c - (CH 2) t' -
−X ^d − or −X ^d − (CH ₂ ) _{t ′} −
[In the formula, s'and t'have the same meaning as above. ]
Is.

In the above formula, X ^c is
-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 -,
_{-O- (CH 2) u '-Si} (R 33) 2 -O-Si (R 33) 2 -CH 2 CH 2 -Si (R 33) 2 -O-Si (R 33) 2 -,
_{-O- (CH 2) u '-Si} (OCH 3) 2 OSi (OCH 3) 2 -,
_{^{-CONR 34 - (CH 2) u}} '- (Si (R 33) 2 O) m' -Si (R 33) 2 -,
_{^{-CONR 34 - (CH 2) u}} '-N (R 34) -, or ^-CONR 34 - (o-, m- or p- _phenylene) -Si ^(R 33) ₂ -
[In the formula, R ³³ , R ³⁴ and m'have the same meaning as above.
u'is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. ] Is represented. ^Xc is preferably −O−.

In the above formula, X ^d is
-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) u}} '-N (R 34) -, or ^-CONR 34 - (o-, m- or p- _phenylene) -Si ^(R 33) ₂ -
[In the formula, each symbol has the same meaning as above. ]
Represents.

More preferably, the above X ¹ is
C _1-20 alkylene group,
_{- (CH 2) s' -X} c - (CH 2) t '-, or _{^{-X d - (CH 2) t}} ' -
[In the formula, each symbol has the same meaning as above. ]
Can be.

Even more preferably, the above X ¹ is
C _1-20 alkylene 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) -
[In the formula, R ³³ , m', s', t'and u'have the same meaning as above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3. It is an integer. ]
Is.

In the above formula, − (C _v H _2v ) − may be a straight chain or a branched chain, for example, −CH ₂ CH ₂ −, −CH ₂ CH ₂ CH ₂ −, −CH. It can be (CH ₃ ) −, −CH (CH ₃ ) CH ₂₋ .

Substituted the group ^{X 1} is a fluorine _{atom, C 1-3 (preferably, C 1-3} perfluoroalkyl group) alkyl and _{C 1-3} fluoroalkyl group by one or more substituents selected from It may have been done.

In another embodiment, the group X ^1, for example, the following groups can be mentioned:

[In the formula, R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
D is
-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- (in the formula, Ph means phenyl), and

^{(Wherein, R 42} are each independently a hydrogen _atom, an alkyl group or an alkoxy group _{C 1-6} of _{C 1-6,} preferably methyl group or a methoxy group, more preferably a methyl group.)
Is the group selected from
E is − (CH ₂ ) _n − (n is an integer of 2 to 6).
D binds to the PFPE of the molecular backbone and E binds to the opposite group to the PFPE. ]

Specific examples of the above X ^{1 include:}
-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 OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) _2- ,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₃ −,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSI (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ −,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₂ −,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSI (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _2- ,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
-(CH ₂ ) _6- ,
-(CH ₂ ) _2- Si (CH ₃ ) _2- (CH ₂ ) _2- ,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
-CON (Ph)-(CH ₂ ) _3- (In the formula, Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
-CON (CH ₃ )-(CH ₂ ) _6- ,
-CON (Ph)-(CH ₂ ) _6- (In the formula, Ph means phenyl),
-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- ,
-OCH _2- ,
−O (CH ₂ ) ₃ −,
-OCFHCF _2- ,

などが挙げられる。

And so on.

In yet another embodiment, X ¹ is a group represented by the formula: ^{− (R 16} ) _x − (CFR ¹⁷ ) _y − (CH ₂ ) _{z −.} In the formula, x, y and z are independently integers from 0 to 10, the sum of x, y and z is 1 or more, and the order of existence of each repeating unit enclosed in parentheses is in the formula. Is optional.

In the above ^{formula, R 16} are each independently at each occurrence, an oxygen atom, a phenylene, carbazolylene, ^{-NR 26} - ^{(wherein, R 26} represents a hydrogen atom or an organic group) or a divalent organic group is there. Preferably, R ¹⁶ is an oxygen atom or a divalent polar group.

As the "divalent polar group" is not particularly limited, -C (O) -, - C (= NR 27) -, and -C (O) ^{NR 27} - (in these ^{formulas, R 27} is , Representing a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, which may be substituted with one or more fluorine atoms.

In the above formula, R ¹⁷ is independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group at each appearance, and is preferably a fluorine atom. The "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and more preferably a trifluoromethyl group. It is a pentafluoroethyl group, more preferably a trifluoromethyl group.

In this embodiment, X ¹ is preferably the equation: _{− (O) x} − (CF ₂ ) _y − (CH ₂ ) _z − (in the equation, x, y and z have the same meaning as above and are in parentheses. The order of existence of each repeating unit enclosed in brackets is arbitrary in the equation).

The above formula: As _{a group represented by − (O) x} − (CF ₂ ) _y − (CH ₂ ) _z −, for example, − (O) _{x ′} − (CH ₂ ) _{z ”} −O− [(CH). ₂ ) _z''''- O-] _{z ""} , and-(O) _x' -(CF ₂ ) _{y "} -(CH ₂ ) _z" -O-[(CH ₂ ) _{z ""} -O- ] _{Z ""} (In the formula, x'is 0 or 1, y ", z" and z "" are independently integers from 1 to 10, and z "" is 0 or 1. The left end of these groups is bonded to the PFPE side.

In another preferred ^{embodiment, X} 1 _{^{is, -O-CFR 13 - (CF}} 2) e - a.

Each of R ¹³ independently 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, a pentafluoroethyl group, and even more preferably a trifluoromethyl group. Is.

The above e is 0 or 1 independently of each other.

In one specific example, R ¹³ is a fluorine atom and e is 1.

In yet another embodiment, examples of X ¹ groups include the following groups:

[During the ceremony,
Each R ⁴¹ is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C _1-6 alkoxy group, preferably a methyl group;
In each group X ^1, some of any of T, then the following groups bonded to the PFPE molecule backbone:
-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- (In the formula, Ph means phenyl), or

^{Wherein, R 42} are each independently a hydrogen _atom, an alkyl group or an alkoxy group _{C 1-6} of _{C 1-6,} preferably methyl group or a methoxy group, more preferably a methyl group. ]
And some of the other Ts are groups opposite to the PFPE of the molecular backbone (ie, carbon atoms in formulas (A1), (A2), (D1) and (D2), and the formula below (ie). _{-(CH 2} ) _{n "} -(n" is an integer of 2 to 6) that binds to (Si atom in B1), (B2), (C1) and (C2), and if present, the rest is Each can be independently a methyl group, a phenyl group, a C _1-6 alkoxy group or a radical trapping group or an ultraviolet absorbing group.

The radical trapping group is not particularly limited as long as it can trap radicals generated by light irradiation, but for example, benzophenones, benzotriazoles, benzoic acid esters, phenyl salicylate, crotonic acids, malonic acid esters, organoacrylates, etc. , Hindered amines, hindered phenols, or triazine residues.

The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays, and for example, benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, etc. Included are residues of oxanilides, benzoxadinones and benzoxazoles.

が挙げられる。 In a preferred embodiment, the preferred radical scavenging group or UV absorbing group is

Can be mentioned.

In this embodiment ^{, each X 1} can be an independently 3-10 valent organic group.

In the above formula, t is an integer of 1 to 10 independently of each other. In a preferred embodiment, t is an integer of 1-6. In another preferred embodiment, t is an integer of 2-10, preferably an integer of 2-6.

In the above formula, X ² independently represents a single bond or a divalent organic group at each appearance. X ² is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably − (CH ₂ ) _u − (in the formula, u is an integer of 0 to 2).

The compounds represented by the preferred formulas (A1) and (A2) are the following formulas (A1') and (A2'):

[During the ceremony:
PFPEs are independent of each other and formula:
− (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d −
(In the equation, a, b, c and d are independently integers from 0 to 200, the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d. The order of existence of each repeating unit enclosed in parentheses with a mark is arbitrary in the formula.)
It is a group represented by;
Rf represents an alkyl group having 1 to 16 carbon atoms which may be independently substituted with one or more fluorine atoms at each appearance;
R ¹ represents a hydrolyzable group independently at each appearance;
R ² independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each appearance;
R ¹¹ independently represents a hydrogen or halogen atom at each appearance;
R ¹² independently represents a hydrogen atom or a lower alkyl group at each appearance;
n1 is an integer of 1-3, preferably 3.
X ^{1 _{is, -O-CFR 13 - (CF}} 2) e - a is;
R ¹³ is a fluorine atom or lower fluoroalkyl group;
e is 0 or 1;
X ² is − (CH ₂ ) _u −;
u is an integer from 0 to 2 (when u is 0, X ² is a single bond);
t is an integer from 1 to 10. ]
It is a compound represented by.

The compounds represented by the above formulas (A1) and (A2) are, for example, using a perfluoro (poly) ether derivative corresponding to the Rf-PFPE- moiety as a raw material, introducing iodine at the terminal, and then −CH ₂ CR ^{12 _{(X 2 -SiR 1 n1 R 2}} 3-n1) - in can be obtained by reacting a vinyl monomer corresponding.

Equations (B1) and (B2):

In the above formula (B1) and ^{(B2), Rf, PFPE,} R 1, R 2 and n1 are as defined herein relates to the above formula (A1) and (A2).

In the above formula, X ⁵ independently represents a single bond or a 2 to 10 valent organic group. The X ⁵ is a perfluoro (poly) ether portion (Rf-PFPE portion or -PFPE- portion) that mainly provides water repellency, surface slipperiness, etc. in the compounds represented by the formulas (B1) and (B2). When _{^{(specifically, 1 n1 R 2 3-n1}} -SiR) silane unit that provides a binding capability to a substrate it is understood as a linker connecting the. Therefore, the X ⁵ may be any organic group as long as the compounds represented by the formulas (B1) and (B2) can be stably present.

Β in the above equation is an integer of 1 to 9 independently, and β'is an integer of 1 to 9 independently of each other. These β and β'are ^{determined according to the valence of X 3} , and in the formula (B1), the sum of β and β'is the same as the valence of ^{X 5.} For example, if X ⁵ is a 10-valent organic group, the sum of β and β'is 10, for example β is 9 and β'is 1, β is 5 and β'is 5, or β is 1 and β. 'Can be 9. When X ⁵ is a divalent organic group, β and β'are 1. In formula (B2), beta is a value obtained by subtracting 1 from the valence of the value of X ^5.

It said ^{X 5} is preferably 2-7 valence, more preferably divalent to tetravalent, more preferably divalent organic group.

In one embodiment, X ⁵ is a 2-4 valent organic group, β is 1-3, and β'is 1.

In another embodiment, X ⁵ is a divalent organic group, β is 1, and β'is 1. In this case, the formulas (B1) and (B2) are represented by the following formulas (B1') and (B2').

Examples of the above-mentioned X ⁵ are not particularly limited, and examples thereof include the same as those described for ^{X 1.}

Among them, the preferable specific X ⁵ is
-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 OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) _2- ,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₃ −,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSI (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ −,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₂ −,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSI (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _2- ,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
-(CH ₂ ) _6- ,
-(CH ₂ ) _2- Si (CH ₃ ) _2- (CH ₂ ) _2- ,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
-CON (Ph)-(CH ₂ ) _3- (In the formula, Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
-CON (CH ₃ )-(CH ₂ ) _6- ,
-CON (Ph)-(CH ₂ ) _6- (In the formula, Ph means phenyl),
-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- ,
-OCH _2- ,
−O (CH ₂ ) ₃ −,
-OCFHCF _2- ,

などが挙げられる。

And so on.

The compounds represented by the preferred formulas (B1) and (B2) are the following formulas (B1') and (B2'):

[During the ceremony:
PFPEs are independent of each other and formula:
− (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d −
(In the equation, a, b, c and d are independently integers from 0 to 200, the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d. The order of existence of each repeating unit enclosed in parentheses with a mark is arbitrary in the formula.)
It is a group represented by;
Rf represents an alkyl group having 1 to 16 carbon atoms which may be independently substituted with one or more fluorine atoms at each appearance;
R ¹ represents a hydrolyzable group independently at each appearance;
R ² independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each appearance;
n1 is an integer of 1-3, preferably 3.
X ⁵ is −CH ₂ O (CH ₂ ) ₂ −, −CH ₂ O (CH ₂ ) ₃ − or −CH ₂ O (CH ₂ ) ₆ −]
It is a compound represented by.

The compounds represented by the above formulas (B1) and (B2) can be produced by a known method, for example, the method described in Patent Document 1 or an improved method thereof. For example, the compounds represented by the formulas (B1) and (B2) are represented by the following formulas (B1-4) or (B2-4):

[During the ceremony:
PFPEs are independent of each other and formula:
− (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d −
(In the equation, a, b, c and d are independently integers from 0 to 200, the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d. The order of existence of each repeating unit enclosed in parentheses with a mark is arbitrary in the formula.)
It is a group represented by;
Rf represents an alkyl group having 1 to 16 carbon atoms which may be independently substituted with one or more fluorine atoms at each appearance;
X ^{5 'are} each independently a single bond or an 2-10 monovalent organic group;
β are each independently an integer of 1-9;
β'is an integer from 1 to 9 independently of each other;
R ⁹² is a single bond or divalent organic group. ]
The compound represented by is HSiM ₃ (in the formula, M is a halogen atom, R ¹ or R ² , respectively, and R ¹ is an independently hydrolyzable group at each appearance. Yes, R ² is an independent hydrogen atom or alkyl group with 1-22 carbon atoms at each appearance) to convert the ^{halogen atom to R 1} or R ^{2 as needed.} Then, the formula (B1 ") or (B2"):

[In the formula, PFPE, Rf, X ^5' , β, β'and R ⁹² have the same meaning as above;
n1 is an integer from 0 to 3. ]
It can be obtained as a compound represented by.

In the formula (B1 ") or (B2"), from _{^{X 5 'R 92 -CH 2 CH}} 2 - moiety of up corresponds to ^{X 5} in the formula (B1) or (B2).

Equations (C1) and (C2):

In the above formulas (C1) and (C2), Rf and PFPE have the same meaning as the description with respect to the above formulas (A1) and (A2).

In the above formula, X ⁷ independently represents a single bond or a 2 to 10 valent organic group. The X ⁷ is a perfluoro (poly) ether portion (Rf-PFPE portion or -PFPE- portion) that mainly provides water repellency, surface slipperiness, etc. in the compounds represented by the formulas (C1) and (C2). It is understood as a linker that links the ^{silane portion (specifically, -SiR a} _k1 R ^b _l1 R ^c _m1 group) that provides the binding ability to the base material. Therefore, the X ⁷ may be any organic group as long as the compounds represented by the formulas (C1) and (C2) can be stably present.

In the above equation, γ is an integer of 1 to 9 independently, and γ'is an integer of 1 to 9 independently. These γ and γ'are ^{determined according to the valence of X 7} , and in the formula (C1), the sum of γ and γ'is the same as the valence of ^{X 7.} For example, when X ⁷ is a 10-valent organic group, the sum of γ and γ'is 10, for example, γ is 9 and γ'is 1, γ is 5 and γ'is 5, or γ is 1 and γ. 'Can be 9. When X ⁷ is a divalent organic group, γ and γ'are 1. In equation (C1), γ is the value obtained by subtracting 1 from the value of the valence ^{of X 7.}

The X ⁷ is preferably a 2-7 valent, more preferably 2-4 valent, and even more preferably a divalent organic group.

In one embodiment, X ⁷ is a 2-4 valent organic group, γ is 1-3 and γ'is 1.

In another embodiment, X ⁷ is a divalent organic group, γ is 1, and γ'is 1. In this case, the formulas (C1) and (C2) are represented by the following formulas (C1') and (C2').

Examples of the above-mentioned X ⁷ are not particularly limited, and examples thereof include the same as those described for ^{X 1.}

Among them, the preferable specific X ⁷ is
-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 OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) _2- ,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₃ −,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSI (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ −,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₂ −,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSI (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _2- ,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
-(CH ₂ ) _6- ,
-(CH ₂ ) _2- Si (CH ₃ ) _2- (CH ₂ ) _2- ,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
-CON (Ph)-(CH ₂ ) _3- (In the formula, Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
-CON (CH ₃ )-(CH ₂ ) _6- ,
-CON (Ph)-(CH ₂ ) _6- (In the formula, Ph means phenyl),
-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- ,
-OCH _2- ,
−O (CH ₂ ) ₃ −,
-OCFHCF _2- ,

などが挙げられる。

And so on.

In the above formula, ^{R a} is independently at each occurrence ^{represents _{-Z 1 -SiR 71 p1 R 72 q1}} R 73 r1.

In the formula, Z ¹ independently represents an oxygen atom or a divalent organic group at each appearance.

The Z ¹ is preferably a divalent organic group and forms a siloxane bond with ^a Si atom (Si atom to which Ra is bonded) at the end of the molecular main chain in the formula (C1) or the formula (C2). Does not include what to do.

Z ¹ is preferably a C _1-6 alkylene group, − (CH ₂ ) _g −O− (CH ₂ ) _h − (in the formula, g is an integer of 1 to 6, and h is 1 to 1. It is an integer of 6) or −phenylene − (CH ₂ ) _i − (in the formula, i is an integer of 0 to 6), more preferably a C _1-3 alkylene group. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _{2-6 alkynyl group.} ..

^{Wherein, R 71} are each independently at each occurrence, it represents a R ^{a '.} R ^{a 'are} as defined ^{R a.}

During R ^a, Si is connected to the linear via Z ¹ group is five at the maximum. That is, the in R ^a, when R ⁷¹ is present at least one, but Si atom connected to R ^a linear through the Z ¹ group in the there are two or more, via such Z ¹ group The maximum number of Si atoms linked linearly is five. The phrase "through the Z ¹ group in R ^a number of Si atoms linearly linked" is equal to the repetition number of -Z ¹ -Si- being linearly linked in a R ^a Become.

For example, an example in which the Si atoms are linked via Z ¹ group in a R ^a below (simply by the following indicated as "Z").

In the above formula, * means a site that binds to Si in the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In the case, it means the end point of the repetition of ZSi. The number on the right shoulder of Si means the number of occurrences of Si linearly connected via the Z group counted from *. That is, the chain in which the ZSi repetition is completed in ^{Si 2} has "the number of Si atoms linearly connected via ^one Z ^{group in Ra ", and similarly, Si 3} and Si. ^The chains in which the ZSi repetition is completed in 4 and Si ^{5 have "the number of Si atoms linearly connected via one} Z ^{group in Ra} " of 3, 4 and 5, respectively. As is apparent from the above equation, is in the R ^a, but ZSi chain there are multiple, they need not be all the same length, each may be of any length.

In a preferred embodiment, as shown below, " ^{the number of Si atoms linearly linked via one} Z ^{group in Ra} " is one (left formula) or two (left formula) in all chains. Right formula).

In one embodiment, the number of Si atoms linearly linked via ^one Z ^{group in Ra is one or two, preferably one.}

In the formula, R ⁷² represents a hydrolyzable group independently at each appearance.

The "hydrolyzable group" as used herein means a group capable of undergoing a hydrolyzing reaction. Examples of hydrolyzable groups are -OR, -OCOR, -ON = C (R) ₂ , -N (R) ₂ , -NHR, halogen (in these formulas, R is substituted or unsubstituted. (Representing an alkyl group having 1 to 4 carbon atoms) and the like, preferably −OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.

Preferably, R ⁷² is -OR (in the formula, R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

In the formula, R ⁷³ independently represents a hydrogen atom or a lower alkyl group at each appearance. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

In the equation, p1 is an integer from 0 to 3 independently at each appearance; q1 is an integer from 0 to 3 independently at each appearance; r1 is an integer from 0 to 3 independently at each appearance. It is an integer of 0 to 3. However, the sum of p1, q1 and r1 is 3.

In a preferred embodiment, ^{'(if R a'} is absent, ^{R a)} terminal of ^{R a} in ^{R a} in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.

In a preferred embodiment, at least one of the ends of ^{Ra is -Si (-Z 1-} SiR ⁷² _q R ⁷³ _r ) ₂ or -Si (-Z ^1- Si R ⁷² _q ^{R 73} _r ) ₃ , preferably-. It can be Si (−Z ¹ −SiR ⁷² _q R ⁷³ _r ) ₃ . ^Wherein, - the unit of _{^{(Z 1 -SiR 72 q R 73}} r) is preferably ^(-Z 1 -SiR ⁷² _3). In a further preferred embodiment, the distal end of the ^{R a,} all _{^{-Si (-Z 1 -SiR 72 q R}} 73 r) 3, preferably may be _{^{-Si (-Z 1 -SiR 72 3)}} 3.

In the above formulas (C1) and (C2), there is at least one R ⁷² .

In the above formula, R ^b represents a hydrolyzable group independently at each appearance.

R ^b is preferably −OR, −OCOR, −ON = C (R) ₂ , −N (R) ₂ , −NHR, halogen (in these formulas, R is substituted or unsubstituted carbon. (Representing an alkyl group of numbers 1 to 4), preferably −OR. R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. More preferably, R ^b is −OR (in the formula, R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group).

In the above formula, R ^c independently represents a hydrogen atom or a lower alkyl group at each appearance. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

In the equation, k1 is an integer of 1-3 independently for each appearance; l1 is an integer of 0-2 independently for each appearance; m1 is an independent integer for each appearance. It is an integer of 0 to 2. However, the sum of k1, l1 and m1 is 3.

The compounds represented by the above formulas (C1) and (C2) are, for example, using a perfluoro (poly) ether derivative corresponding to the Rf-PFPE- moiety as a raw material, introducing a hydroxyl group at the terminal, and then an unsaturated bond at the end. A group having an unsaturated bond is introduced, the group having an unsaturated bond is reacted with a silyl derivative having a halogen atom, and a hydroxyl group is further introduced into the silyl group at the terminal, and the introduced group having an unsaturated bond and the silyl derivative are used. Can be obtained by reacting. For example, it can be obtained as follows.

The compounds represented by the preferred formulas (C1) and (C2) are the following formulas (C1 ″) and (C2 ″) :.

[During the ceremony:
PFPEs are independent of each other and formula:
− (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d −
(In the equation, a, b, c and d are independently integers from 0 to 200, the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d. The order of existence of each repeating unit enclosed in parentheses with a mark is arbitrary in the formula.)
It is a group represented by;
Rf represents an alkyl group having 1 to 16 carbon atoms which may be independently substituted with one or more fluorine atoms at each appearance;
X ⁷ represents −CH ₂ O (CH ₂ ) ₂ −, −CH ₂ O (CH ₂ ) ₃ − or −CH ₂ O (CH ₂ ) ₆ −;
R ^a independently represents ^{−Z 1 −} SiR ⁷¹ _p1 R ⁷² _q1 R ⁷³ _r1 at each appearance;
Z ¹ represents a C _1-6 alkylene group;
R ⁷¹ is independently at each occurrence, represents a R ^{a ';}
R ^{a 'is} located in the same meaning as ^{R a;}
During R ^a, Si is connected to the linear via Z ¹ group is five at the maximum;
R ⁷² represents a hydrolyzable group independently at each appearance;
R ⁷³ independently represents a hydrogen atom or lower alkyl group at each appearance;
p1 is an integer from 0 to 2 independently for each occurrence;
q1 is an integer of 1-3, preferably 3 independently of each occurrence;
r1 is an integer from 0 to 2 independently for each occurrence;
However, in one ^Ra , the sum of p1, q1 and r1 is 3. ]
It is a compound represented by.

The compounds represented by the above formulas (C1) and (C2) can be produced, for example, as follows. The following formula (C1-4) or (C2-4):

[During the ceremony:
PFPEs are independent of each other and formula:
− (OC ₄ F ₈ ) _a − (OC ₃ F ₆ ) _b − (OC ₂ F ₄ ) _c − (OCF ₂ ) _d −
(In the equation, a, b, c and d are independently integers from 0 to 200, the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d. The order of existence of each repeating unit enclosed in parentheses with a mark is arbitrary in the formula.)
It is a group represented by;
Rf represents an alkyl group having 1 to 16 carbon atoms which may be independently substituted with one or more fluorine atoms at each appearance;
X ^{7 'each} independently represents a single bond or 2-10 monovalent organic group;
γ is an integer of 1 to 9 independently of each other;
γ'is an integer from 1 to 9 independently of each other;
R ⁹² is a single bond or divalent organic group. ]
The compound represented by is HSiR ⁹³ _k1 R ^b _l1 R ^c _m1 (in the formula, R ⁹³ is a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, and R ^b is Each appearance independently represents a hydrolyzable group, R ^c independently represents a hydrogen atom or a lower alkyl group at each appearance, k1 is an integer of 1-3, l1 and m1. Are independently integers from 0 to 2, and the sum of k1, l1 and m1 is 3), respectively, by reacting with a compound represented by the formula (C1-5) or (C2-5). :

［式中、Ｒｆ、ＰＦＰＥ、Ｒ^９２、Ｒ^９３、Ｒ^ｂ、Ｒ^ｃ、γ、γ’、Ｘ^７’、ｋ１、ｌ１およびｍ１は、上記と同意義である。］
で表される化合物を得る。

[In the formula, Rf, PFPE, R ⁹² , R ⁹³ , R ^b , R ^c , γ, γ', X ^7' , k1, l1 and m1 have the same meanings as described above. ]
Obtain the compound represented by.

The obtained compound represented by the formula (C1-5) or (C2-5) was used as Hal-J-R ⁹⁴ -CH = CH ₂ (in the formula, H is a halogen atom (for example, I, Br, Cl, F, etc.), J represents Mg, Cu, Pd or Zn, and R ⁹⁴ represents a single bond or a divalent organic group) by reacting with a compound represented by the formula (C1-6). Or (C2-6):

［式中、Ｒｆ、ＰＦＰＥ、Ｒ^９２、Ｒ^９４、Ｒ^ｂ、Ｒ^ｃ、γ、γ’、Ｘ^７’、ｋ１、ｌ１およびｍ１は、上記と同意義である。］
で表される化合物を得る。

[In the formula, Rf, PFPE, R ⁹² , R ⁹⁴ , R ^b , R ^c , γ, γ', X ^7' , k1, l1 and m1 have the same meanings as described above. ]
Obtain the compound represented by.

The obtained compound represented by the formula (C1-6) or (C2-6) is HSiM ₃ (in the formula, M is a halogen atom, R ⁷² or R ⁷³ , respectively, and R ⁷² is , Representing a hydrolyzable group ^{independently at each appearance, and R 73} independently representing a hydrogen atom or a lower alkyl group at each appearance), as required above. Converting the halogen atom to R ⁷² or R ⁷³ , the formula (C1''') or (C2'''):

[In the formula, Rf, PFPE, R ⁷² , R ⁷³ , R ⁹² , R ⁹⁴ , R ^b , R ^c , γ, γ', X ^7' , k1, l1 and m1 have the same meaning as above;
q1 is an integer of 1-3 independently for each occurrence;
r1 is an integer of 0 to 2 independently for each occurrence. ]
The compound represented by is obtained.

In the formula (C1 ''') or (C2'''), from _{^{X 7 'R 92 -CH 2 CH}} 2 - moiety until the, corresponding to ^{X 7} in formula (C1) or (C2), -R ^94- CH ₂ CH _2- corresponds to Z in equation (C1) or (C2).

Equations (D1) and (D2):

In the above formulas (D1) and (D2), Rf and PFPE have the same meaning as the description relating to the above formulas (A1) and (A2).

In the above formula, X ⁹ independently represents a single bond or a 2- to 10-valent organic group. The X ⁹ is a perfluoro (poly) ether portion (that is, Rf-PFPE portion or -PFPE-) that mainly provides water repellency, surface slipperiness, etc. in the compounds represented by the formulas (D1) and (D2). Part) and the part that provides the ability to bind to the substrate (that is, the group enclosed in parentheses with δ) are interpreted as a linker. Therefore, the X ⁹ may be any organic group as long as the compounds represented by the formulas (D1) and (D2) can be stably present.

In the above equation, δ is an integer of 1 to 9 independently, and δ'is an integer of 1 to 9 independently of each other. These δ and δ'can vary depending on the valence of ^{X 9.} In formula (D1), the sum of δ and δ'is the same as the valence of ^{X 9.} For example, if X ⁹ is a 10-valent organic group, the sum of δ and δ'is 10, for example, δ is 9 and δ'is 1, δ is 5 and δ'is 5, or δ is 1 and δ. 'Can be 9. Further, when X ⁹ is a divalent organic group, δ and δ'are 1. In equation (D2), δ is ^{the valence of X 9} minus one.

The X ⁹ is preferably 2 to 7 valent, more preferably 2 to 4 valent, and even more preferably a divalent organic group.

In one embodiment, X ⁹ is a 2-4 valent organic group, δ is 1-3 and δ'is 1.

In another embodiment, X ⁹ is a divalent organic group, δ is 1, and δ'is 1. In this case, the formulas (D1) and (D2) are represented by the following formulas (D1') and (D2').

Examples of the above-mentioned X ⁹ are not particularly limited, and examples thereof include the same as those described for ^{X 1.}

Among them, the preferable specific X ⁹ is
-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 OCF ₂ CHFOCF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF _2- ,
-CH ₂ OCF ₂ CHFOCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF _2- ,
-CH ₂ OCH ₂ CHFCF ₂ OCF (CF ₃ ) CF ₂ OCF ₂ CF ₂ CF _2- ,
-CH ₂ OCH ₂ (CH ₂ ) ₇ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) _2- ,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₃ −,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSI (OCH ₂ CH ₃ ) ₂ (CH ₂ ) ₃ −,
−CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSI (OCH ₃ ) ₂ (CH ₂ ) ₂ −,
-CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₂ OSI (OCH ₂ CH ₃ ) ₂ (CH ₂ ) _2- ,
-(CH ₂ ) _2- ,
-(CH ₂ ) _3- ,
- _{(CH 2)} 4 -,
-(CH ₂ ) _5- ,
-(CH ₂ ) _6- ,
-(CH ₂ ) _2- Si (CH ₃ ) _2- (CH ₂ ) _2- ,
-CONH- (CH ₂ ) _3- ,
-CON (CH ₃ )-(CH ₂ ) _3- ,
-CON (Ph)-(CH ₂ ) _3- (In the formula, Ph means phenyl),
-CONH- (CH ₂ ) _6- ,
-CON (CH ₃ )-(CH ₂ ) _6- ,
-CON (Ph)-(CH ₂ ) _6- (In the formula, Ph means phenyl),
-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- ,
-OCH _2- ,
−O (CH ₂ ) ₃ −,
-OCFHCF _2- ,

などが挙げられる。

And so on.

In the above formula, ^{R d} are each, independently at each ^occurrence, represents a _{^{-Z 2 -CR 81 p2 R 82 q2}} R 83 r2.

In the formula, Z ² independently represents an oxygen atom or a divalent organic group at each appearance.

Z ² is preferably a C _1-6 alkylene group, − (CH ₂ ) _g −O − (CH ₂ ) _h − (in the formula, g is an integer of 0 to 6, for example, an integer of 1 to 6. Yes, h is an integer from 0 to 6, for example an integer from 1 to 6) or −phenylene − (CH ₂ ) _i − (in the equation, i is an integer from 0 to 6), and more. It is preferably a C _1-3 alkylene group. These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _{2-6 alkynyl group.} ..

In the formula, R ⁸¹ independently represents ^{R d'} at each occurrence. R ^d' has the same meaning ^{as R d.}

In R ^d , the maximum number of Cs that are linearly connected via ^{two Z groups is five.} That is, in the above R ^d , when at least one ^{R 81} is present, two or more Si atoms linearly linked via ^{two Z groups are present in R d} , but ^{through such two} Z groups. The maximum number of C atoms linked linearly is five. The phrase "through the Z ² group in R ^d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 ^-C- being linearly linked in a R ^d Become. This is the same as the description regarding ^Ra in the formulas (C1) and (C2).

In a preferred embodiment, the " ^{number of C atoms linearly linked via two} Z ^{groups in R d} " is one or two in all chains.

In one embodiment, the number of C atoms linearly linked via ^two Z ^{groups in R d is one or two, preferably one.}

In the formula, R ⁸² independently represents −Y—SiR ⁸⁵ _n2 R ⁸⁶ _{3-n2 at each appearance.}

Y independently represents a divalent organic group at each appearance.

In a preferred embodiment, Y is a C _1-6 alkylene group,-(CH ₂ ) _g'- O- (CH ₂ ) _h' -(in the formula, g'is an integer of 0-6, eg, 1-6. It is an integer, h'is an integer from 0 to 6, for example, an integer from 1 to 6), or -phenylene- (CH ₂ ) _i' -(in the formula, i'is an integer from 0 to 6). ). These groups may be substituted with one or more substituents selected from, for example, a fluorine atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, and a C _{2-6 alkynyl group.} ..

In one embodiment, Y _{is, C 1-6} alkylene _{group, -O- (CH 2) h '} - or - phenylene - _(CH 2) _i' - may be. When Y is the above group, light resistance, especially UV resistance, can be higher.

The R ⁸⁵ represents a hydrolyzable group independently at each appearance.

The "hydrolyzable group" as used herein means a group capable of undergoing a hydrolyzing reaction. Examples of hydrolyzable groups are -OR, -OCOR, -ON = C (R) ₂ , -N (R) ₂ , -NHR, halogen (in these formulas, R is substituted or unsubstituted. (Representing an alkyl group having 1 to 4 carbon atoms) and the like, preferably −OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.

Preferably, R ⁸⁵ is -OR (in the formula, R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably an ethyl group or a methyl group, particularly a methyl group).

The R ⁸⁶ independently represents a hydrogen atom or a lower alkyl group at each appearance. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

n2 represents an integer of 1 to 3 independently for each unit (-Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 ), preferably 2 or 3, and more preferably 3.

The R ⁸³ independently represents a hydrogen atom or a lower alkyl group at each appearance. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

In the equation, p2 is an integer from 0 to 3 independently at each appearance; q2 is an integer from 0 to 3 independently at each appearance; r2 is an integer from 0 to 3 independently at each appearance. It is an integer of 0 to 3. However, the sum of p2, q2 and r2 is 3.

In a preferred embodiment, ^{'(if R d'} is absent, ^{R d)} end of ^{R d} in ^{R d} in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.

In a preferred embodiment, at least one of the ends of ^{R d is -C (-Y-SiR 85} _q2 R ⁸⁶ _r2 ) ₂ or -C (-Y-SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) ₃ , preferably -C (. -Y-SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) ₃ can be. _{^{Wherein, (- Y-SiR 85 q2}} R 86 r2) units is preferably ^{(-Y-SiR 85} _3). In a more preferred embodiment, ^{the ends of R d} can all be -C (-Y-SiR ⁸⁵ _q2 R ⁸⁶ _r2 ) ₃ , preferably -C (-Y-SiR ⁸⁵ ₃ ) ₃ .

In the above formula, ^{R e} is independently at each ^occurrence, represents a _{^{-Y-SiR 85 n2 R 86 3}} -n2. Here, Y, R ⁸⁵ , R ⁸⁶ and n2 have the same meaning as the description in ^{R 82 above.}

In the above formula, R ^f independently represents a hydrogen atom or a lower alkyl group at each appearance. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

In the equation, k2 is an integer from 0 to 3 independently at each appearance; l2 is an integer from 0 to 3 independently at each appearance; m2 is an integer from 0 to 3 independently at each appearance. It is an integer of 0 to 3. However, the sum of k2, l2 and m2 is 3.

In one embodiment, at least one k2 is 2 or 3, preferably 3.

In one embodiment, k2 is 2 or 3, preferably 3.

In one embodiment, l2 is 2 or 3, preferably 3.

In the above formulas (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3. That is, there are at least two -Y-SiR ⁸⁵ _n2 R ⁸⁶ _3-n2 groups in the formula.

The perfluoro (poly) ether group-containing silane compound represented by the formula (D1) or the formula (D2) can be produced by combining known methods. For example, the compound represented by the formula (D1') in which X is divalent can be produced, but is not limited to, as follows.

A group containing a double bond in a polyhydric alcohol represented by HO-X-C (YOH) ₃ (in the formula, X and Y are independently divalent organic groups) (preferably). Is allyl), and halogen (preferably bromo) is introduced, and Hal-X-C (YO-R-CH = CH ₂ ) ₃ (In the formula, H is halogen, for example Br, and R is two. A double bond-containing halide represented by a valent organic group, for example, an alkylene group) is obtained. Next, the terminal halogen is reacted with a perfluoro (poly) ether group-containing alcohol represented by ^{R PFPE-} OH (in the formula, R ^{PFPE is a perfluoro (poly) ether group-containing group).} , R ^PFPE- O-X-C ( _{YO-R-CH = CH 2} ) ₃ is obtained. Then, a -CH = _CH 2 end, ^is reacted with HSiCl ₃ and an alcohol or ^{_{HSiR 85 3, R PFPE -O-}} X-C (Y-O-R-CH 2 -CH 2 -SiR 85 3) 3 Can be obtained.

The perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) are particularly selected. It may have a number average molecular weight of ^{5 × 10 2} to 1 × 10 ⁵ , but not limited to. The number average molecular weight may be preferably 2,000 to 30,000, more preferably 3,000 to 10,000, and even more preferably 3,000 to 8,000.

The number average molecular weight is measured by GPC (gel permeation chromatography) analysis.

The number average molecular weight of the PFPE moiety in the perfluoro (poly) ether group-containing silane compound is not particularly limited, but is preferably 1,500 to 30,000, more preferably 2,500 to 10,000. More preferably, it can be 3,000 to 8,000.

Compound (H) is represented by the formula: R ^111- PFPE-R ^113.
(In the formula, PFPE is a perfluoro (poly) ether group, R ¹¹¹ and R ¹¹³ are independently F, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, and 1 to 16 carbon atoms. Alkyl fluorinated group, alkoxy group fluorinated with 1 to 16 carbon atoms, -R ^114- X ¹¹¹ (R ¹¹⁴ is a single-bonded or divalent organic group, X ¹¹¹ is -NH ₂ , -OH, -COOH, -CH = CH ₂ , -OCH ₂ CH = CH ₂ , halogen, phosphoric acid, phosphate ester, carboxylic acid ester, thiol, thioether, alkyl ether (which may be substituted with fluorine), aryl, aryl ether or amide)) It is represented by.
As X ¹¹¹ , at least one selected from the group consisting of -OH, -COOH, thiol (-SH), -CH = CH ₂ and -OCH ₂ CH = CH _{2 is preferable.} Examples of the divalent organic group include an alkylene group, a fluorinated alkylene group, and a group in which an oxygen atom is bonded to the terminal thereof. The number of carbon atoms of the divalent organic group is not particularly limited, but may be, for example, 1 to 16.

The R ¹¹¹ and R ¹¹³ are independently F, an alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, or -R ^114- X ¹¹¹ (R ¹¹⁴ and X ¹¹¹ are as described above). Is preferable, and F, a fully fluorinated alkyl group having 1 to 3 carbon atoms or -R ^114- X ¹¹¹ (R ¹¹⁴ and X ¹¹¹ are as described above) is more preferable.

As PFPE, for example
Formula:-(CX ¹¹² ₂ CF ₂ CF ₂ O) _n111 (CF (CF ₃ ) CF ₂ O) _n112 (CF ₂ CF ₂ O) _n113 (CF ₂ O) _n114 (C ₄ F ₈ O) _n115-
(N111, n112, n113, n114 and n115 are independently integers of 0 or 1 or more, X ¹¹² is H, F or Cl, and the order of existence of each repeating unit is arbitrary).
Formula:-(OC ₂ F _4- R ¹¹⁸ ) _f-
(R ¹¹⁸ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , and f is an integer of 2 to 100).

It is preferable that n111 to n115 are integers of 0 to 200, respectively. The total amount of n111 to n115 is preferably 1 or more, more preferably 5 to 300, further preferably 10 to 200, and particularly preferably 10 to 100.

R ¹¹⁸ is _{a group selected from OC 2} F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of two or three groups selected independently of these groups. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but is, for example, -OC ₂ F ₄ OC ₃ F _6- , -OC. _{2 F 4 OC 4 F 8 -} , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F _{8 -, - OC 4 F 8} OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC _{4 F 8 -, - OC 2} F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, _{-OC 3 F 6 OC 2 F 4} OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 -, - OC 3 F 6 OC 3 F 6 OC 2 F 4 -, and _-OC 4 F ₈ OC ₂ F ₄ OC ₂ F ₄ -etc. The above f is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either straight chain or branched chain, and are preferably straight chain. In this embodiment, the formula:-(OC ₂ F _4- R ¹¹⁸ ) _f -is preferably the formula:-(OC ₂ F _4- OC ₃ F ₆ ) _f -or the formula:-(OC ₂ F _4- OC). ₄ F ₈ ) _f −.

The weight average molecular weight of compound (H) is preferably 500 to 100,000, more preferably 50,000 or less, further preferably 10,000 or less, and particularly preferably 6,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

Commercially available compounds (H) include brand names Demnam (manufactured by Daikin Industries, Ltd.), Fomblin (manufactured by Solvay Specialty Polymers Japan), Varierta (manufactured by NOK Cluber), and Crytox (manufactured by DuPont). Can be mentioned.

In the laminate of the present invention, the transparent layer is a poly formed by further curing a curable resin, a resin obtained by curing a curable monomer, and a silicon-containing compound. It is also one of the preferred embodiments to include at least one resin selected from the group consisting of resins containing a siloxane structure.

By using these resins, the transparent layer can be formed relatively easily. Further, since the obtained transparent layer has high mechanical strength and hardness and high scratch resistance, the durability of the laminated body can be enhanced.

The laminate of the present invention further contains a resin obtained by curing a curable resin, a resin obtained by curing a curable monomer, and a polysiloxane structure formed by using a silicon-containing compound. It is also one of the preferred embodiments to include a resin layer containing at least one resin selected from the group consisting of.

When the laminate contains the resin layer, the characteristics of the resin layer and the characteristics of the transparent layer are fully exhibited, although the layer structure is slightly complicated. Properties of the resin layer include transparency, low scattering property, low reflection property, scratch resistance, flexibility and the like.

The resin constituting the resin layer preferably has a hardness of 1H or more when a pencil hardness test based on JIS K5600-5-4 is performed.

The curable resin may be either a photocurable resin or a thermosetting resin, and is not particularly limited as long as it has heat resistance and strength, but a photocurable resin is preferable, and an ultraviolet curable resin is preferable. More preferable.

Examples of the curable resin include acrylic polymers, polycarbonate polymers, polyester polymers, polyamide polymers, polyimide polymers, polyether sulfone polymers, cyclic polyolefin polymers, and fluorine-containing polyolefin polymers (PTFE, etc.). Fluorescent cyclic non-crystalline polymers (Cytop (registered trademark), Teflon (registered trademark) AF, etc.) and the like can be mentioned.

Specific examples of the curable resin or the monomer constituting the curable resin include alkyl vinyl ethers such as cyclohexylmethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and ethyl vinyl ether, glycidyl vinyl ether, vinyl acetate, vinyl pivalate, and various types (meth). Acrylate: Phenoxyethyl acrylate, benzyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate , Trimethylol, propanetriacrylate, pentaaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfreel acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene Glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N-vinylpyrrolidone, Dimethylaminoethyl methacrylate Silicon-based acrylate, maleic anhydride, vinylene carbonate, chain side chain polyacrylate, cyclic side chain polyacrylate polynorbornene, polynorbornadiene, polycarbonate, polysulfonic acid amide, fluorocyclic non-crystalline polymer (Cytopp) (Registered trademark), Teflon (registered trademark) AF, etc.) and the like.

The curable monomer may be either a photocurable monomer or a thermosetting monomer, but an ultraviolet curable monomer is preferable.
Examples of the curable monomer include (a) urethane (meth) acrylate, (b) epoxy (meth) acrylate, (c) polyester (meth) acrylate, (d) polyether (meth) acrylate, and (e) silicon. Examples thereof include (meth) acrylate and (f) (meth) acrylate monomer.

Specific examples of the curable monomer include the following.
Examples of the urethane (meth) acrylate include poly [(meth) acryloyloxyalkyl] isocyanurate represented by tris (2-hydroxyethyl) isocyanurate diacrylate and tris (2-hydroxyethyl) isocyanurate triacrylate. Can be mentioned.
(B) The epoxy (meth) acrylate is obtained by adding a (meth) acryloyl group to an epoxy group, and generally uses bisphenol A, bisphenol F, phenol novolac, or an alicyclic compound as a starting material.
(C) Polyhydric alcohols constituting the polyester portion of the polyester (meth) acrylate include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, and the like. Polypropylene glycol, pentaerythritol, dipentaerythritol and the like can be mentioned, and examples of the polybasic acid include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid and alkenyl succinic acid.
Examples of the (d) polyether (meth) acrylate include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyethylene glycol-polypropylene glycol di (meth) acrylate.
(E) Silicon (meth) acrylate is a dimethylpolysiloxane having a molecular weight of 1,000 to 10,000 in which one end or both ends are modified with a (meth) acryloyl group. For example, the following compounds may be used. Illustrated.

(F) Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Se-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl-n-hexyl (meth) ) Acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate , 3-Chloro-2-hydroxypropyl (meth) acrylate, (1,1-dimethyl-3-oxobutyl) (meth) acrylicate, 2-acetoacetoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1, Examples thereof include 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, trimethylpropantriacrylate, and pentaerythritol tetraacrylate.

Among the curable resins and curable monomers, the following are preferable and available on the market.

Examples of the curable resin include silicon resins, PAK-01, PAK-02 (manufactured by Toyo Synthetic Chemical Co., Ltd.), nanoimprint resin NIF series (manufactured by Asahi Glass Co., Ltd.), nanoimprint resin OCNL series (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and NIAC2310 (manufactured by Tokyo Ohka Kogyo Co., Ltd.). Daicel Chemical Industry Co., Ltd.), Epoxy acrylate resins EH-1001, ES-4004, EX-C101, EX-C106, EX-C300, EX-C501, EX-0202, EX-0205, EX-5000, etc. (Kyoeisha Chemical Co., Ltd.) , Hexamethylene diisocyanate-based polyisocyanates, Sumijour N-75, Sumijuru N3200, Sumijuru HT, Sumijuru N3300, Sumijuru N3500 (manufactured by Sumitomo Bavarian Urethane Co., Ltd.) and the like.

Among the curable monomers, the silicone acrylate resins include silaplane FM-0611, silaplane FM-0621, silaplane FM-0625, both-terminal (meth) acrylic-based silaplane FM-7711, and silaplane. FM-7721 and silaplane FM-7725 etc., silaplane FM-0411, silaplane FM-0421, silaplane FM-0428, silaplane FM-DA11, silaplane FM-DA21, silaplane-DA25, single-ended type ( Meta) Examples thereof include acrylic-based silaplane FM-0711, silaplane FM-0721, silaplane FM-0725, silaplane TM-0701 and silaplane TM-0701T (manufactured by JCN).
Examples of polyfunctional acrylates include A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, and A. -TMPT, A-TMMT (manufactured by Shin-Nakamura Kogyo Co., Ltd.) and the like can be mentioned.
Examples of polyfunctional methacrylates include TMPT (manufactured by Shin-Nakamura Kogyo Co., Ltd.).
Examples of the alkoxysilane group-containing (meth) acrylate include 3- (meth) acryloyloxypropyltrichlorosisilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 3-(. Meta) Acryloyloxypropyltriisopropoxysilane (also known as (triisopropoxysilyl) propylmethacrylate (abbreviation: TISMA) and (triisopropoxysilyl) propylacrylate), 3- (meth) acrylicoxyisobutyltrichlorosilane, 3- (meth) ) Acrylooxyisobutyltriethoxysilane, 3- (meth) acrylicoxyisobutyltriisopropoki 3- (meth) acrylicoxyisobutyltrimethoxysilanesisilane and the like.

Since the above resin is excellent in transparency and scratch resistance, a resin obtained by curing a resin such as an acrylic polymer, a polycarbonate polymer, a polyimide polymer, a polyether sulfone polymer, or a cyclic polyolefin polymer, Resins obtained by curing curable monomers such as polyfunctional (meth) acrylates, silicon (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable.

The resin is selected from the group consisting of a resin obtained by curing a composition containing a curable resin and a cross-linking catalyst, and a resin obtained by curing a composition containing a curable monomer and a cross-linking catalyst. It may be at least one kind.
Examples of the cross-linking catalyst include a radical polymerization initiator and an acid generator.
The radical polymerization initiator is a compound that generates radicals by heat or light, and examples thereof include a radical thermal polymerization initiator and a radical photopolymerization initiator. In the present invention, the radical photopolymerization initiator is preferable.

Examples of the radical thermal polymerization initiator include diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, and diisopropyl peroxydicarbonate. Peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, peroxide compounds such as alkylperesters such as t-butylperoxyoctate and t-butylperoxybenzoate, and azobisiso. Examples thereof include radical-generating azo compounds such as butyronitrile.

The radical photopolymerization initiator includes an initiator having an absorption wavelength in the ultraviolet light region and an initiator having an absorption wavelength in the visible light region, and is an initiator having an absorption wavelength in both of them. Also, for example, -diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, thioxanthone, 2,4-diethylthioxanthone and thioxanthone-4. -Thioxanthones such as sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, benzophenone such as 4,4'-bis (diethylamino) benzophenone, acetphenone, 2- (4-toluenesulfonyloxy) -2 -Phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl Acetphenones such as -2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, anthraquinone, quinones such as 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, 4-dimethylamino Amino benzoic acids such as ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, phenacylloride, trihalomethylphenylsulfone and the like. Examples thereof include halogen compounds, acylphosphine oxides, and peroxides such as di-t-butyl peroxide.

Examples of commercially available products of the radical photopolymerization initiator include the following.
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one,
IRGACURE 184: 1-Hydroxy-Cyclohexyl-Phenyl-Ketone,
IRGACURE 2959: 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one,
IRGACURE 127: 2-Hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one,
IRGACURE 907: 2-Methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one,
IRGACURE 369: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,
IRGACURE 379: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone,
IRGACURE 819: Bis (2,4,6-trimethylbenzoyl) -Phenylphosphine oxide,
IRGACURE 784: bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium,
IRGACURE OXE 01: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)],
IRGACURE OXE 02: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime),
IRGACURE261, IRGACURE369, IRGACURE500,
DAROCUR 1173: 2-Hydroxy-2-methyl-1-phenyl-propane-1-one,
DAROCUR TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
DAROCUR1116, DAROCUR2959, DAROCUR1664, DAROCUR4043,
IRGACURE 754 Oxyphenylacetic Acid: A mixture of 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester,
IRGACURE 500: A mixture of IRGACURE 184 and benzophenone (1: 1),
IRGACURE 1300: A mixture of IRGACURE 369 and IRGACURE 651 (3: 7),
IRGACURE 1800: A mixture of CGI403 and IRGACURE 184 (1: 3),
IRGACURE 1870: A mixture of CGI403 and IRGACURE 184 (7: 3),
DAROCUR 4265: A mixture of DAROCUR TPO and DAROCUR 1173 (1: 1).
IRGACURE is manufactured by Ciba Specialty Chemicals, and DAROCUR is manufactured by Merck Japan.

When a radical photopolymerization initiator is used as the cross-linking catalyst, diethyl thioxanthone, isopropyl thioxanthone, or the like can be used in combination as the sensitizer, and DAROCUR EDB (ethyl-4-dimethylaminobenzoate) can be used as the polymerization accelerator. ), DAROCUR EHA (2-ethylhexyl-4-dimethylaminobenzoate) and the like may be used in combination.

When the sensitizer is used, the blending amount of the sensitizer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin or the curable monomer. More preferably, it is 0.1 to 2 parts by mass.
When the polymerization accelerator is used, the amount of the polymerization accelerator to be blended is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin or the curable monomer. More preferably, it is 0.1 to 2 parts by mass.

The acid generator is a material that generates an acid by applying heat or light, and examples thereof include a thermoacid generator and a photoacid generator. In the present invention, a photoacid generator is preferable.
Examples of the thermoacid generator include benzoin tosylate, nitrobenzyl tosylate (particularly 4-nitrobenzyl tosylate), and alkyl esters of other organic sulfonic acids.

The photoacid generator is composed of a color-developing group that absorbs light and an acid precursor that becomes an acid after decomposition. By irradiating a photoacid generator having such a structure with light of a specific wavelength, light is emitted. The acid generator is excited to generate acid from the acid precursor portion.
Examples of the photoacid generator include diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, CF ₃ SO ₃ , p-CH ₃ PhSO ₃ , p-NO ₂ PhSO ₃ (where Ph is a phenyl group) and the like. Examples thereof include salts, organic halogen compounds, orthoquinone-diazidesulfonyl chlorides, and sulfonic acid esters. In addition, as photoacid generators, 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compound, 2-trihalo Methyl-5-hydroxyphenyl-1,3,4-oxadiazole compounds and the like can also be mentioned.
The organic halogen compound is a compound that forms a hydrohalic acid (for example, hydrogen chloride).

The following are exemplified as commercially available products of the photoacid generator.
WPAG-145 [bis (cyclohexylsulfonyl) diazomethane], WPAG-170 [bis (t-butylsulfonyl) diazomethane], WPAG-199 [bis (p-toluenesulfonyl) diazomethane], WPAG-281 manufactured by Wako Pure Chemical Industries, Ltd. [Triphenylsulfonium trifluoromethanesulfonate], WPAG-336 [diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate], WPAG-376 [diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate], Ciba Specialty. IRGACURE PAG103 [(5-propylsulfonyloxymino-5H-thiophen-2-iriden)-(2-methylphenyl) acetonitrile] manufactured by Chemicals, IRGACURE PAG108 [(5-octylsulfonyloxymino-5H-thiophen-2-) Iliden)-(2-methylphenyl) acetonitrile)], IRGACURE PAG121 [(5-p-toluenesulfonyloxymino-5H-thiophen-2-iriden)-(2-methylphenyl) acetonitrile], IRGACURE PAG203, CGI725, 3 TFE-triazine [2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine], TME-triazine [2- [2- (5) -Methylfuran-2-yl) ethenyl] -4,6-bis (tri-chloromethyl) -s-triazine] MP-triazine [2- (methoxyphenyl) -4,6-bis (trichloromethyl) -s- Triazine], dimethoxy [2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (tri-chloromethyl) -s-triazine].

The blending amount of the cross-linking catalyst is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable resin or the curable monomer. Within such a range, a sufficiently cured product can be obtained. The blending amount of the cross-linking catalyst is more preferably 0.3 to 5 parts by mass, and further preferably 0.5 to 2 parts by mass.

When the acid generator is used as the cross-linking catalyst, the diffusion of the acid generated from the acid generator may be controlled by adding an acid scavenger as needed.
The acid trapping agent is not particularly limited, but a basic compound such as an amine (particularly an organic amine), a basic ammonium salt, or a basic sulfonium salt is preferable. Among these acid scavengers, organic amines are more preferable because of their excellent image performance.

Specific examples of the acid trapping agent include 1,5-diazabicyclo [4.3.0] -5-nonen, 1,8-diazabicyclo [5.4.0] -7-undecene, and 1,4-. Diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, pyridinium p-toluenesulfonate , 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine and the like. Among these, 1,5-diazabicyclo [4.3.0] -5-nonen, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] Organic amines such as octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, triethylamine and tributylamine are preferred.

The blending amount of the acid scavenger is preferably 20 parts by mass or less, more preferably 0.1 to 10 parts by mass, and further preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the acid generator. 5 parts by mass.

As the silicon-containing compound, a silicon-containing compound capable of forming a polysiloxane structure by a reaction, preferably a sol-gel reaction, is preferable.

In one embodiment, the silicon-containing compound can be an organosilicon compound containing carbon and silicon.

Examples of the organic silicon compound include Si—H compounds having a Si—H bond; Si—N compounds having a Si—N bond such as aminosilane compound, silazane, silylacetamide, and silylimidazole; monoalkoxysilane, dialkoxysilane, and tri. Si—O compounds having a Si—O bond such as alkoxysilane, tetraalkoxysilane, siloxane, silylester, silanol; Si—Cl compounds having a Si—Cl bond such as monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, etc. Halogenosilane, Si- (C) 4 compound, Si—Si compound having a Si—Si bond, vinylsilane, allylsilane, ethynylsilane and the like can be mentioned. That is, the organosilicon compound is at least one selected from the group consisting of Si—H compound, Si—N compound, halogenosilane, Si— (C) ₄ compound, Si—Si compound, vinylsilane, allylsilane, and ethynylsilane. It is preferably a compound of. As the organosilicon compound, a compound in which at least one atom selected from the group consisting of hydrogen, oxygen and halogen is bonded to Si is more preferable.

Specific examples of the above-mentioned organosilicon compound are shown below.
[Si—H compound]

[Si-N compound]

[Si—O compound]

[Harogenosilane]
Si-Cl compound:

Halogenosilanes other than Si-Cl compounds:

[Si- (C) ₄ compounds]

[Si-Si compound]

[Vinylsilane, allylsilane, and ethynylsilane]

The organosilicon compound has the following formula (2):
{Si (R ^a1 ) _s (R ^b1 ) _t (R ^c1 ) _u (R ^d1 ) _v (R ^e1 ) _w } _x (2)
[In the formula, R ^a1 , R ^b1 , R ^c1 and R ^d1 are independently hydrogen atom, halogen atom, alkoxyl group having 1 to 10 carbon atoms, amino group having 1 to 10 carbon atoms, and carbon number 1 to 1 respectively. It is an alkyl group of 10, an aryl group having 6 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, or a glycidyl group having 3 to 10 carbon atoms. ^Re1 is independently an -O-, -NH-, -C≡C-, or silane bond. s, t, u and v are independently 0 or 1, w is an integer of 0-4, and x is 1-20. When x is 1, s + t + u + v is 4, and w is 0. When x is 2 to 20, s + t + u + v are independently 0 to 4, w is independently 0 to 4, and when w is an integer of 1 or more, at least two. Si is connected in a straight line, a ladder type, an annular shape, or a double annular shape via ^Re1. ) Is more preferable. R ^a1 , R ^b1 , R ^c1 , and R ^d1 are monovalent groups attached to Si. ^Re1 is a divalent group attached to two Sis.

In formula (2), R ^a1 , R ^b1 , R ^c1 and R ^d1 are independent of each other, and at least one of them is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Other than that, it is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, or a glycidyl group having 3 to 10 carbon atoms. .. When x is 2 to 20, s + t + u + v are each independently 1 to 3, and w is preferably 1 to 3.

In the formula (2), R ^a1 , R ^b1 , R ^c1 and R ^d1 are independently alkyl groups having 1 to 6 carbon atoms, aryl groups having 6 to 8 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms, respectively. , Or an amino group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms.

In the above R ^a1 , R ^b1 , R ^c1 and R ^d1 , the number of carbon atoms of the alkyl group is preferably 1 to 5. The alkyl group may be chained, cyclic or branched. Further, the hydrogen atom may be replaced with a fluorine atom or the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like. For example, R ^a1 , R ^b1 , R ^c1 or R ^d1 includes a methyl group, an ethyl group and a propyl group, respectively. It is preferably a group or an isopropyl group. More preferably, it may be a methyl group or an ethyl group. The aryl group is preferably, for example, a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, or a dimethylphenyl group. As the halogen atom, fluorine, chlorine, bromine, or iodine is preferable, and chlorine is particularly preferable.

In the above R ^a1 , R ^b1 , R ^c1 and R ^d1 , the number of carbon atoms of the alkoxy group is preferably 1 to 5. The alkoxy group may be chain-like, cyclic, or branched. Further, the hydrogen atom may be replaced with a fluorine atom or the like. As the alkoxy group, a methoxy group, an ethoxy group, a propyroxy group, or a butoxy group is preferable, and a methoxy group or an ethoxy group is more preferable.

^Re1 is independently an -O-, -NH-, -C≡C-, or silane bond. As R ^e1 , -O-, -NH-, or -C≡C- is preferable. R ^e1 is a divalent group bonded to two ^Sis , and two or more silicon atoms are bonded to two or more silicon atoms ^{via Re1} in a linear, ladder-type, cyclic, or double-cyclic structure. Can be done. When x is an integer of 2 or more, silicon atoms may be bonded to each other. As a specific example of a preferable silicon-containing compound, one Si such as the above-mentioned Si-H compound, Si-N compound, halogenosilane, Si- (C) ₄ compound, Si-Si compound, vinylsilane, allylsilane, and ethynylsilane is used. Alternatively, a compound containing two or more can be mentioned.

In one embodiment, the silicon-containing compound is represented by the formula (3):
SiR ⁵ ₄ (3)
Or equation (4):
_{^{Si y O z R 6 4y-}} 2z (4)
It is a compound represented by.

In the above formula (3), R ⁵ independently represents a halogen atom or a hydrolyzable group.

In the above formula (4), R ⁶ independently represents a halogen atom or a hydrolyzable group. y is 2 or more, z is 1 or more, and 4y-2z is greater than 0.

It is also one of the preferred embodiments that the laminate of the present invention further contains an adhesive layer. If the adhesive layer is arranged between the decorative layer and the transparent layer, the decorative layer and the transparent layer can be firmly adhered to each other. When the laminate of the present invention has the resin layer between the decorative layer and the transparent layer, the resin layer and the decorative layer, or the resin layer and the transparent layer The resin layer and the decorative layer or the resin layer and the transparent layer can be firmly adhered to each other by arranging between the two.

The adhesive used for the adhesive layer is preferably one capable of forming a transparent layer, and examples thereof include an acrylic adhesive, a urethane adhesive, an epoxy adhesive, and a polyester adhesive. The film thickness is usually preferably 5 to 300 μm from the viewpoint of good cost and transparency. It is more preferably 10 to 100 μm, still more preferably 10 to 50 μm.

It is also one of the preferred embodiments that the present invention further includes a transparent substrate layer. The transparent base material layer is preferably arranged between the decorative layer and the transparent layer (Aspect 1). Further, when the laminate of the present invention has the resin layer between the decorative layer and the transparent layer, the transparent base material layer may be arranged between the resin layer and the decorative layer. Preferred (Aspect 2). Further, when the laminate of the present invention has the adhesive layer between the decorative layer and the transparent layer, the transparent base material layer is arranged between the transparent layer and the adhesive layer. Is also preferable (Aspect 3). Further, when the laminate of the present invention has the resin layer between the decorative layer and the transparent layer, and has the adhesive layer between the decorative layer and the resin layer, the above It is also preferable to arrange the transparent base material layer between the resin layer and the adhesive layer (Aspect 4).
Aspects 3 and 4 described above are more preferable, and Aspect 3 is even more preferable.

The material constituting the transparent base material layer is not particularly limited as long as it is transparent, and examples thereof include synthetic resin, glass, and ceramic.

Examples of the synthetic resin include cellulose-based resins such as triacetyl cellulose (TAC), diacetyl cellulose, and acetate butyrate cellulose, polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA). Polyetherketone, cyclic polyolefin, modified polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), polytrimethylpentene, poly (meth) acrylonitrile, etc. Ionomer, poly (meth) acrylic resin, polymethylmethacrylate, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), poly Polyether such as butylene terephthalate (PBT) and polycyclohexane terephthalate (PCT), polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyethersulfon, polysulfone, polyacetal (POM), Polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, fluororubber-based, Various thermoplastic elastomers such as chlorinated polyethylene, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester, silicone resin, polyurethane resin, etc., or copolymers, blends, polymer alloys mainly composed of these. Etc., and one or a combination of two or more of these can be used (for example, as a laminate of two or more layers). Among them, triacetyl cellulose, diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, poly (meth) acrylic resin, polyurethane resin, polyester, polycarbonate, polysulfone, polyether, polytrimethylpentene, polyether ketone, poly (Meta) acrylonitrile is preferred.

The transparent base material layer can be formed by a method such as molding.

In the laminated body of the present invention, it is one of the preferred embodiments that the transparent layer is arranged on the decorative layer. FIG. 1 is a cross-sectional view showing an embodiment of the laminated body of the present invention. The laminated body 10 shown in FIG. 1 includes a decorative layer 11 and a transparent layer 12 arranged on the decorative layer 11. The transparent layer 12 may contain only a compound having a perfluoro (poly) ether group, or may contain a compound having a perfluoro (poly) ether group and other resins. Other resins include a group consisting of a resin obtained by curing a curable resin, a resin obtained by curing a curable monomer, and a resin containing a polysiloxane structure formed by using a silicon-containing compound. At least one resin selected from the above is preferable.

In the laminated body of the present invention, it is also one of the preferred embodiments that the resin layer is arranged on the decorative layer and the transparent layer is arranged on the resin layer. .. FIG. 2 is a cross-sectional view showing an embodiment of the laminated body of the present invention. The laminate 20 shown in FIG. 2 includes a decorative layer 21, a resin layer 22 arranged on the decorative layer 21, and a transparent layer 23 arranged on the resin layer 22. The transparent layer 23 may contain only a compound having a perfluoro (poly) ether group, or may contain a compound having a perfluoro (poly) ether group and other resins.

In the laminate 20, the resin layer 22 is a resin obtained by curing a curable resin, a resin obtained by curing a curable monomer, and a resin containing a polysiloxane structure formed by using a silicon-containing compound. It is preferable that the transparent layer 23 contains a compound having a perfluoro (poly) ether group, and contains at least one resin selected from the group consisting of. In this embodiment, the transparent layer can be formed thinly, and both the resin layer and the transparent layer can have the fine concavo-convex structure. In the laminate 20 shown in FIG. 2, a relatively thin transparent layer 23 is arranged on the resin layer 22, and a fine uneven pattern is provided on both the resin layer 22 and the transparent 23.

In the laminated body of the present invention, it is one of the preferable embodiments that the adhesive layer is arranged on the decorative layer and the transparent layer is arranged on the adhesive layer. Is. FIG. 3 is a cross-sectional view showing an embodiment of the laminated body of the present invention. The laminate 30 shown in FIG. 3 includes a decorative layer 31, an adhesive layer 32 arranged on the decorative layer 31, and a transparent layer 33 arranged on the adhesive layer 32.

In the laminate of the present invention, the adhesive layer is arranged on the decorative layer, the resin layer is arranged on the adhesive layer, and the resin layer is placed on the resin layer. It is also one of the preferred embodiments that the transparent layer is arranged. FIG. 4 is a cross-sectional view showing an embodiment of the laminated body of the present invention. The laminate 40 shown in FIG. 4 is arranged on the decorative layer 41, the adhesive layer 42 arranged on the decorative layer 41, the resin layer 43 arranged on the adhesive layer 42, and the resin layer 43. Includes the transparent layer 44 and the like.

In the laminate of the present invention, the adhesive layer is arranged on the decorative layer, the transparent base material layer is arranged on the adhesive layer, and the transparent base material layer is arranged. It is one of the preferable aspects that the transparent layer is arranged on the top. FIG. 5 is a cross-sectional view showing an embodiment of the laminated body of the present invention. The laminate 50 shown in FIG. 5 includes a decorative layer 31, an adhesive layer 32 arranged on the decorative layer 31, a transparent base layer 51 arranged on the adhesive layer 32, and a transparent base layer. The transparent layer 33 arranged on the 51 is included. That is, in the laminated body 50 shown in FIG. 5, the transparent base material layer 51 is arranged between the adhesive layer 32 and the transparent layer 33 of the laminated body shown in FIG.
Further, in the laminate of the present invention, the adhesive layer is arranged on the decorative layer, the transparent base material layer is arranged on the adhesive layer, and the transparent base material is arranged. The resin layer is arranged on the layer, and the transparent layer is arranged on the resin layer (for example, between the adhesive layer 42 and the resin layer 43 of the laminate shown in FIG. 4). In addition, the transparent base material layer is arranged) is also one of the preferred embodiments.
Further, the transparent base material layer is arranged between the decorative layer 11 and the transparent layer 12 of the laminated body shown in FIG. 1 and between the decorative layer 21 and the resin layer 22 of the laminated body shown in FIG. You may.

It is also preferable that the adhesive layer is arranged under the decorative layer in each of the above-mentioned laminates because the laminate of the present invention can be applied to various uses. As an example, in a laminated body in which the transparent layer is arranged on the decorative layer, an embodiment in which the adhesive layer is arranged under the decorative layer will be described. FIG. 6 is a cross-sectional view showing an embodiment of the laminated body of the present invention. The laminate 60 shown in FIG. 6 includes an adhesive layer 61, a decorative layer 11 arranged on the adhesive layer 61, and a transparent layer 12 arranged on the decorative layer 11. That is, in the laminated body 60 shown in FIG. 6, the adhesive layer 61 is arranged under the decorative layer 11 of the laminated body shown in FIG.

The laminate of the present invention can be produced by a production method including the step of forming the decorative layer and the step of forming the transparent layer. In the above manufacturing method, the execution order of each step is not limited.

The method for forming the decorative layer is as described above.

Examples of the method for forming the transparent layer include a method of applying a composition containing the compound having a perfluoro (poly) ether group.

The composition can further contain at least one selected from the group consisting of the above-mentioned curable resin, the above-mentioned curable monomer, and the above-mentioned silicon-containing compound. In this case, it is formed by using a resin obtained by curing a curable resin by heating or light irradiation after the above application, a resin obtained by curing a curable monomer, and a silicon-containing compound. It is possible to form the transparent layer containing at least one resin selected from the group consisting of resins containing a polysiloxane structure.

Examples of the light include active energy rays, for example, electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, γ-rays, and the like.

It is preferable that the composition contains a solvent because the composition can be easily applied. Examples of the solvent include perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, bis). (Trifluoromethyl) benzene); Polyfluoroaliphatic hydrocarbons; Hydrofluoro ether (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 ) and other alkyl perfluoroalkyl ethers (perfluoroalkyl groups). And alkyl groups may be linear or branched)), hydrochlorofluorocarbons (Asahiclin AK-225 (trade name), etc.), methyl cellosolves, ethyl cellosolves, methyl cellosolve acetates, ethyl cellosolve acetates and other cellosolvents. Solvents; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, Ester solvents such as ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol Protinic glycol solvents such as monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; methanol , Ethanol, propanol, isopropanol, butanol, diacetone alcohol and other alcohol solvents; aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or as a mixture of two or more. Of these, hydrofluoro ether, propylene glycol solvent, ester solvent, ketone solvent, and alcohol solvent are preferable, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or perfluorobutyl ethyl ether (C _4). F ₉ OC ₂ H ₅ ), propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol are particularly preferable.

The composition may also contain the above-mentioned cross-linking catalyst, the above-mentioned sensitizer, the above-mentioned acid supplement, and the like.

Methods of applying the above composition include immersion coating, spin coating, flow coating, spray coating, slit coating, roll coating, gravure coating, microgravure coating, bar coating, die coating, screen printing and similar methods. ..

When the transparent layer has the fine concavo-convex pattern, in the step of forming the transparent layer, the composition is applied to form the transparent layer, and then the mold is pressed against the transparent layer to make the transparent layer transparent. The fine uneven pattern can be formed on the layer.

The pressing of the mold is preferably carried out after applying the composition and before the heating or the light irradiation.

The material of the mold can be appropriately selected depending on the purpose and necessity, and examples thereof include polymer resins such as metals, metal oxides, quartz and silicone, semiconductors, insulators, and composites thereof. Can be mentioned.

The shape of the mold is not particularly limited and may be a roll shape or a flat plate shape. Of these, a roll-shaped film having a fine concavo-convex structure formed on the outer peripheral surface is preferable because a roll-to-roll method for continuously producing a nanoimprint film for a long time can be performed.

As a method for forming the fine unevenness pattern on the transparent layer, in addition to pressing the mold, for example, a copying method such as a heat pressing method (embossing method), an injection molding method, a sol-gel method, or laminating a fine unevenness shaping sheet. Examples thereof include a method, and a suitable method can be appropriately selected depending on the material to be used and the like.

When the laminate of the present invention contains the transparent base material layer, it is preferable to apply the composition on the transparent base material layer in the step of forming the transparent base material layer. In this aspect, after the step of forming the transparent layer, it is preferable to arrange the decorative layer on the surface of the transparent base material layer opposite to the transparent layer.

When the laminate of the present invention contains the resin layer, it can be produced by a production method including a step of forming the decorative layer, a step of forming the resin layer, and a step of forming the transparent layer. In the above manufacturing method, the execution order of each step is not limited.

The method for forming the decorative layer is as described above.

As a method for forming the resin layer, a composition (a) containing at least one selected from the group consisting of the above-mentioned curable resin, the above-mentioned curable monomer and the above-mentioned silicon-containing compound is applied and then heated or heated. A method of irradiating light can be mentioned.

It is preferable that the composition (a) contains a solvent because the composition (a) can be easily applied. Examples of the solvent include perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, bis). (Trifluoromethyl) benzene); Polyfluoroaliphatic hydrocarbons; Hydrofluoro ether (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 ) and other alkyl perfluoroalkyl ethers (perfluoroalkyl groups). And alkyl groups may be linear or branched)), hydrochlorofluorocarbons (Asahiclin AK-225 (trade name), etc.), methyl cellosolves, ethyl cellosolves, methyl cellosolve acetates, ethyl cellosolve acetates and other cellosolvents. Solvents; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, Ester solvents such as ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol Protinic glycol solvents such as monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; methanol , Ethanol, propanol, isopropanol, butanol, diacetone alcohol and other alcohol solvents; aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or as a mixture of two or more. Of these, hydrofluoro ether, propylene glycol solvent, ester solvent, ketone solvent, and alcohol solvent are preferable, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or perfluorobutyl ethyl ether (C _4). F ₉ OC ₂ H ₅ ), propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol are particularly preferable.

The composition (a) may also contain the above-mentioned cross-linking catalyst, the above-mentioned sensitizer, the above-mentioned acid supplement, and the like.

Examples of the method of applying the composition (a) include immersion coating, spin coating, flow coating, spray coating, slit coating, roll coating, gravure coating, microgravure coating, bar coating, die coating, screen printing and similar methods. Can be mentioned.

Examples of the light include active energy rays, for example, electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, γ-rays, and the like.

Examples of the method for forming the transparent layer include a method of applying the composition (b) containing the compound having a perfluoro (poly) ether group.

It is preferable that the composition (b) contains a solvent because the composition (b) can be easily applied. Examples of the solvent include perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms (for example, perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (for example, bis). (Trifluoromethyl) benzene); Polyfluoroaliphatic hydrocarbons; Hydrofluoro ether (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 ) and other alkyl perfluoroalkyl ethers (perfluoroalkyl groups). And alkyl groups may be linear or branched)), hydrochlorofluorocarbons (Asahiclin AK-225 (trade name), etc.), methyl cellosolves, ethyl cellosolves, methyl cellosolve acetates, ethyl cellosolve acetates and other cellosolvents. Solvents; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, ethyl acetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, Ester solvents such as ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol Protinic glycol solvents such as monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; methanol , Ethanol, propanol, isopropanol, butanol, diacetone alcohol and other alcohol solvents; aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or as a mixture of two or more. Of these, hydrofluoro ether, propylene glycol solvent, ester solvent, ketone solvent, and alcohol solvent are preferable, and perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) and / or perfluorobutyl ethyl ether (C _4). F ₉ OC ₂ H ₅ ), propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol are particularly preferable.

The method of applying the composition (b) includes immersion coating, spin coating, flow coating, spray coating, slit coating, roll coating, gravure coating, microgravure coating, bar coating, die coating, screen printing and similar methods. Can be mentioned.

When the transparent layer has the fine concavo-convex pattern, in the step of forming the transparent layer, the composition (b) is applied to the resin layer to form the transparent layer, and then the transparent layer is molded. The fine concavo-convex pattern can be formed on the resin layer and the transparent layer by pressing.

Further, after applying the composition (b) to the mold, the mold may be pressed against the resin layer to form the transparency, and at the same time, the fine uneven pattern may be formed on the resin layer and the transparent layer. Good.

The pressing of the mold is preferably carried out after applying the composition (a) or the compositions (a) and (b) and before the heating or the light irradiation.

The material of the mold can be appropriately selected depending on the purpose and necessity, and examples thereof include polymer resins such as metals, metal oxides, quartz and silicone, semiconductors, insulators, and composites thereof. Can be mentioned.

The shape of the mold is not particularly limited and may be a roll shape or a flat plate shape. Of these, a roll-shaped film having a fine concavo-convex structure formed on the outer peripheral surface is preferable because a roll-to-roll method for continuously producing a nanoimprint film for a long time can be performed.

As a method for forming the fine unevenness pattern on the resin layer and the transparent layer, in addition to pressing the mold, for example, a heat pressing method (embossing method), an injection molding method, a duplication method such as a sol-gel method, or fine unevenness addition. Examples thereof include a method of laminating a shape sheet, and a suitable method can be appropriately selected depending on the material to be used and the like.

When the laminate of the present invention contains the transparent base material layer, it is preferable to apply the composition (a) on the transparent base material layer in the step of forming the resin layer. In this embodiment, after the step of forming the resin layer and the step of forming the transparent layer, it is preferable to arrange the decorative layer on the surface of the transparent base material layer opposite to the resin layer.

Any of the above-mentioned manufacturing methods may include a step of forming an adhesive layer. For example, as a method for producing the laminate 30 shown in FIG. 3, after the step of forming the transparent layer, the adhesive is applied to the transparent layer or the decorative layer, and the decorative layer and the transparent layer are combined. There is a method of sticking together via the above-mentioned adhesive layer.

The adhesive can be applied by a method such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, die coating and the like. When applying the above adhesive, any diluting solvent such as 1-methoxy-2-propanol, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, acetone and the like can be used, if necessary.

The laminate of the present invention can be arranged on the surface of various parts, and can be suitably used as, for example, an automobile interior part. For example, it can be applied to the following applications.
Center panel, center cluster, center console area, in-vehicle touch panel, audio panel / navigation area, door ornaments, small parts around the seat, wheel ornaments, heater control panel, display cover, instrument panel (instrument panel), console Box, Air Conditioner Outlet, Cup Holder, Grab Box, Shift Panel, Ash Tray, Door Trim Ornament, Garnish, Meter Cluster, Senkra Side Panel, Meter Bezel, Ornament Panel, Meter Cover, Door Lock Pezel, Steering Wheel, Power Window Switch Base, Dashboard

The laminate of the present invention can also be applied to the following uses.
Interior / exterior parts of various vehicles: Furniture for trains, aircraft, ships, etc., Home appliances: Front panels for AV equipment, furniture products, etc., buttons, emblems, surface decorative materials, housing for mobile phones, display windows, buttons, etc. Building materials: Furniture Exterior materials, wall surfaces, ceilings, floors and other building interior materials, siding and other exterior walls, walls, roofs, gates, windshields and other building exterior materials, window frames, doors, handrails, thresholds, lintels and other surface makeup Materials and others: Various packaging containers such as bottles, cosmetic containers, accessory cases, packaging materials, miscellaneous goods such as accessories

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

Example 1
(Manufacturing of mold)
A cylindrical nickel (Ni) sleeve having a radius of about 300 mm and a roll width of about 1500 mm was prepared. After the nickel sleeve was alkaline degreased, it was washed with pure water (washing step). Next, the nickel sleeve was immersed in an electrodeposition liquid, and a resin was formed on the surface of the nickel sleeve by an electrodeposition treatment (electrodeposition step). The voltage was 30 to 40 V, and the electrodeposition treatment was performed for 300 seconds. As a result, an electrodeposition film (insulating film) having a thickness of 7 μm was formed.
Subsequently, an aluminum (Al) film having a film thickness of 10 μm was formed on the insulating film by sputtering coating.
Next, the nickel sleeve was immersed in a 0.1 mol / l oxalic acid solution, electrolyzed at 18 ° C. for 35 seconds, and then immersed in pure water for washing with water (anodizing step). Subsequently, it was immersed in a 0.3 mol / l phosphoric acid solution and etched at 18 ° C. for 19 minutes, and then immersed in pure water again and washed with water (etching step).
The cycle of the above anodizing step and etching step was repeated 6 times, and finally the anodizing step was performed to complete the step. By continuously repeating such anodizing step and etching step, abnormally grown particles are formed, the distance between the bottom points of adjacent holes (recesses) is 380 nm or less, and the aluminum film is formed. It is possible to form a large number of minute holes having a tapered shape (tapered shape) toward the inside.
From this, a cylindrical mold on the surface of _{alumina (Al 2} O _{3) was completed.}

(Manufacturing of antifouling agent A (compound having a perfluoro (poly) ether group))
First, in the reactor, 57 g of "Sumijour N3300" (cyclic trimer of hexamethylene diisocyanate, NCO group content: 21.9%) manufactured by Sumitomo Bayer Urethane Co., Ltd. was added to "Zeorolla" manufactured by Nippon Zeon Co., Ltd. It was dissolved in 1300 g of "H" (registered trademark), and 0.1 g of dibutyltin dilaurate (primary reagent) manufactured by Wako Pure Chemical Industries, Ltd. was added. Thereafter, while stirring at room temperature, it was added dropwise to _{"CF 3 CF 2 O- (CF 2} CF 2 CF 2 O) 11 -CF 2 CF 2 CH 2 OH " 244 g, and stirring was continued at room temperature overnight. Then, the temperature was increased to 40 ° C., and 24.4 g of hydroxyethyl acrylate was added dropwise and stirred. The end point of the reaction was the time when the absorption of NCO was completely eliminated by IR. As a result, antifouling agent A was obtained. The content of the active ingredient in the antifouling agent A was 20% by weight.

(Manufacturing of laminate)
As the transfer resin, urethane acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (product name: UA-7100): 31% by weight, polyfunctional acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (product name: ATM-35E): 40% by weight, Polyfunctional acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (product name: A-TMM-3LM-N): 27.5% by weight, photopolymerization initiator manufactured by BASF (product name: IRGACURE819): 1.5% by weight To the mixed monomer mixture, 5% of the antifouling agent A was added, and the solution was applied onto the triacetyl cellulose by the gravure coating method. Using the prepared mold, the fine concavo-convex structure was transferred by a roll-to-roll method at a transfer rate of about 5 m / min, and then the resin was cured by UV irradiation at ^{600 mJ / cm 2 to prepare a laminated film.} ..
The laminate film thus obtained was laminated on a black film separately prepared as a decorative layer to obtain a laminate I.

Comparative Example 1
A laminate II was obtained by using the same method as in Example 1 except that the antifouling agent A was not added.

The contact angle on the transparent layer side of the laminates obtained in Examples and Comparative Examples was measured, and the antifouling property and design property were verified by the following methods. The results are shown in Table 1.

(Contact angle / antifouling property)
Using a contact angle measuring device (contact angle meter DM701 manufactured by Kyowa Interface Science Co., Ltd.), 1 μl of water or 2 μl of n-hexadecane (HD) was dropped, and then the contact angle was measured 1 second after the dropping. After the measurement, each droplet was wiped with a tissue, and the wiping property was evaluated as follows.
◯: No trace of droplets remains.
Δ: A slight trace of droplets remains.
X: Traces of droplets remain clearly.

(Creativity)
The appearance of the black color of the decorative layer of the laminated body under the light of a fluorescent lamp was visually evaluated as follows.
◯: There is almost no reflection of the fluorescent lamp, and the black color of the decorative layer looks jet black.
Δ: There is a slight reflection of the fluorescent lamp, and the black color of the decorative layer is not so jet black.
X: The reflection of the fluorescent lamp is intense, and the black color of the decorative layer is not jet black.

Further, the fluorine content (Fatamic conc.) On the outermost surface of the laminate obtained in Examples and Comparative Examples on the transparent layer side was measured by measuring the surface elements with the X-ray photoelectron analyzer ESCA-3400 manufactured by Shimadzu Corporation. (Approximately 10 nm in the depth direction). The results are shown in Table 1.

10, 20, 30, 40, 50, 60 Laminated body 11, 21, 31, 41 Decorative layer 12, 23, 33, 44 Transparent layer 22, 43 Resin layer 32, 42, 61 Adhesive layer 51 Transparent base material layer

Claims (5)

A laminated body including a decorative layer and a transparent layer.
Wherein a transparent layer is a fine concavo-convex pattern, and a compound having a perfluoroalkyl (poly) ether group seen including,
The compound contained in the transparent layer
A group consisting of a compound obtained by curing a compound (F) having a perfluoro (poly) ether group and a curable moiety, and a compound (G) having a perfluoro (poly) ether group and a hydrolyzable group. At least one of the more selected
The laminate is a laminate characterized by being a component for an automobile interior. The perfluoro (poly) ether group is
Formula:-(OC ₄ F ₈ ) _a- (OC ₃ F ₆ ) _b- (OC ₂ F ₄ ) _c- (OCF ₂ ) _d-
(In the equation, a, b, c and d are independently integers of 0 or 1 or more, the sum of a, b, c and d is 1 or more, and a, b, c or d denoted the order of the repeating units enclosed in parentheses is optional in the formula.) a group represented by claim 1 laminate according. The transparent layer is further composed of a resin obtained by curing a curable resin, a resin obtained by curing a curable monomer, and a resin containing a polysiloxane structure formed by using a silicon-containing compound. The laminate according to claim 1 or 2, which contains at least one resin selected from the group. Further, it is selected from the group consisting of a resin obtained by curing a curable resin, a resin obtained by curing a curable monomer, and a resin containing a polysiloxane structure formed by using a silicon-containing compound. The laminate according to claim 1, 2 or 3, which comprises a resin layer containing at least one kind of resin. The laminate according to claim 1, 2, 3 or 4 , further comprising an adhesive layer.

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