JP7125592B2 - Novel compound having isocyanuric skeleton and composition containing same - Google Patents

Description

TECHNICAL FIELD The present invention relates to novel compounds having an isocyanuric skeleton and compositions containing the same.

Certain fluorine-containing silane compounds are known to provide excellent water repellency, oil repellency, antifouling properties, etc. when used for surface treatment of substrates. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as a "surface treatment layer") can be applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. It is

Patent Document 1 describes an antifouling coating agent containing an isocyanuric acid compound represented by the following formula.

(Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independently alkyl groups having 1 to 6 carbon atoms, n and m are independently integers of 0 to 2, q is an integer of 1 to 20 )

Korean Patent Publication No. 10-2014-0018556

However, there is a constant need for new antifouling agents to impart superior antifouling properties to a wide variety of substrates.

An object of the present invention is to provide a novel compound that can be suitably used as an antifouling agent in view of the above situation.

The present invention is a compound characterized by being represented by formula (1).

Formula (1):

(Wherein, R ¹ is a monovalent organic group containing a polyether chain, X ¹ and X ² independently represent a monovalent group, and the polyether chain is
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary) is the chain represented)

At least one or both of X ¹ and X ² are independently monovalent organic groups comprising a polyether chain, the polyether chain comprising:
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary) Preferred are the chains represented.

X ¹ is preferably a monovalent crosslinkable group.

X ² is preferably a monovalent crosslinkable group.

X ¹ and X ² are preferably independently monovalent crosslinkable groups.

X ¹ is a monovalent crosslinkable group containing a polyether chain, and the polyether chain is
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary) Preferred are the chains represented.

^X2 is a monovalent crosslinkable group comprising a polyether chain, the polyether chain comprising
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary) Preferred are the chains represented.

X ¹ and X ² are independently monovalent crosslinkable groups comprising a polyether chain, the polyether chain comprising:
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary) Preferred are the chains represented.

The crosslinkable group includes a monovalent Si-containing group, an acryloyl group, a methacryloyl group, an epoxy group, a glycidyl group, an oxetane group, an isocyanate group, a vinyl group, an allyl group, a vinyloxy group, a carboxyl group, a mercapto group, an amino group, a hydroxy group, phosphonyl group, cyclic acid anhydride group, lactone group, lactam group, -OC(O)Cl group, triazine group, imidazole group, conjugated olefin group, acetylene group, diazo group, aldehyde group, ketone group, alkyl boron group , an alkylaluminum group, an alkyltin group, an alkylgermanium group, an alkylzircone group, and a monovalent group containing any of these groups.

X ¹ is H, alkyl group, halogenated alkyl group, alkyl ester group, halogenated alkyl ester group, alkyl ether group, halogenated alkyl ether group, alkylamide group, halogenated alkylamide group, uryl group, halogenated uril group, urea group, halogenated urea group, —OCOOR ^j (R ^j is an alkyl group or a halogenated alkyl group), —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group) , a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, an aryl halide group, a silicone residue (excluding those having a reactive group) and a silyl It is preferably at least one selected from the group consisting of sesquioxane residues (excluding those having reactive groups).

X2 is H, alkyl group, halogenated alkyl group, alkyl ester group, halogenated alkyl ester group, alkyl ether group, halogenated alkyl ether group, alkylamide group, halogenated alkylamide group, ^uryl group, halogenated uril group, urea group, halogenated urea group, —OCOOR ^j (R ^j is an alkyl group or a halogenated alkyl group), —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group) , a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, an aryl halide group, a silicone residue (excluding those having a reactive group) and a silyl It is preferably at least one selected from the group consisting of sesquioxane residues (excluding those having reactive groups).

X ¹ and X ² are independently H, an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkylamide group, a halogenated alkylamide group, uryl group, halogenated uryl group, urea group, halogenated urea group, —OCOOR ^j (R ^j is an alkyl group or a halogenated alkyl group), —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, a halogenated aryl group, a silicone residue (with a reactive group and silsesquioxane residues (excluding those having a reactive group).

Since the novel compound of the present invention has the above structure, it exhibits excellent antifouling properties and can be suitably used as an antifouling agent. In addition, it exhibits excellent releasability and can be suitably used as a release agent.

The present invention will be specifically described below.

The compound of the present invention is characterized by being represented by formula (1).

（式中、Ｒ^１はポリエーテル鎖を含む一価の有機基、Ｘ^１及びＸ^２は、独立に、一価の基を表し、上記ポリエーテル鎖は、
式：－（ＯＣ_６Ｆ_１２）_ｍ１１－（ＯＣ_５Ｆ_１０）_ｍ１２－（ＯＣ_４Ｆ_８）_ｍ１３－（ＯＣ_３Ｘ^１０ _６）_ｍ１４－（ＯＣ_２Ｆ_４）_ｍ１５－（ＯＣＦ_２）_ｍ１６－
（式中、ｍ１１、ｍ１２、ｍ１３、ｍ１４、ｍ１５およびｍ１６は、独立に、０又は１以上の整数、Ｘ^１０は独立にＨ、Ｆ又はＣｌ、各繰り返し単位の存在順序は任意である）で表される鎖である） Formula (1):

(Wherein, R ¹ is a monovalent organic group containing a polyether chain, X ¹ and X ² independently represent a monovalent group, and the polyether chain is
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary) is the chain represented)

R ¹ is preferably a monovalent organic group containing a polyether chain (excluding those containing a urethane bond).

As ^X10 , F is preferred.
Each of m11 to m16 is preferably an integer of 0 to 200, more preferably an integer of 0 to 100. In total, m11 to m16 are preferably an integer of 1 or more, more preferably an integer of 5 or more, and still more preferably an integer of 10 or more. The sum of m11 to m16 is preferably an integer of 200 or less, more preferably an integer of 100 or less. In total, m11 to m16 are preferably an integer of 10-200, more preferably an integer of 10-100.

In the above polyether chain, each repeating unit may be linear or branched, preferably linear. For example, - _{( OC6F12} )- is - _{( OCF2CF2CF2CF2CF2CF2} )-, - _{( OCF ( CF3 ) CF2CF2CF2CF2 )} -, - _{( OCF 2} CF (CF ₃ ) CF ₂ CF ₂ CF ₂ )-, - (OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ )-, - (OCF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ )- , -(OCF ₂ CF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, etc., but preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-. - _{( OC5F10} )- is - _{( OCF2CF2CF2CF2CF2} )-, - _{( OCF ( CF3} ) _CF2CF2CF2 )-, - _{( OCF2CF ( CF3} ) CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, but preferably -( OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )—. -( _OC4F8 )- is - _{( OCF2CF2CF2CF2} )-, - ₍ OCF _{( CF3} ) _CF2CF2 )-, - _{( OCF2CF ( CF3} ) _CF2 )- , -( _OCF2CF2CF ( _CF3 ))-, -(OC( _CF3 ) _2CF2 )-, -( _{OCF2C (CF3)2 ) -} , -(OCF _{( CF3} )CF( Any of CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-, preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- is any of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF ₂ CF(CF ₃ ))- but preferably -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- or -(OCF(CF ₃ ))-, but is preferably -(OCF ₂ CF ₂ )- be.

In one embodiment, the polyether chain is a chain represented by -(OC ₃ F ₆ ) _m14 -, where m14 is an integer from 1 to 200. The polyether chain is preferably a chain represented by -(OCF ₂ CF ₂ CF ₂ ) _m14 - (wherein m14 is an integer from 1 to 200) or -(OCF(CF ₃ )CF ₂ ) _m14 — (wherein m14 is an integer of 1 to 200), more preferably —(OCF ₂ CF ₂ CF ₂ ) _m14 — (wherein m14 is an integer of 1 to 200) is a chain represented by m14 is preferably an integer of 5-200, more preferably an integer of 10-200.

In another embodiment, the polyether chain is -(OC ₄ F ₈ ) _m13 -(OC ₃ F ₆ ) _m14 -(OC ₂ F ₄ ) _m15 -(OCF ₂ ) _m16 -, where m13 and m14 are , are each integers of 0 to 30, and m15 and m16 are each integers of 1 to 200. m13 to m16 are a total of integers of 5 or more.The order of existence of each repeating unit is arbitrary. is a chain represented by Each of m15 and m16 is preferably an integer of 5-200, more preferably an integer of 10-200. m13 to m16 are preferably an integer of 10 or more in total. The polyether chain is preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _m13 -(OCF ₂ CF ₂ CF ₂ ) _m14 -(OCF ₂ CF ₂ ) _m15 -(OCF ₂ ) _m16 -. In one embodiment, the polyether chain is -(OC ₂ F ₄ ) _m15 -(OCF ₂ ) _m16 -, where m15 and m16 are each an integer from 1 to 200. The presence of each repeating unit The order may be arbitrary). Each of m15 and m16 is preferably an integer of 5-200, more preferably an integer of 10-200.

In yet another aspect, the polyether chain is a group represented by -(R ^m1 -R ^m2 ) _m17 -. wherein R ^m1 is OCF ₂ or OC ₂ F ₄ , preferably OC ₂ F ₄ . wherein R ^m2 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 independently selected from these groups is a combination of two or three groups that are Preferably R ^m1 is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ or from OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ selected groups or a combination of two or three groups independently selected from 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 for example -OC ₂ F ₄ OC ₃ F ₆ -, -OC _{2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F _ _ _ _ _ _ _ _ _ _ 8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC _ _ _ _ _ _ _ _ _ _ 4F8- , -OC2F4OC3F6OC2F4- , -OC2F4OC3F6OC3F6- , -OC2F4OC4F8OC2F4- , _ _ _ _ _ _ _ _ _ _ _ _ -OC3F6OC2F4OC2F4- , -OC3F6OC2F4OC3F6- , -OC3F6OC3F6OC2F4- , and -OC4F _ _ _ _ _ _ _ _ _ _ _ 8} OC ₂ F ₄ OC ₂ F ₄ - and the like. m17 is an integer of 2 or more, preferably 3 or more, more preferably 5 or more, and 100 or less, preferably 50 or less. _In the above _formula , _OC2F4 , _{OC3F6 , OC4F8} , _OC5F10 and _OC6F12 may be _linear or _branched , preferably linear . In this aspect, the polyether chain is preferably -(OC ₂ F ₄ -OC ₃ F ₆ ) _m17 - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _m17 -.

In the polyether chain, the ratio of m15 to m16 (hereinafter referred to as "m15/m16 ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2 , more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By setting the m15/m16 ratio to 10 or less, the surface treatment layer is further improved in slipperiness, friction durability and chemical resistance (for example, durability against artificial perspiration). The smaller the m15/m16 ratio, the more improved the lubricity and friction durability of the surface treatment layer. On the other hand, by setting the m15/m16 ratio to 0.1 or more, the stability of the compound can be further enhanced. The higher the m15/m16 ratio, the more stable the compound.

The polyether chain is
Formula: _- ( _OCF2CF2CX112 ) ⁿ¹¹ ( _{OCF2CF ( CF3} )) _{n12 ( OCF2CF2} ) _{n13 ( OCF2} ) _{n14 ( OC4F8} ) _n15 -
(Wherein, ⁿ¹¹ , n12, n13, n14 and n15 are independently integers of 0 or 1 or more, X11 is independently H, F or Cl, and the order of existence of each repeating unit is arbitrary) chain, and
Formula: -(OC ₂ F ₄ -R ¹¹ ) _f -
wherein R ¹¹ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ and f is an integer from 2 to 100. At least one strand may be selected.

X ¹¹ is preferably F.
Each of n11 to n15 is preferably an integer of 0 to 200. The sum of n11 to n15 is preferably an integer of 2 or more, more preferably an integer of 5 to 300, still more preferably an integer of 10 to 200, and an integer of 10 to 100. is particularly preferred.

R ¹¹ 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 independently selected from 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 for example -OC ₂ F ₄ OC ₃ F ₆ -, -OC _{2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F _ _ _ _ _ _ _ _ _ _ 8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC _ _ _ _ _ _ _ _ _ _ 4F8- , -OC2F4OC3F6OC2F4- , -OC2F4OC3F6OC3F6- , -OC2F4OC4F8OC2F4- , _ _ _ _ _ _ _ _ _ _ _ _ -OC3F6OC2F4OC2F4- , -OC3F6OC2F4OC3F6- , -OC3F6OC3F6OC2F4- , and -OC4F _ _ _ _ _ _ _ _ _ _ _ 8} OC ₂ F ₄ OC ₂ F ₄ - and the like. f is an integer of 2-100, preferably an integer of 2-50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be linear or branched, preferably linear. In this aspect, the formula -(OC ₂ F ₄ -R ¹¹ ) _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 −.

In the compound of the present invention, the number average molecular weight of the polyether chain portion is not particularly limited, but is for example 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10 , 000. The number average molecular weight is a value measured by ¹⁹ F-NMR.

In another aspect, the number average molecular weight of the polyether chain portion is from 500 to 30,000, preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, even more preferably from 2,000 to It can be 10,000, such as 3,000 to 6,000.

In another aspect, the polyether chain portion may have a number average molecular weight of 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.

R ¹ has the formula: R ³ -(OR ² ) _a -L-((OR ² ) _a is the above polyether chain, R ³ is an alkyl group or a fluorinated alkyl group, L is a single bond or a divalent link group) is preferably a monovalent organic group.

The number of carbon atoms in R ³ is preferably 1-16, more preferably 1-8.
R ³ may be linear or branched, and is preferably a linear or branched alkyl group having 1 to 16 carbon atoms or a fluorinated alkyl group. A branched C 1-8 alkyl group or a fluorinated alkyl group is more preferable, and a linear or branched C 1-6 alkyl group or a fluorinated alkyl group is even more preferable. , a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group is even more preferable, and a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms or a fluorinated alkyl group is particularly preferable.

R ³ is preferably a fluorinated alkyl group having 1 to 16 carbon atoms, more preferably a CF ₂ H—C _1-15 fluoroalkylene group or a perfluoroalkyl group having 1 to 16 carbon atoms. More preferably, it is a perfluoroalkyl group of number 1-16.

The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, preferably linear or branched and having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms. and 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 .

L is a single bond or a divalent linking group that directly bonds to the ring of formula (1). L is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, a single bond, an alkylene group having 1 to 10 carbon atoms, Alternatively, a C 1-10 divalent hydrocarbon group containing at least one bond selected from the group consisting of an ether bond and an ester bond is more preferred.

As L
Formula: -(CX ¹²¹ X ¹²² ) _o -(L ¹ ) _p -(CX ¹²³ X ¹²⁴ ) _q -
(Wherein, X ¹²¹ to X ¹²⁴ are independently H, F, OH, or —OSi(OR ¹²¹ ) ₃ (three R ¹²¹ are independently alkyl groups having 1 to 4 carbon atoms), L ¹ is , -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, or -NHC(=O)NH- (the left side of each bond is bound to CX ¹²¹ X ¹²² ), o is an integer of 0 to 10, p is 0 or 1, q is an integer of 1 to 10) More preferred.
L ¹ is preferably -O- or -C(=O)O-.
As L
Formula: -(CF ₂ ) _m11 -(CH ₂ ) _m12 -O-(CH ₂ ) _m13 -
(wherein m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, m13 is an integer of 1 to 3),
Formula: -(CF ₂ ) _m14 -(CH ₂ ) _m15 -O-CH ₂ CH(OH)-(CH ₂ ) _m16 -
(wherein m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, m16 is an integer of 1 to 3),
Formula: -(CF ₂ ) _m17 -(CH ₂ ) _m18 -
(Wherein, m17 is an integer of 1 to 3, m18 is an integer of 1 to 3), or
Formula: -(CF ₂ ) _m19 -(CH ₂ ) _m20 -O-CH ₂ CH(OSi(OCH ₃ ) ₃ )-(CH ₂ ) _m21 -
(wherein m19 is an integer of 1 to 3, m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3) is particularly preferred.

L is not particularly limited, but specifically includes -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH ) —CH ₂ —, —(CF ₂ ) _n — (n is an integer of 0 to 4), —CH ₂ —, —C ₄ H ₈ —, —(CF ₂ ) _n —(CH ₂ ) _m —(n , m are independently integers of 0 to 4), -CF ₂ CF ₂ CH ₂ OCH ₂ CH(OH)CH ₂ -, -CF ₂ CF ₂ CH ₂ OCH ₂ CH (OSi(OCH ₃ ) ₃ ) CH ₂ — and the like.

At least one or both of X ¹ and X ² may independently be a monovalent organic group comprising a polyether chain as described above. Suitable groups for the above organic groups are the same as for R ¹ .

X ¹ may be a monovalent crosslinkable group.

X ² may also be a monovalent crosslinkable group.

Also, X ¹ and X ² may independently be monovalent crosslinkable groups.

The above-mentioned crosslinkable group contributes to adhesiveness with a substrate and contributes to a crosslinking reaction. The crosslinkable groups may chemically react with the material of the substrate. Moreover, the crosslinkable groups may react with each other, or may react with a curable resin, a curable monomer, or the like, which will be described later.

As the crosslinkable group, a monovalent crosslinkable group having thermal crosslinkability or photocrosslinkability is preferable.

The crosslinkable group includes a monovalent Si-containing group, an acryloyl group, a methacryloyl group, an epoxy group, a glycidyl group, an oxetane group, an isocyanate group, a vinyl group, an allyl group, a vinyloxy group, a carboxyl group, a mercapto group, an amino group, a hydroxy group, phosphonyl group, cyclic acid anhydride group, lactone group, lactam group, -OC(O)Cl group, triazine group, imidazole group, conjugated olefin group, acetylene group, diazo group, aldehyde group, ketone group, alkyl boron group , an alkylaluminum group, an alkyltin group, an alkylgermanium group, an alkylzircone group, and at least one crosslinkable group selected from the group consisting of monovalent groups containing any of these groups, At least selected from the group consisting of monovalent Si-containing groups, acryloyl groups, epoxy groups, glycidyl groups, vinyl groups, allyl groups, hydroxy groups, ketone groups, and monovalent groups containing any of these groups More preferably, it is one type of crosslinkable group.

"A monovalent group containing any of these groups" includes a monovalent crosslinkable group containing a hydrocarbon chain containing any of these groups at the side chain end or main chain end, any of these groups and a monovalent crosslinkable group containing a polyether chain containing at the side chain end or at the main chain end.

That is, X ¹ may be a monovalent crosslinkable group containing the above polyether chain.

Alternatively, ^X2 may be a monovalent crosslinkable group containing the above polyether chain.

Also, X ¹ and X ² may independently be monovalent crosslinkable groups containing the above polyether chains.

The polyether chain is
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary) is the chain represented.
The polyether chain is
Formula: _- ( _OCF2CF2CX112 ) ⁿ¹¹ ( _{OCF2CF ( CF3} )) _{n12 ( OCF2CF2} ) _{n13 ( OCF2} ) _{n14 ( OC4F8} ) _n15 -
(Wherein, ⁿ¹¹ , n12, n13, n14 and n15 are independently integers of 0 or 1 or more, X11 is independently H, F or Cl, and the order of existence of each repeating unit is arbitrary) chain, and
Formula: -(OC ₂ F ₄ -R ¹¹ ) _f -
wherein R ¹¹ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ and f is an integer from 2 to 100. At least one strand may be selected.

Chains suitable as the polyether chain are the same as ^R1 .

The Si-containing group is preferably at least one group selected from the group consisting of silane-containing reactive cross-linking groups, silicone residues, silsesquioxane residues and silazane groups.

As the silane-containing reactive cross-linking group,
Formula: -L ² -{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n
(wherein L ² is a single bond or a divalent linking group, R ^a , R ^b and R ^c are the same or different and are hydrogen, halogen, an alkoxy group having 1 to 10 carbon atoms, an amino group having 1 to 10 carbon atoms, acetoxy group having 1 to 10 carbon atoms, allyl group having 3 to 10 carbon atoms, or glycidyl group having 3 to 10 carbon atoms, and R ^d is the same or different and is -O-, -NH-, -C ≡C- or a silane bond, s, t and u are the same or different and are 0 or 1, v is an integer of 0 to 3, and n is an integer of 1 to 20. n is if 1, s + t + u is 3 and v is 0. if n is 2 to 20, s + t + u are the same or different and are 0 to 2, v is the same or different and is 0 to 2; When v is an integer of 1 or more, at least two Si are bonded via R ^d in a linear, ladder-like, cyclic, or polycyclic manner.) is preferred. R ^a , R ^b and R ^c are monovalent groups bonded to Si. R ^d is a divalent group bonded to two Si.

R ^a , R ^b and R ^c are the same or different, and at least one is hydrogen, halogen, an alkoxy group having 1 to 10 carbon atoms, or an amino group having 1 to 10 carbon atoms; It is preferably an acetoxy group having 1 to 10 carbon atoms, an allyl group having 3 to 10 carbon atoms, or a glycidyl group having 3 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. When n is 2-20, s+t+u are the same or different, preferably 0-2, and v is 0-2.

In R ^a , R ^b and R ^c , the halogen is preferably Cl, Br or I, more preferably Cl.

In R ^a , R ^b and R ^c , the alkoxy group preferably has 1 to 5 carbon atoms. The alkoxy group may be linear, cyclic, or branched. Moreover, a hydrogen atom may be substituted with a fluorine atom or the like. The alkoxy group is preferably a methoxy group, an ethoxy group, a propyloxy group or a butoxy group, more preferably a methoxy group or an ethoxy group.

R ^d are the same or different and are —O—, —NH—, —C≡C—, or a silane bond. R ^d is preferably -O-, -NH- or -C≡C-. R ^d is a divalent group bonded to two Si, and two or more silicon atoms are bonded by R ^d via R ^d in a linear, ladder-shaped, cyclic, or multicyclic manner. can be done. When n is an integer of 2 or more, silicon atoms may be bonded to each other.

R ^d may also be the same or different and may be a group represented by -Z-SiR ^d1 _p' R ^d2 _q' R ^d3 _r' .

In the formula, Z is the same or different and represents a single bond or a divalent linking group.

Z specifically includes -C ₂ H ₄ -, -C ₃ H ₆ -, -CO-O-CH ₂ -CH(OH)-CH ₂ -, -CH ₂ -, -C ₄ H ₈ - etc.

In the formula, R ^d1 is the same or different and represents R ^d' . ^Rd' has the same meaning as ^Rd .

In ^Rd , the maximum number of Sis connected in a straight chain via the Z group is five. That is, when at least one R ^d1 is present in R ^d above, two or more Si atoms linked in a straight chain via a Z group are present in R ^d . The maximum number of Si atoms linked in a chain is five. The “number of Si atoms linearly linked via Z groups in R ^d ” is equal to the repeating number of —Z—Si— linearly linked in R ^d .

For example, the following shows an example in which a Si atom is linked via a Z group in ^Rd .

In the above formula, * means the site of bonding to Si in the main chain, ... is that a predetermined group other than ZSi is bonded, that is, all three bonds of the Si atom are ... , it means the end point of the ZSi iteration. In addition, the number on the right side of Si means the number of occurrences of Si linked in a straight chain via Z groups counted from *. That is, the chain in which the ZSi repeat terminates at Si ² has "the number of Si atoms connected in a straight chain via the Z group in R ^d " of 2. Similarly, Si ³ and Si ⁴ and the chains with ZSi repeats terminating at Si ⁵ have 3, 4 and 5 “number of Si atoms linearly linked via Z groups in R ^d ”, respectively. As is clear from the above formula, a plurality of ^ZSi chains are present in Rd, but they do not have to all have the same length, and each may have an arbitrary length.

In a preferred embodiment, as shown below, "the number of Si atoms linearly linked via a Z group in R ^d " is 1 (left formula) or 2 (right formula) in all chains. formula).

In one embodiment, the number of Si atoms linearly linked via a Z group in R ^d is 1 or 2, preferably 1.

In the formula, R ^d2 are the same or different and represent a hydroxyl group or a hydrolyzable group. The hydroxyl group is not particularly limited, but may be one produced by hydrolysis of a hydrolyzable group.

Preferably, R ^d2 is -OR, wherein R represents a substituted or unsubstituted C _1-3 alkyl group, more preferably a methyl group.

In the formula, R ^d3 are the same or different and represent a hydrogen atom or a lower alkyl group. 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 still more preferably a methyl group.

wherein p is the same or different and is an integer of 0-3; q is the same or different and is an integer of 0-3; r is the same or different and is an integer of 0-3. However, the sum of p', q' and r' is 3.

In a preferred embodiment, at the terminal R ^d ' (R ^d when R ^d ' does not exist) at the end of R ^d , q' is preferably 2 or more, for example 2 or 3, more preferably 3. .

In a preferred embodiment, R ^d is terminally endowed with at least one —Si(—Z—SiR ^d2 _q′ R ^d3 _r′ ) ₂ or —Si(—Z—SiR ^d2 _q′ R ^d3 _r′ ) ₃ , It may preferably have -Si(-Z-SiR ^d2 _q' R ^d3 _r' ) ₃ . In the formula, the unit of (-Z-SiR ^d2 _q' R ^d3 _r' ) is preferably (-Z-SiR ^d2 ₃ ). In a further preferred embodiment, all of the terminal portions of R ^d are preferably -Si(-Z-SiR ^d2 _q' R ^d3 _r' ) ₃ , more preferably -Si(-Z-SiR ^d2 ₃ ) ₃ could be.

From the viewpoint of improving crosslinkability, the silane-containing reactive crosslinkable group preferably has an allyl group having 1 to 5 carbon atoms, a glycidyl group having 1 to 5 carbon atoms, an acryl group, or a methacryl group. That is, in the silane-containing reactive cross-linking group, at least one of R ^a , R ^b and R ^c is an allyl group having 1 to 5 carbon atoms, a glycidyl group having 1 to 5 carbon atoms, an acryl group, or a methacryl group. is preferred.

L2 is a single bond or a ^divalent linking group that directly bonds to the ring of formula (1). L ² is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, and is a single bond or an alkylene group having 1 to 10 carbon atoms. , or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond and an ester bond is more preferable.

Specific examples of L ² include -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH)-CH ₂ -, -CH ₂ -, -C ₄ H ₈ - and the like.

Examples of the silane-containing reactive cross-linking groups include -L ² -SiR ⁵ ₃ , -L ² -Si(OR ⁶ ) ₃ , -L ² -Si(NR ⁶ ₂ ) ₃ , -L ² -Si(OCOR ⁶ ). ₃ (in each formula, L ² is as described above, R ⁵ is a halogen atom, and R ⁶ is independently an alkyl group having 1 to 4 carbon atoms).

Examples of the silicone residue include the following groups.

(In each formula, L ² is a single bond or a divalent linking group, n is an integer of 1 to 20, m is an integer of 0 to 10, R ³¹ is each independently a monovalent group, and each At least one of the R ³¹ of the group is a reactive group)

Each of the plurality of R ³¹ contained in each group is independently a monovalent group and may be the above reactive group or a group other than the above reactive group. However, at least one of the plurality of R ³¹ contained in each group is the above reactive group.

Examples of the reactive group include H, a halogen atom or —OR ³² (R ³² is an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 20 carbon atoms), —L ³ —SiR ⁵ ₃ (L ³ is a single a bond or an alkylene group having 1 to 10 carbon atoms, R ⁵ is a halogen atom), -L ³ -Si(OR ⁶ ) ₃ (L ³ is as described above, and R ⁶ is independently an alkyl group having 1 to 4 carbon atoms) , -L ³ -Si(NR ⁶ ₂ ) ₃ (L ³ and R ⁶ are as described above), -L ³ -Si(OCOR ⁶ ) ₃ (L ³ and R ⁶ are as described above), and At least one selected from the group consisting of groups containing either is preferred.

Examples of groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, and uryl groups. , a halogenated uryl group, a urea group, a halogenated urea group, —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, At least one selected from the group consisting of an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group is preferred.

L2 is a single bond or a ^divalent linking group that directly bonds to the ring of formula (1). Suitable values for L2 ^are as described above.

Examples of the silicone residue also include the following groups.

(In each formula, L ² is a single bond or a divalent linking group, R ³⁴ is each independently a monovalent group, and at least one of the R ³⁴ in each group is a reactive group.)

Each of the plurality of R ³⁴ contained in each group is independently a monovalent group and may be the above reactive group or a group other than the above reactive group. However, at least one of the plurality of R ³⁴ contained in each group is the above reactive group.

Examples of the reactive groups include -H, -OR ³⁵ (R ³⁵ is an alkyl group having 1 to 4 carbon atoms), halogen atom, -OH, -O-CR ³⁵ =CH ₂ (R ³⁵ is as described above), —OCOR ³⁵ (R ³⁵ is as described above), —OCOOR ^j (R ^j is an alkyl group or halogenated alkyl group), —NR ³⁵ ₂ (R ³⁵ is as described above) and groups containing any of these groups At least one selected from the group consisting of is preferred.

Examples of groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, and uryl groups. , a halogenated uryl group, a urea group, a halogenated urea group, —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, At least one selected from the group consisting of an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group is preferred.

L2 is a single bond or a ^divalent linking group that directly bonds to the ring of formula (1). Suitable values for L2 ^are as described above.

Examples of the silsesquioxane residue include the following groups.

(In each formula, L ² is a single bond or a divalent linking group, R ³⁷ is each independently a monovalent group, and at least one of the R ³⁷ possessed by each group is a reactive group, p is independently an integer from 0 to 5000)

Each of the plurality of R ³⁷ contained in each group is independently a monovalent group and may be the above reactive group or a group other than the above reactive group. However, at least one of a plurality of R ³⁷ contained in each group is the above reactive group.

Examples of the reactive groups include -H, -OR ³⁵ (R ³⁵ is an alkyl group having 1 to 4 carbon atoms), halogen atom, -OH, -O-CR ³⁵ =CH ₂ (R ³⁵ is as described above), —OCOR ³⁵ (R ³⁵ is as described above), —OCOOR ^j (R ^j is an alkyl group or halogenated alkyl group), —NR ³⁵ ₂ (R ³⁵ is as described above) and groups containing any of these groups At least one selected from the group consisting of is preferred.

Examples of groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, and uryl groups. , a halogenated uryl group, a urea group, a halogenated urea group, —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, At least one selected from the group consisting of an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group is preferred.

L2 is a single bond or a ^divalent linking group that directly bonds to the ring of formula (1). Suitable values for L2 ^are as described above.

Either one or both of X ¹ and X ² may be a group different from the above-described monovalent organic group containing a polyether chain and the above-described crosslinkable group.

That is, X ¹ is H, an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkylamide group, a halogenated alkylamide group, a uryl group, a halogen uryl group, urea group, urea halide group, —OCOOR ^j (R ^j is an alkyl group or a halogenated alkyl group), —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group), sugar chain-containing group, alkylene polyether group, arene group, halogenated arene group, group containing heterocycle, aryl group, halogenated aryl group, silicone residue (excluding those having a reactive group) and silsesquioxane residues (excluding those having a reactive group).

X2 is H, an alkyl group, a halogenated alkyl group, an alkyl ester group, a halogenated alkyl ester group, an alkyl ether group, a halogenated alkyl ether group, an alkylamide group, a halogenated alkylamide group, a ^uryl group, a halogen uryl group, urea group, urea halide group, —OCOOR ^j (R ^j is an alkyl group or a halogenated alkyl group), —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group), sugar chain-containing group, alkylene polyether group, arene group, halogenated arene group, group containing heterocycle, aryl group, halogenated aryl group, silicone residue (excluding those having a reactive group) and silsesquioxane residues (excluding those having a reactive group).

X ¹ and X ² are independently H, alkyl group, halogenated alkyl group, alkyl ester group, halogenated alkyl ester group, alkyl ether group, halogenated alkyl ether group, alkylamide group, halogenated alkylamide group, uryl group, halogenated uryl group, urea group, halogenated urea group, —OCOOR ^j (R ^j is an alkyl group or a halogenated alkyl group), —CONR ^k COR ^l (R ^k and R ^l are independently H, alkyl group or halogenated alkyl group), sugar chain-containing group, alkylene polyether group, arene group, halogenated arene group, group containing heterocycle, aryl group, halogenated aryl group, silicone residue (however, reactive group and silsesquioxane residues (excluding those having a reactive group).

Examples of the silicone residue (excluding those having a reactive group) include the following groups. The above reactive groups are those exemplified as reactive groups that can constitute R ³⁷ .

(In each formula, L ⁴ is a single bond or a divalent linking group, R ⁴¹ is each independently a group other than a monovalent reactive group)

Examples of groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, and uryl groups. , a halogenated uryl group, a urea group, a halogenated urea group, —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, At least one selected from the group consisting of an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group is preferred.

L4 is a single bond or divalent linking group that directly bonds to the ring of formula ( ¹ ). L ⁴ is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, a single bond, and an alkylene group having 1 to 10 carbon atoms. , or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond and an ester bond is more preferable.

Specific examples of L ⁴ include -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH)-CH ₂ - and the like.

Examples of the silsesquioxane residue (excluding those having a reactive group) include the following groups. The above reactive groups are those exemplified as reactive groups that can constitute R ³⁷ .

(In each formula, L ⁴ is a single bond or a divalent linking group, R ⁴¹ is each independently a group other than a monovalent reactive group, and p is independently an integer of 0 to 5000.)

Examples of groups other than the above reactive groups include alkyl groups, halogenated alkyl groups, alkyl ester groups, halogenated alkyl ester groups, alkyl ether groups, halogenated alkyl ether groups, alkylamide groups, halogenated alkylamide groups, and uryl groups. , a halogenated uryl group, a urea group, a halogenated urea group, —CONR ^k COR ^l (R ^k and R ^l are independently H, an alkyl group or a halogenated alkyl group), a group containing a sugar chain, an alkylene polyether group, At least one selected from the group consisting of an arene group, a halogenated arene group, a group containing a heterocycle, an aryl group, and a halogenated aryl group is preferred.

L4 is a single bond or divalent linking group that directly bonds to the ring of formula ( ¹ ). Suitable for ^L4 are as described above.

Examples of the silazane group include the following groups.

(In each formula, L ⁵ is a single bond or a divalent linking group, m is an integer of 2 to 100, n is an integer of 100 or less, R ⁴² is each independently H, alkyl having 1 to 10 carbon atoms group, alkenyl group, cycloalkyl group having 5 to 12 carbon atoms, aryl group having 6 to 10 carbon atoms, alkylsilyl group, alkylcyano group, alkoxy group having 1 to 4 carbon atoms)

^L5 is a single bond or divalent linking group that directly bonds to the ring of formula (1). L ⁵ is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, and is a single bond or an alkylene group having 1 to 10 carbon atoms. , or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond and an ester bond is more preferable.

Specific examples of L ⁵ include -C ₂ H ₄ -, -C ₃ H ₆ -, -C ₄ H ₈ -O-CH ₂ -, -CO-O-CH ₂ -CH(OH)-CH ₂ - and the like.

Specific examples of the silazane group include the following groups.

In the compound of the present invention, the average molecular weight of R ¹ is not particularly limited, but is 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. .

The compounds of the present invention may have an average molecular weight of, but not limited to, 5×10 ² to 1×10 ⁵ . Among them, preferably having an average molecular weight of 2,000 to 30,000, more preferably 2,500 to 12,000, from the viewpoint of UV resistance and friction durability. In the present invention, "average molecular weight" refers to number average molecular weight, and "average molecular weight" is a value measured by ¹⁹ F-NMR.

Next, the method for producing the compound of the present invention will be explained. The compounds of the invention have the formula:

（式中、Ｘ^１及びＸ^２は上述したとおり、Ｌ^２１は単結合又は二価の連結基）で表されるイソシアヌル酸誘導体化合物と、式：Ｒ^２１－Ｘ^２１（式中、Ｒ^２１は、－Ｏ－Ｌ^２１－とともに、上述したＲ^１を構成する一価の有機基、Ｘ^２１はＣｌ、Ｂｒ又はＩ）とを、反応させることにより製造できる。

(Wherein, X ¹ and X ² are as described above, L ²¹ is a single bond or a divalent linking group) and an isocyanuric acid derivative compound represented by the formula: R ²¹ -X ²¹ (wherein R ²¹ is , —OL ²¹ — and the above-mentioned monovalent organic group constituting R ¹ , X ²¹ being Cl, Br or I), can be reacted.

Since R ²¹ constitutes R ¹ described above together with —OL ²¹ —, it naturally includes the above polyether chain. This reaction produces a monovalent organic group represented by R ²¹ -OL ²¹ -. R ²¹ is R ³ —(OR ² ) _a —L ²² — ((OR ² ) _a is the above polyether chain, R ³ is an alkyl group or a fluorinated alkyl group, L ²² is —OL ²¹ — and a single bond or a divalent linking group constituting L described above) is more preferable.

Compounds of the invention may also have the formula:

（式中、Ｘ^１及びＸ^２は上述したとおり、Ｌ^２３は単結合又は二価の連結基）で表されるイソシアヌル酸誘導体化合物と、式：Ｒ^２２－ＣＯＯＨ（式中、Ｒ^２２は、－ＣＯＯ－ＣＨ_２ＣＨ（ＯＨ）－Ｌ^２３－とともに、上述したＲ^１を構成する一価の有機基）とを、反応させることにより製造できる。

(Wherein, X ¹ and X ² are as described above, L ²³ is a single bond or a divalent linking group) and an isocyanuric acid derivative compound represented by the formula: R ²² —COOH (wherein R ²² is --COO--CH.sub.2CH ₍ OH)-- ^L.sub.23 --and the ^monovalent organic group constituting R.sub.1 described above) can be reacted with each other.

Since R ²² constitutes R ¹ described above together with —COO—CH ₂ CH(OH)—L ²³ —, it naturally includes the above polyether chain. This reaction produces a monovalent organic group represented by R ²² —COO—CH ₂ CH(OH)—L ²³ —. R ²² is R ³ —(OR ² ) _a —L ²⁴ —((OR ² ) _a is the above polyether chain, R ³ is an alkyl group or a fluorinated alkyl group, L ²⁴ is —COO—CH ₂ CH A monovalent organic group represented by (OH)—L ²³ — and a single bond or divalent linking group constituting L described above) is preferred.

Compounds of the invention may also have the formula:

（式中、Ｘ^１及びＸ^２は上述したとおり、Ｌ^２５は単結合又は二価の連結基、Ｘ^２５はＣｌ、Ｂｒ又はＩ）で表されるイソシアヌル酸誘導体化合物と、式：Ｒ^２３－ＯＨ（式中、Ｒ^２３は、－Ｏ－Ｌ^２５－とともに、上述したＲ^１を構成する一価の有機基）とを、反応させることにより製造できる。

( ^Wherein , X ¹ and X ² are as described above, L ²⁵ is a single bond or a divalent linking group, X ²⁵ is Cl, Br or I); It can be produced by reacting OH (wherein R ²³ is —OL ²⁵ — together with the monovalent organic group constituting R ¹ described above).

Since R ²³ constitutes R ¹ described above together with —OL ²⁵ —, it naturally includes the above polyether chain. This reaction produces a monovalent organic group represented by R ²³ —OL ²⁵ —. R ²³ is R ³ —(OR ² ) _a —L ²⁶ — ((OR ² ) _a is the above polyether chain, R ³ is an alkyl group or a fluorinated alkyl group, L ²⁶ is —OL ²⁵ — and a single bond or a divalent linking group constituting L described above) is more preferable.

Compounds of the invention may also have the formula:

（式中、Ｘ^１及びＸ^２は上述したとおり、Ｌ^２７は単結合又は二価の連結基）で表されるイソシアヌル酸誘導体化合物と、式：Ｒ^２４－ＯＨ（式中、Ｒ^２４は、－Ｏ－ＣＨ_２ＣＨ（ＯＨ）－Ｌ^２７－とともに、上述したＲ^１を構成する一価の有機基）とを、反応させることにより製造できる。

(Wherein, X ¹ and X ² are as described above, L ²⁷ is a single bond or a divalent linking group) and an isocyanuric acid derivative compound represented by the formula: R ²⁴ —OH (wherein R ²⁴ is It can be produced by reacting —O—CH ₂ CH(OH)—L ²⁷ — with the above-mentioned monovalent organic group constituting R ¹ ).

Since R ²⁴ together with —O—CH ₂ CH(OH)—L ²⁷ — constitutes R ¹ described above, it is natural to include the above polyether chain. This reaction produces a monovalent organic group represented by R ²⁴ —O—CH ₂ CH(OH)—L ²⁷ —. R ²⁴ is R ³ —(OR ² ) _a —L ²⁸ —((OR ² ) _a is the above polyether chain, R ³ is an alkyl group or a fluorinated alkyl group, L ²⁸ is —O—CH ₂ CH A monovalent organic group represented by (OH)—L ²⁷ — and a single bond or divalent linking group constituting L described above) is preferred.

Compounds of the invention may also have the formula:

（式中、Ｘ^１及びＸ^２は上述したとおり、Ｌ^２９は単結合又は二価の連結基）で表されるイソシアヌル酸誘導体化合物と、式：Ｒ^２５－Ｏ－ＳＯ_２Ｒ^２６（式中、Ｒ^２５は、－Ｌ^２９－とともに、上述したＲ^１を構成する一価の有機基、Ｒ^２６は、アルキル基又はフッ素化アルキル基）、又は、Ｒ^２５－Ｘ^２６（式中、Ｒ^２５は上述したとおり、Ｘ^２６はＣｌ、Ｂｒ又はＩ）とを、反応させることにより製造できる。

(Wherein, X ¹ and X ² are as described above, L ²⁹ is a single bond or a divalent linking group) and an isocyanuric acid derivative compound represented by the formula: R ²⁵ —O—SO ₂ R ²⁶ (wherein , R ²⁵ is a monovalent organic group constituting R ¹ described above together with -L ²⁹ -, R ²⁶ is an alkyl group or a fluorinated alkyl group), or R ²⁵ -X ²⁶ (wherein R ²⁵ can be prepared by reacting with Cl, ^Br or I) as described above.

Since R ²⁵ constitutes R ¹ described above together with -L ²⁹ -, it is natural to include the above polyether chain. This reaction produces a monovalent organic group represented by R ²⁵ -L ²⁹ -. R ²⁵ includes R ³ —(OR ² ) _a —L ³⁰ — ((OR ² ) _a is the above polyether chain, R ³ is an alkyl group or a fluorinated alkyl group, L ³⁰ is —L ²⁹ — together with A monovalent organic group represented by a single bond or a divalent linking group constituting L described above) is more preferable.

When either one or both of X ¹ and X ² are the crosslinkable groups, in any of the above reactions, the crosslinkable groups and other compounds may be reacted after the completion of the reaction. good. For example, when X ¹ is a group containing a double bond (preferably an allyl group), the double bond of X ¹ and the formula: H-{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n (wherein R ^a , R ^b , R ^c , R ^d , s, t, u, v and n are as described above) to react with a compound represented by the formula :-L ² -{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n (wherein L ² , R ^a , R ^b , R ^c , R ^d , s, t, u, v and n are as described above) can be introduced into the compound.
Further, among the production methods described above, a monovalent organic group represented by R ²² —COO—CH ₂ CH(OH)—L ²³ —, or R ²⁴ —O—CH ₂ CH(OH)—L ²⁷ In the method of producing a monovalent organic group represented by -, a compound represented by the formula: H-{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n is Since it also reacts with the OH group in the organic group, a structure represented by —O—{Si(R ^a ) _s (R ^b ) _t (R ^c ) _u (R ^d ) _v } _n can be introduced into the compound. .
Further, when X ¹ is a group containing a double bond (preferably an allyl group), oxidation using an oxidizing agent such as metachloroperbenzoic acid, peracetic acid or hydrogen peroxide, or direct air oxidation using a catalyst. ^A group containing an epoxy group can be introduced into the compound by oxidation and epoxidation of the double bond of X1.
Furthermore, when X ¹ is a group containing a double bond (preferably an allyl group), the double bond of X ¹ is reacted with hydroxyalkyl (meth)acrylate to obtain a group containing an acryloyl group or a methacryloyl group. can be introduced into the compound.

The compounds of the invention can be used in a variety of applications. Next, examples of uses of the compounds of the present invention are described.

The compounds of the invention can be used with polymerizable coating monomers. A composition characterized by containing the above compound and a polymerizable coating agent monomer is also one aspect of the present invention (herein sometimes referred to as composition (a)). Since the composition (a) has the above structure, it has a large static contact angle with water or n-hexadecane, is transparent, has excellent releasability, is resistant to fingerprints, and can be completely wiped off even if fingerprints are attached. A coating film is obtained which can be

Among the above compounds, those in which X ¹ is a monovalent crosslinkable group having photocrosslinkability are suitable for the composition (a).

As the polymerizable coating agent monomer, a monomer having a carbon-carbon double bond is preferred.

Examples of the polymerizable coating agent monomer include, but are not particularly limited to, monofunctional and/or polyfunctional acrylates and methacrylates (hereinafter, acrylates and methacrylates are collectively referred to as "(meth)acrylates"), It means a composition containing compounds that are monofunctional and/or polyfunctional urethane (meth)acrylates, monofunctional and/or polyfunctional epoxy (meth)acrylates. The composition forming the matrix is not particularly limited, but is generally a hard coating agent or an antireflection agent, such as a hard coating agent containing a polyfunctional (meth)acrylate. Alternatively, an antireflection agent containing a fluorine-containing (meth)acrylate may be used. The hard coating agent is, for example, Beamset 502H, 504H, 505A-6, 550B, 575CB, 577, 1402 (trade name) from Arakawa Chemical Industries, Ltd., Daicel Cytec Co., Ltd. as EBECRYL40 (trade name), HR300. (trade name) from Yokohama Rubber Co., Ltd. The antireflection agent is commercially available from Daikin Industries, Ltd. as OPTOOL AR-110 (trade name), for example.

Composition (a) further contains an antioxidant, a thickener, a leveling agent, an antifoaming agent, an antistatic agent, an antifogging agent, an ultraviolet absorber, pigments, dyes, inorganic fine particles such as silica, aluminum paste, and talc. , glass frit, fillers such as metal powder, and polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).

Composition (a) preferably further comprises a solvent. Examples of the solvent include fluorine-containing organic solvents and non-fluorine-containing organic solvents.

Examples of the fluorine-containing organic solvent include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamine (Fluorinert (trade name) etc.), perfluoroalkyl ether, perfluorobutyltetrahydrofuran, polyfluoroaliphatic hydrocarbon (Asahiklin AC6000 (trade name)), hydrochlorofluorocarbon (Asahiklin AK-225 (trade name), etc.), hydrofluoroether (Novec (trade name), HFE-7100 (trade name), HFE-7300 (trade name), etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorine-containing alcohol, perfluoroalkyl bromide , perfluoroalkyl iodide, perfluoropolyether (Krytox (trade name), Demnum (trade name), Fomblin (trade name), etc.), 1,3-bistrifluoromethylbenzene, methacrylic acid 2-(perfluoro alkyl)ethyls, 2-(perfluoroalkyl)ethyl acrylates, perfluoroalkylethylenes, freon 134a, and hexafluoropropene oligomers.

Examples of the fluorine-free organic solvent include acetone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol. monobutyl ether acetate, dipropylene glycol dimethyl ether pentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglyme, triglyme, ethyl acetate , butyl acetate, dimethylformamide, dimethylsulfoxide, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.

Among them, the solvent is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, 2-butanone, cyclohexanone, ethyl acetate, diacetone alcohol or 2-propanol.

One of the above solvents may be used alone, or two or more thereof may be used in combination.

The above solvent is preferably used in the composition (a) in an amount of 30 to 95% by mass. More preferably, it is 50 to 90% by mass.

For example, an antifouling layer can be formed by applying the composition (a) to a substrate. It is also possible to form an antifouling layer by polymerizing after coating. Examples of the substrate include resins (particularly, non-fluororesins), metals, and metal oxides.

Glass etc. are mentioned as said metal oxide.

When the substrate is glass, one or both of X ¹ and X ² are preferably the crosslinkable groups from the viewpoint of adhesion between the substrate and the antifouling layer. More preferably, one or both of X ¹ and X ² are monovalent Si-containing groups, and more preferably one or both of X ¹ and X ² are silane-containing reactive cross-linking groups.

The compounds of the invention can be used with curable resins or curable monomers. A composition characterized by containing the aforementioned compound and a curable resin or curable monomer is also one aspect of the present invention (herein sometimes referred to as composition (b)). Since the composition (b) has the above structure, it is possible to obtain a coating film which is resistant to fingerprints and which can be completely wiped off even if fingerprints are attached.

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 is preferably a photocurable resin, and an ultraviolet curable resin. more preferred.

Examples of the curable resin include acrylic polymers, polycarbonate polymers, polyester polymers, polyamide polymers, polyimide polymers, polyethersulfone polymers, cyclic polyolefin polymers, fluorine-containing polyolefin polymers (such as PTFE), Fluorine-containing cyclic amorphous polymers (Cytop (registered trademark), Teflon (registered trademark) AF, etc.) and the like.

Specific examples of the curable resin or monomers constituting the curable resin include alkyl vinyl ethers such as cyclohexylmethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, glycidyl vinyl ether, vinyl acetate, vinyl pivalate, various (meth) Acrylates: 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, propane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl 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, fluorine-containing cyclic amorphous polymer (Cytop (registered trademark), Teflon (registered trademark) AF, etc.).

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

Specific examples of the curable monomer include the following.
(a) Urethane (meth)acrylates include poly[(meth)acryloyloxyalkyl]isocyanurates typified by tris(2-hydroxyethyl)isocyanurate diacrylate and tris(2-hydroxyethyl)isocyanurate triacrylate. mentioned.
(b) Epoxy (meth)acrylate is obtained by adding a (meth)acryloyl group to an epoxy group, and bisphenol A, bisphenol F, phenol novolak, and alicyclic compounds are generally used as starting materials.
(c) Polyhydric alcohols constituting the polyester portion of polyester (meth)acrylate include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, Polypropylene glycol, pentaerythritol, dipentaerythritol, etc., and polybasic acids include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, alkenylsuccinic acid, and the like.
(d) Polyether (meth)acrylates include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol di(meth)acrylate and the like.
(e) Silicon (meth)acrylate is a dimethylpolysiloxane with a molecular weight of 1,000 to 10,000 modified with (meth)acryloyl groups at one or both ends. exemplified.

(f) (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate , sec-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 ) 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)acrylate, 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 include 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.

Among the above curable resins and curable monomers, commercially available and preferred ones are listed below.

Examples of the curable resin include silicone resins PAK-01 and PAK-02 (manufactured by Toyo Gosei Chemical Co., Ltd.), nanoimprint resin NIF series (manufactured by Asahi Glass Co., Ltd.), nanoimprint resin OCNL series (manufactured by Tokyo Ohka Kogyo Co., Ltd.), NIAC2310 (Daicel Kagaku Kogyo 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. (manufactured by Sumitomo Bayern Urethane), hexamethylene diisocyanate-based polyisocyanates, Sumidule N-75, Sumidule N3200, Sumidule HT, Sumidule N3300, and Sumidule N3500 (manufactured by Sumitomo Bayern Urethane).

Among the above curable monomers, silicone acrylate resins include Silaplane FM-0611, Silaplane FM-0621, Silaplane FM-0625, double-ended (meth)acrylic 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 ( Meth)acrylic Silaplane FM-0711, Silaplane FM-0721, Silaplane FM-0725, Silaplane TM-0701 and Silaplane TM-0701T (manufactured by JCN) and the like.
Polyfunctional acrylates include A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A -TMPT, A-TMMT (manufactured by Shin-Nakamura Kogyo Co., Ltd.) and the like.
Examples of polyfunctional methacrylates include TMPT (manufactured by Shin-Nakamura Kogyo Co., Ltd.).
Alkoxysilane group-containing (meth)acrylates include 3-(meth)acryloyloxypropyltrichlorosilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-( meth)acryloyloxypropyltriisopropoxysilane (also known as (triisopropoxysilyl)propyl methacrylate (abbreviation: TISMA) and triisopropoxysilyl)propyl acrylate), 3-(meth)acryloxyisobutyltrichlorosilane, 3-(meth) acryloxyisobutyltriethoxysilane, 3-(meth)acryloxyisobutyltriisopropoxy, 3-(meth)acryloxyisobutyltrimethoxysilane, silane and the like.

Composition (b) also preferably comprises a cross-linking catalyst. Examples of the cross-linking catalyst include radical polymerization initiators and acid generators.
The radical polymerization initiator is a compound that generates radicals by heat or light, and examples thereof include radical thermal polymerization initiators and radical photopolymerization initiators. In the present invention, the above radical photopolymerization initiator is preferred.

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, diisopropyl peroxydicarbonate, Peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, peroxide compounds such as alkyl peresters such as t-butyl peroxybenzoate, and azobis iso Radical-generating azo compounds such as butyronitrile and the like are included.

Examples of the radical photopolymerization initiator include -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- Thioxanthones such as diethylthioxanthone and thioxanthone-4-sulfonic acid, benzophenones such as benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, acetophenone, 2-(4- Toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1 -propanone, acetophenones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, anthraquinone, quinones such as 1,4-naphthoquinone, 2-dimethylaminobenzoic acid aminobenzoic acids such as ethyl, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, phenacyl chloride, Examples thereof include halogen compounds such as trihalomethylphenylsulfone, acylphosphine oxides, and peroxides such as di-t-butyl peroxide.

Commercially available products of the radical photopolymerization initiator are exemplified below.
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethan-1-one,
IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl-ketone,
IRGACURE 2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one,
IRGACURE 127: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one,
IRGACURE 907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-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-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,
IRGACURE OXE 01: 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)],
IRGACURE OXE 02: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime),
IRGACURE261, IRGACURE369, IRGACURE500,
DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propan-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 BASF, and DAROCUR is manufactured by Merck Japan.

Further, when a radical photopolymerization initiator is used as the crosslinking catalyst, diethylthioxanthone, isopropylthioxanthone, or the like can be used in combination as a sensitizer, and DAROCUR EDB (ethyl-4-dimethylaminobenzoate) can be used as a polymerization accelerator. ), DAROCUR EHA (2-ethylhexyl-4-dimethylaminobenzoate), etc. may be used in combination.

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

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

The photoacid generator is composed of a chromophore that absorbs light and an acid precursor that becomes an acid after decomposition. The acid generator is excited to generate acid from the acid precursor portion.
Examples of the photoacid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, CF ₃ SO ₃ , p-CH ₃ PhSO ₃ , p-NO ₂ PhSO ₃ (where Ph is a phenyl group) and the like. Salts, organic halogen compounds, orthoquinone-diazide sulfonyl chlorides, sulfonate esters, and the like can be mentioned. In addition, as photoacid generators, 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds, 2-trihalo Also included are methyl-5-hydroxyphenyl-1,3,4-oxadiazole compounds.
The organic halogen compound is a compound that forms a hydrohalic acid (for example, hydrogen chloride).

Commercially available products of the photoacid generator are exemplified below.
Wako Pure Chemical Industries, Ltd. WPAG-145 [bis (cyclohexylsulfonyl) diazomethane], WPAG-170 [bis (t-butylsulfonyl) diazomethane], WPAG-199 [bis (p-toluenesulfonyl) diazomethane], WPAG-281 [triphenylsulfonium trifluoromethanesulfonate], WPAG-336 [diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate], WPAG-367 [diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate], Ciba Specialty Chemicals IRGACURE PAG103 [(5-propylsulfonyloximino-5H-thiophen-2-ylidene) -(2-methylphenyl) acetonitrile], IRGACURE PAG108 [(5-octylsulfonyloximino-5H-thiophene-2- ylidene)-(2-methylphenyl)acetonitrile)], IRGACURE PAG121 [(5-p-toluenesulfonyloximino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile], IRGACURE PAG203, CGI725, three 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 amount of the cross-linking catalyst compounded 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 sufficient cured product can be obtained. The blending amount of the crosslinking catalyst is more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 2 parts by mass.

When the acid generator is used as the cross-linking catalyst, an acid scavenger may be added as necessary to control the diffusion of the acid generated from the acid generator.
Although the acid scavenger is not particularly limited, basic compounds such as amines (especially organic amines), basic ammonium salts, and basic sulfonium salts are preferred. Among these acid scavengers, organic amines are more preferable from the viewpoint of excellent image performance.

Specific examples of the acid scavenger include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, 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, and tetrabutylammonium lactate, triethylamine, tributylamine and the like. Among these, 1,5-diazabicyclo[4.3.0]-5-nonene, 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 amount of the acid scavenger compounded is preferably 20 parts by mass or less, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the acid generator. 5 parts by mass.

Composition (b) may contain a solvent. Examples of the solvent include water-soluble organic solvents, organic solvents (especially oil-soluble organic solvents), water, and the like.
Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene Glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol diacetate, tripropylene glycol, 3-methoxybutyl acetate (MBA), 1,3-butylene glycol diacetate, cyclohexanol acetate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve , cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol and the like.
Examples of the organic solvent include chloroform, HFC141b, HCHC225, hydrofluoroether, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, and acetic acid. butyl, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane and the like.
These solvents may be used alone or in combination of two or more.
As the solvent, PGMEA and MBA are particularly preferred from the viewpoint of the solubility and safety of the components contained in the resist composition.

The above solvent is preferably used in the composition (b) in an amount of 30 to 95% by mass. More preferably, it is 50 to 90% by mass.

For example, a resist film can be formed by applying the composition (b) to a substrate. Examples of materials for the base material include silicon, synthetic resin, glass, metal, and ceramics.

Examples of the synthetic resin include cellulose resins such as triacetyl cellulose (TAC), polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA), cyclic polyolefins, modified Polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly-(4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluorine Various thermoplastic elastomers such as styrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, fluororubber-based, and chlorinated polyethylene-based resins, epoxy resins, phenolic resins, urea resins, melamine resins, unsaturated polyesters, silicone resins , polyurethane, etc., or copolymers, blends, polymer alloys, etc. mainly composed of these, and the like, and these may be used alone or in combination of two or more (for example, as a laminate of two or more layers). can.

The above resist film can be used for nanoimprinting. For example, a step of pressing a mold having a fine pattern formed on its surface against the resist film to transfer the fine pattern, a step of curing the resist film on which the transfer pattern is formed, and obtaining a cured resist having the transfer pattern; And, a pattern-transferred cured resist can be obtained by a production method including the step of releasing the cured resist from the mold.

The compounds of the invention can be used with solvents. A composition characterized by containing the above compound and a solvent is also one aspect of the present invention (sometimes referred to herein as composition (c)).

In the composition (c), the concentration of the compound is preferably 0.001 to 1% by mass, more preferably 0.005 to 0.5% by mass, even more preferably 0.01 to 0.2% by mass.

As the solvent, a fluorine-based solvent is preferable. Examples of the fluorine-based inert solvent include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and dichloropentafluoropropane (HCFC-225).

Composition (c) also preferably contains a fluorine-containing oil. As the fluorine-containing oil,
Formula: R ¹¹¹ -(R ¹¹² O) _m -R ¹¹³
(R ¹¹¹ and R ¹¹³ are independently F, an alkyl group having 1 to 16 carbon atoms, a fluorinated alkyl group having 1 to 16 carbon atoms, —R ¹¹⁴ —X ¹¹¹ (R ¹¹⁴ is a single bond or X ¹¹¹ is -NH ₂ , -OH, -COOH, -CH=CH ₂ , -OCH ₂ CH=CH ₂ , halogen, phosphoric acid, phosphoric acid ester, carboxylic acid ester, thiol, thioether, alkyl Ether (which may be substituted with fluorine), aryl, aryl ether, amide), R ¹¹² is a fluorinated alkylene group having 1 to 4 carbon atoms, and m is an integer of 2 or more) are more preferred.

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 preferably F, a fully fluorinated alkyl group having 1 to 3 carbon atoms or —R ¹¹⁴ —X ¹¹¹ (R ¹¹⁴ is a single bond or an alkylene group having 1 to 3 carbon atoms, X ¹¹¹ is —OH or —OCH ₂ CH= CH ₂ ) is more preferred.

As m, an integer of 300 or less is preferable, and an integer of 100 or less is more preferable.

R ¹¹² is preferably a fully fluorinated alkylene group having 1 to 4 carbon atoms. —R ¹¹² O— is, 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, 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).

Each of n111 to n115 is preferably an integer of 0 to 200. The sum of n111 to n115 is preferably 1 or more, more preferably 5 to 300, even more 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 independently selected from 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 for example -OC ₂ F ₄ OC ₃ F ₆ -, -OC _{2F4OC4F8- , -OC3F6OC2F4- , -OC3F6OC3F6- , -OC3F6OC4F8- , -OC4F8OC4F _ _ _ _ _ _ _ _ _ _ 8- , -OC4F8OC3F6- , -OC4F8OC2F4- , -OC2F4OC2F4OC3F6- , -OC2F4OC2F4OC _ _ _ _ _ _ _ _ _ _ 4F8- , -OC2F4OC3F6OC2F4- , -OC2F4OC3F6OC3F6- , -OC2F4OC4F8OC2F4- , _ _ _ _ _ _ _ _ _ _ _ _ -OC3F6OC2F4OC2F4- , -OC3F6OC2F4OC3F6- , -OC3F6OC3F6OC2F4- , and -OC4F _ _ _ _ _ _ _ _ _ _ _ 8} OC ₂ F ₄ OC ₂ F ₄ - and the like. f is an integer of 2-100, preferably an integer of 2-50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be linear or branched, preferably linear. In this aspect, 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 fluoropolyether preferably has a weight average molecular weight of 500 to 100,000, more preferably 50,000 or less, still more 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 fluoropolyethers include Demnum (manufactured by Daikin Industries, Ltd.), Fomblin (manufactured by Solvay Specialty Polymers Japan), Barrierta (manufactured by NOK Klüber), Krytox (manufactured by DuPont), and the like. mentioned.

Composition (c) can be used to form a release layer on a substrate. The release layer can be formed by a method of immersing the substrate in the composition (c), a method of exposing the substrate to the vapor of the composition (c) for vapor deposition, or printing the composition (c) on the substrate. and a method of applying the composition (c) to the base material using an inkjet method. After the immersion, vapor deposition, printing, and application, drying may be performed. A mold having an uneven pattern formed thereon can be used as the substrate, and the mold having a release layer formed thereon can be used for nanoimprinting.

When one or both of X ¹ and X ² are the crosslinkable groups, the release layer can be firmly adhered to the substrate.
Moreover, when both X ¹ and X ² are groups different from the crosslinkable group, the release layer can be easily removed from the base material. For example, if the mold release layer is formed on the mold and used for nanoimprinting, the mold release property can be imparted by attaching the compound to the transferred material.

Examples of the substrate include metals, metal oxides, quartz, polymeric resins such as silicone, semiconductors, insulators, and composites thereof.

The present invention also provides an antifouling agent comprising the above compound or composition.

The antifouling agent can be used by applying it to a substrate such as a resin (particularly, a non-fluororesin), metal, or glass.

The above-mentioned antifouling agent can be used in a variety of articles (especially optical materials) that require surface antifouling properties and swelling properties. Examples of articles include front protective plates for displays such as PDP and LCD, antireflection plates, polarizing plates, anti-glare plates, devices such as mobile phones and personal digital assistants, touch panel sheets, DVD discs, optical discs such as CD-R and MO. , spectacle lenses, and optical fibers.

Optical materials such as optical discs contain carbon-carbon double bond-containing compositions or carbon-carbon double bond-containing compositions and carbon-carbon double bond-containing compositions It is preferable that the surface is coated with a film formed by adding perfluoropolyether (PFPE) to the polymer of the contained monomer so that the content is 0.01% by weight to 10% by weight. At 0.01% by weight to 10% by weight, the characteristic physical properties of PFPE addition (antifouling, etc.) appear, the surface hardness is high, and the transmittance is high.

The present invention also provides a mold release agent comprising the above compound or the above composition.

A release layer can be formed on the substrate from the release agent. The release layer can be formed by a method of immersing the base material in the release agent, a method of exposing the base material to the vapor of the release agent for vapor deposition, a method of printing the composition on the base material, or an inkjet method. and a method of applying the composition to the base material using the above method. After the immersion, vapor deposition, printing, and application, drying may be performed. A mold having an uneven pattern formed thereon can be used as the substrate, and the mold having a release layer formed thereon can be used for nanoimprinting.

Examples of the substrate include metals, metal oxides, quartz, polymeric resins such as silicone, semiconductors, insulators, and composites thereof.

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited only to these examples. In the present examples, the chemical formulas shown below all represent average compositions, and repeating units constituting the perfluoropolyether (for example, -CF ₂ CF ₂ CF ₂ O-, -CF ₂ CF ₂ O-, - CF ₂ O—) can be present in any order.

Each numerical value in the examples was measured by the following method.

(static contact angle)
The static contact angle was measured by the following method using a fully automatic contact angle meter DropMaster700 (manufactured by Kyowa Interface Science Co., Ltd.).
<Method for measuring static contact angle>
The static contact angle was obtained by dropping 2 μL of water or n-hexadecane from a microsyringe onto a horizontally placed substrate, and taking a still image 1 second after dropping with a video microscope.

Example 1 Method for producing compound (A) containing perfluoropolyether (PFPE) 34 g of CF ₃ CF ₂ CF ₂ O—(CF ₂ CF ₂ CF ₂ O) ₁₁ —CF ₂ CF ₂ CH ₂ OH and 1 , 3-diallyl-5-(2-chloroethyl)isocyanurate 6 g was dissolved in a mixed solvent of m-hexafluoroxylene and diethylene glycol dimethyl ether. 20 g of a 20% by weight potassium hydroxide aqueous solution and 4 g of tetrabutylammonium bromide were added and heated while stirring. The end point of the reaction was confirmed by ¹⁹ F-NMR and ¹ H-NMR. The PFPE-containing compound (A) was obtained by concentrating and extracting the reaction solution.
PFPE-containing compound (A):

Example 2 Method for producing perfluoropolyether (PFPE)-containing compound (B) 6 g of 1,3-diallyl-5-(2-chloroethyl)isocyanurate in Example 1 A PFPE-containing compound (B) was obtained in the same manner as in Example 1, except that it was changed to 6.2 g.
PFPE-containing compound (B):

Example 3 Method for producing perfluoropolyether (PFPE)-containing compound (C) 2.0 g of 1,3-diallyl-isocyanuric acid was dissolved in a mixed solvent of m-hexafluoroxylene and dimethylformamide. 1.0 g of potassium carbonate was added and heated with stirring. 4.0 g of CF ₃ CF ₂ CF ₂ O—(CF ₂ CF ₂ CF ₂ O) ₂₃ —CF ₂ CF ₂ CH ₂ -trifluoromethanesulfonate dissolved in m-hexafluoroxylene was added, and the mixture was further heated and stirred. rice field. The end point of the reaction was confirmed by ¹⁹ F-NMR and ¹ H-NMR. Pure water was added to the reaction solution and the mixture was separated to obtain a PFPE-containing compound (C).
PFPE-containing compound (C):

Example 4 Method for producing perfluoropolyether (PFPE)-containing compound (D) CF ₃ CF ₂ CF ₂ O—(CF ₂ CF ₂ CF ₂ O) ₂₃ —CF ₂ CF ₂ CH ₂ —trifluoromethane of Example 3 In the same manner as in Example 3, except that 8.0 g of CF ₃ CF ₂ CF ₂ O—(CF ₂ CF ₂ CF ₂ O) ₁₁ —CF ₂ CF ₂ CH ₂ Cl was used instead of 4.0 g of the sulfonate ester. A PFPE-containing compound (D) was obtained.

Example 5 Method for producing perfluoropolyether (PFPE)-containing compound (E) 30 ml of m-hexafluoroxylene and 11.1 g of meta-chloroperbenzoic acid were placed in a reactor, and the temperature was raised to 60°C while stirring. A solution of 10 g of PFPE-containing compound (D) dissolved in 10 ml of m-hexafluoroxylene was added dropwise thereto. After that, the mixture was stirred at 60°C. The end point of the reaction was confirmed by ¹⁹ F-NMR and ¹ H-NMR. The reaction solution was returned to room temperature, the precipitated white solid was separated by filtration, and the filtrate was concentrated to 20 ml. The precipitated white solid was dissolved by adding 10 ml of diethyl ether, and the lower layer oil was separated. The PFPE-containing compound (E) was obtained by distilling off the residual solvent from the oil.
PFPE-containing compound (E):

Example 6 Method for producing perfluoropolyether (PFPE)-containing compound (F) 2.0 g of 2-hydroxyethyl acrylate was dissolved in a mixed solvent of m-hexafluoroxylene and dimethylformamide. 1.0 g of potassium carbonate was added, and the temperature was raised to 40° C. and stirred. 4.0 g of PFPE-containing compound (E) dissolved in m-hexafluoroxylene was added to this reaction solution, and the mixture was further heated and stirred. The end point of the reaction was confirmed by ¹⁹ F-NMR and ¹ H-NMR. Pure water was added to the reaction solution and the mixture was separated to obtain a PFPE-containing compound (F).
PFPE-containing compound (F):

<Characteristic evaluation of cured film>
Beam set 575CB (manufactured by Arakawa Chemical Industries, Ltd.) 6.0 g, Irgacure 907 (manufactured by BASF) 120 mg as a photopolymerization initiator, PFPE-containing compounds (A), (B), (D), (E), (F ) was added so as to be 2% by mass of the whole, and the mixture was stirred overnight with a rotating mixer under light shielding to obtain PFPE-containing hard coating materials 1 to 5. A hard coat material obtained in the same manner as above, except that PFPE-containing compounds (A), (B), (D), (E), and (F) were changed to DAC-HP (manufactured by Daikin Industries, Ltd.). was used as Comparative Example 1. Comparative Example 2 was a hard coat material of Beamset 575CB (manufactured by Arakawa Chemical Industries, Ltd.) to which no PFPE-containing compound was added.
10 μL of each hard coat material was placed on a slide glass, and a uniform coating film was formed using a bar coater. This was irradiated with light containing UV light of 365 nm at an intensity of 500 mJ/cm ² in a nitrogen atmosphere to cure each hard coat material to obtain a cured film. The static contact angles of these cured films were measured.
(exterior)
The appearance of the cured film was visually confirmed. Evaluation was based on the following criteria.
○: Transparent ×: Whitening (Releasability)
The releasability of the cured film was evaluated by a tape peeling test. Evaluation was based on the following criteria.
◯: Easily peeled off or not adhered.
x: The adhesive layer of the tape adheres.
(fingerprint adhesion)
A finger was pressed against the cured film, and the susceptibility to fingerprints was visually determined. Evaluation was based on the following criteria.
Good: Fingerprints are hard to adhere, or fingerprints are inconspicuous even if adhered.
x: Fingerprints are clearly attached.
(Fingerprint wiping ability)
After the above-mentioned fingerprint adhesion test, the adhered fingerprints were wiped off with a Kimwipe (trade name, manufactured by Jujo Kimberly Co., Ltd.) five times, and the easiness of wiping off the adhered fingerprints was visually determined. Evaluation was based on the following criteria.
Good: Fingerprints can be completely wiped off.
x: Wiping traces of fingerprints spread and are difficult to remove.
Table 1 shows the results obtained in each evaluation.

Example 7 Method for producing perfluoropolyether (PFPE)-containing compound (G) 10.1 g of PFPE-containing compound (C), 40 g of m-hexafluoroxylene, 0.04 g of triacetoxymethylsilane, and 1 part of trichlorosilane 0.93 g was charged and stirred at 10° C. for 30 minutes. Subsequently, 0.115 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated and stirred for 4 hours. Then, after distilling off the volatile matter under reduced pressure, a mixed solution of 0.23 g of methanol and 6.1 g of trimethyl orthoformate was added, followed by heating and stirring for 3 hours. Thereafter, purification was carried out to obtain 9.9 g of the following PFPE-containing compound (G) having a trimethoxysilyl group at the terminal.
PFPE-containing compound (G):

Example 8 Method for producing perfluoropolyether (PFPE)-containing compound (H) 10.0 g of PFPE-containing compound (A), 30 g of m-hexafluoroxylene, 0.06 g of triacetoxymethylsilane, and 3 g of trichlorosilane 0.85 g was charged and stirred at 10° C. for 30 minutes. Subsequently, 0.210 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated and stirred for 3 hours. Then, after distilling off the volatile matter under reduced pressure, a mixed solution of 0.31 g of methanol and 7.5 g of trimethyl orthoformate was added, followed by heating and stirring for 3 hours. Thereafter, purification was carried out to obtain 9.8 g of the following PFPE-containing compound (H) having a trimethoxysilyl group at the terminal.
PFPE-containing compound (H):

Example 9 Method for producing perfluoropolyether (PFPE)-containing compound (I) The PFPE-containing compound (A) in Example 8 was changed to the PFPE-containing compound (B), and the amount of trichlorosilane charged was changed to 4.75 g. A PFPE-containing compound (I) was obtained in the same manner as in Example 8, except that
PFPE-containing compound (I):

Example 10 Method for producing perfluoropolyether (PFPE)-containing compound (J) 10.2 g of PFPE-containing compound (D), 30 g of m-hexafluoroxylene, 0.06 g of triacetoxymethylsilane, and 3 parts of trichlorosilane 0.85 g was charged and stirred at 10° C. for 30 minutes. Subsequently, 0.220 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated and stirred for 4 hours. Then, after evaporating the volatile matter under reduced pressure, a mixed solution of 0.30 g of methanol and 7.5 g of trimethyl orthoformate was added, followed by heating and stirring for 3 hours. Thereafter, purification was performed to obtain 10.0 g of the following PFPE-containing compound (J) having a trimethoxysilyl group at the end.
PFPE-containing compound (J):

Example 11 Method for producing perfluoropolyether (PFPE)-containing compound (L) CF ₃ O— ₍ CF ₂ CF ₂ O) _{m (} CF ₂ O) _n =19) 33 g and 7.1 g of 1,3-diallyl-5-(2-chloroethyl)isocyanurate were dissolved in a mixed solvent of m-hexafluoroxylene and diethylene glycol dimethyl ether. 15 g of a 20% by weight potassium hydroxide aqueous solution and 3 g of tetrabutylammonium bromide were added and heated while stirring. The end point of the reaction was confirmed by ¹⁹ F-NMR and ¹ H-NMR. The PFPE-containing compound (K) was obtained by concentrating and extracting the reaction solution.
PFPE-containing compound (K):

Subsequently, in the same manner as in Example 7 except that the PFPE-containing compound (C) of Example 7 was changed to the PFPE-containing compound (K), the following PFPE-containing compound (L) having a trimethoxysilyl group at the end 9.6 g was obtained.
PFPE-containing compound (L):

Example 12 Method for producing perfluoropolyether (PFPE)-containing compound (N) 2.0 g of 1,3-diallyl-isocyanuric acid was dissolved in a mixed solvent of m-hexafluoroxylene and dimethylformamide. 1.0 g of potassium carbonate was added and heated with stirring. 4.0 g of CF ₃ O—(CF ₂ CF ₂ O) _m (CF ₂ O) _n CF ₂ CH ₂ -trifluoromethanesulfonate (m=22, n=19) dissolved in m-hexafluoroxylene was added. Heating and stirring were continued. The end point of the reaction was confirmed by ¹⁹ F-NMR and ¹ H-NMR. Pure water was added to the reaction solution and the mixture was separated to obtain a PFPE-containing compound (M).
PFPE-containing compound (M):

Subsequently, in the same manner as in Example 7 except that the PFPE-containing compound (C) of Example 7 was changed to the PFPE-containing compound (M), the following PFPE-containing compound (N) having a trimethoxysilyl group at the end 9.8 g was obtained.
PFPE-containing compound (N):

Example 13 Method for producing perfluoropolyether (PFPE)-containing compound (P) 10.0 g of PFPE-containing compound (C), 40 g of m-hexafluoroxylene, 0.04 g of triacetoxymethylsilane, and 1 part of trichlorosilane 0.93 g was charged and stirred at 10° C. for 30 minutes. Subsequently, 0.115 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated and stirred for 4 hours. Then, after evaporating the volatile matter under reduced pressure, 15 g of m-hexafluoroxylene was added, 22 ml of a tetrahydrofuran solution containing 1.0 mol/L of allylmagnesium chloride was added under an ice bath, and then the temperature was raised to room temperature, Stir at this temperature for 10 hours. Thereafter, the mixture was cooled to 5°C, 3 ml of methanol was added, and then perfluorohexane was added and stirred for 30 minutes. Subsequently, 9.4 g of PFPE-containing compound (O) having an allyl group at the terminal was obtained by distilling off the volatile matter under reduced pressure.
PFPE-containing compound (O):

Subsequently, 9.0 g of PFPE-containing compound (O), 30 g of m-hexafluoroxylene, 0.08 g of triacetoxymethylsilane, and 5.60 g of trichlorosilane were charged and stirred at 10° C. for 30 minutes. Subsequently, 0.297 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated and stirred for 4 hours. Then, after evaporating the volatile matter under reduced pressure, a mixed solution of 0.57 g of methanol and 14.1 g of trimethyl orthoformate was added, followed by heating and stirring for 3 hours. Thereafter, purification was carried out to obtain 9.1 g of the following PFPE-containing compound (P) having a trimethoxysilyl group at the terminal.
PFPE-containing compound (P):

Example 14 Method for producing perfluoropolyether (PFPE)-containing compound (R)
10.0 g of PFPE-containing compound (M), 45 g of m-hexafluoroxylene, 0.04 g of triacetoxymethylsilane and 1.41 g of dichloromethylsilane were charged and stirred at 10° C. for 30 minutes. Subsequently, 0.136 ml of a xylene solution containing 2% of Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, followed by heating and stirring. Then, after evaporating the volatile matter, 15 ml of vinylmagnesium chloride (1.6 M THF solution) was added and stirred at room temperature. Thereafter, purification was carried out to obtain 9.5 g of the following PFPE-containing compound (Q) having a methyldivinylsilyl group at the terminal.
PFPE-containing compound (Q):

Subsequently, 9.5 g of PFPE-containing compound (Q), 42 g of m-hexafluoroxylene, 0.04 g of triacetoxymethylsilane, and 2.30 g of trichlorosilane were charged and stirred at 10° C. for 30 minutes. Subsequently, 0.230 ml of a xylene solution containing 2% Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added, and the mixture was heated and stirred for 4 hours. Then, after distilling off the volatile matter, a mixed solution of 0.30 g of methanol and 7.56 g of trimethyl orthoformate was added, followed by heating and stirring. Thereafter, purification was carried out to obtain 9.6 g of the following PFPE-containing compound (R) having a trimethoxysilyl group at the terminal.
PFPE-containing compound (R):

Examples 15-22
The PFPE-containing compounds (G), (H), (I), (J), (L), (N), (P), and (R) obtained in Examples 7 to 14 above are added to a concentration of 1 mass%. Surface treatment agents (1) to (8) were prepared by dissolving in hydrofluoroether (Novec HFE-7300, manufactured by 3M) as follows.

Comparative Examples 3-5
Instead of the PFPE-containing compounds (G), (H), (I), (J), (L), (N), (P), and (R), the following control compounds (1) to (3) were used. Comparative surface treatment agents (1) to (3) were prepared in the same manner as in Examples 15 to 22, except that
Reference compound (1)

Reference compound (2)

Reference compound (3)

The surface treatment agents (1) to (8) prepared above and the comparative surface treatment agents (1) to (3) were applied to chemically strengthened glass (manufactured by Corning, "Gorilla" glass, thickness 0.7 mm) using a spin coater. painted on top.
The spin coating conditions were 300 rpm for 3 seconds and 2000 rpm for 30 seconds. The coated substrate was heated at 140° C. for 30 minutes in a constant temperature bath under the atmosphere to form a cured film.

<Characteristic evaluation of cured film>
(Initial evaluation)
First, as an initial evaluation, after the formation of the cured film, the static contact angle of water was measured with nothing touching the surface.

(Evaluation after wiping with ethanol)
Next, the above-mentioned cured film was wiped with a Kimwipe (trade name, manufactured by Jujo Kimberly Co., Ltd.) saturated with ethanol 5 reciprocations, dried, and then the static contact angle of water was measured.
(fingerprint adhesion)
Next, a finger was pressed against the cured film, and the susceptibility to fingerprints was visually determined. Evaluation was based on the following criteria.
Good: Fingerprints are hard to adhere, or fingerprints are inconspicuous even if adhered.
Δ: Few fingerprints are adhered, but the fingerprints can be sufficiently confirmed.
x: A fingerprint adheres as clearly as an untreated glass substrate.
(Fingerprint wiping ability)
After the above-mentioned fingerprint adhesion test, the adhered fingerprints were wiped off with a Kimwipe (trade name, manufactured by Jujo Kimberly Co., Ltd.) five times, and the easiness of wiping off the adhered fingerprints was visually determined. Evaluation was based on the following criteria.
Good: Fingerprints can be completely wiped off.
Δ: Traces of wiping fingerprints remain.
x: Wiping traces of fingerprints spread and are difficult to remove.
The above series of evaluation results are summarized in Table 2 below.

As shown in Table 2, the cured films of Examples 15 to 22 had high initial water repellency and no change after wiping with ethanol. there were.

Claims (5)

A compound characterized by being represented by formula (1).
Formula (1):

(wherein R ¹ is a monovalent organic group containing a polyether chain (excluding those containing a urethane bond), X ¹ and X ² are independently an acryloyl group, a methacryloyl group, a glycidyl group, an allyl and at least one crosslinkable group selected from the group consisting of monovalent groups containing any of these groups, and the polyether chain is
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, m11 to m16 are total integers of 10 to 200, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary)) At least one or both of X ¹ and X ² independently comprise a polyether chain, said polyether chain comprising:
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, m11 to m16 are total integers of 10 to 200, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary). X ¹ comprises a polyether chain, said polyether chain comprising
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, m11 to m16 are total integers of 10 to 200, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary). X ² comprises a polyether chain, said polyether chain comprising
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, m11 to m16 are total integers of 10 to 200, X ¹⁰ is independently H, F or 3. The compound according to claim 1 or 2, which is a chain represented by Cl, and the order of existence of each repeating unit is arbitrary. X ¹ and X ² independently comprise a polyether chain, said polyether chain comprising
Formula: - (OC ₆ F ₁₂ ) _m11 - (OC ₅ F ₁₀ ) _m12 - (OC ₄ F ₈ ) _m13 - (OC ₃ X ¹⁰ ₆ ) _m14 - (OC ₂ F ₄ ) _m15 - (OCF ₂ ) _m16 -
(Wherein, m11, m12, m13, m14, m15 and m16 are independently integers of 0 or 1 or more, m11 to m16 are total integers of 10 to 200, X ¹⁰ is independently H, F or Cl, the order of existence of each repeating unit is arbitrary).