JP6882998B2 - Laminate - Google Patents

Description

The present invention relates to a laminate including a hard coat layer and an abrasion resistant layer.

For applications that require abrasion resistance, such as displays for electronic devices, a hard coat layer is provided on the surface to protect the article from scratches, and the hard coat layer is further provided with an antifouling layer to prevent dirt from adhering. In some cases.

For example, Patent Documents 1 and 2 describe that the surface of a photocurable hard coat layer is treated with an antifouling coating agent, and perfluoropolyether-modified silane or a hydrolyzed condensate thereof is disclosed as an antifouling coating agent. Has been done.

Further, Patent Document 3 discloses an antifouling optical film in which a hard coat layer is provided on one surface of a transparent resin film and an antifouling treatment is applied to the outermost surface on the hard coat layer side. As a raw material, a silane coupling agent such as an alkylsilane or a fluoroalkylsilane type is exemplified.

Japanese Unexamined Patent Publication No. 2011-93964 JP-A-2007-297543 Japanese Unexamined Patent Publication No. 2004-238455

In applications where a hard coat layer is provided on the surface of an article, abrasion resistance is required, and this abrasion resistance may change depending on the usage environment. However, when using an article, it is desirable that there is little change in wear resistance due to the usage environment such as humidity change. As described above, Patent Documents 1 to 3 describe that an antifouling layer having a specific composition is provided on the hard coat layer, but there is no disclosure of an abrasion resistant layer that is less affected by humidity.

Therefore, the present invention obtains an abrasion-resistant layer further provided on the hard coat layer, which has a small decrease in abrasion resistance in a wet environment, and laminates the hard coat layer and the abrasion-resistant layer. The purpose is to get a body.

The present invention
A laminate including a hard coat layer and an abrasion resistant layer,
The wear-resistant layer has a monovalent group having a perfluoropolyether structure, a condensed structure derived from the first fluorine compound (A) in which a hydrolyzable group is bonded to a silicon atom, and the following formula (b1). ), Which is a layer containing a structure derived from the second fluorine compound (B), which is different from the first fluorine compound (A).

In the above formula (b1),
A ¹ and A ² are independent groups represented by hydrogen atom, fluorine atom, or -SiA ³ _c R ¹⁰ _3-c ^{, A 3} is a hydrolyzable group, and R ¹⁰ has 1 carbon atom. ~ 20 alkyl groups, c is an integer 1-3
Rf ^b11 and Rf ^b12 are independently hydrogen atoms, fluorine atoms, or −CF ₃ , except when − {C (Rf ^b11 ) (Rf ^b12 )} − becomes −CH ₂ −. If Rf ^b11 there are multiple well be different plurality of Rf ^b11 respectively, if Rf ^b12 there are a plurality may be different plurality of Rf ^b12, respectively,
D is -O-, -C (= O) -O-, -OC (= O) -O-, -NR-, -NRCO-, or -CONR- (R is a hydrogen atom, the number of carbon atoms is It represents an alkyl group of 1 to 4 or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when a plurality of Ds are present, the plurality of Ds may be different from each other.
b1 is 0 or more and 5 or less, b2 is 4 or more and 220 or less, and b3 is 0 or more and 190 or less.
A ¹ −, A ² −, b 1 − (CH ₂ ) −, b 2 − {C (Rf ^b11 ) (Rf ^b12 )} −, b 3 − (D) − are A ¹ −, A ^{As long as 2−} is the terminal and −O− is not continuous with −O− to −F, they are combined side by side in any order.

The number average molecular weight of the first fluorine compound (A) is preferably 2,000 or more and 50,000 or less.

The first fluorine compound (A) is preferably represented by the following formula (a1).

In the above formula (a1),
Rf ^a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
R ^11, R ^12, and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, if R ¹¹ there are a plurality may be different plural R ¹¹ are each, R ¹² is If there are two or more may be multiple R ¹² are different from each may be the case where R ¹³ there are a plurality of different plural R ¹³ are each,
^{E 1, E 2, E 3} , E 4, and E ⁵ is, independently represents a hydrogen atom or a fluorine atom, if E ¹ there are a plurality may be different plurality of E ^1, respectively, E ² may be the case where there are plural different multiple E ² respectively, when the E ³ there are a plurality may be different plurality of E ³ respectively, the plurality of E if E ⁴ there are a plurality of ⁴ may be different,
G ¹ and G ² are 2 to 10-valent organosiloxane groups each independently having a siloxane bond.
J ¹ , J ² , and J ³ are independently hydrolyzable groups _{or-(CH 2} ) _e6- Si (OR ¹⁴ ) ₃ , e 6 is 1-5, and R ¹⁴ is a methyl group. or an ethyl group, if J ¹ there are a plurality may be different plurality of J ^1, respectively, when J ² there are a plurality may be different plurality of J ^2, respectively, J ³ is more ^{Multiple J 3s} may be different if they exist
L ¹ and L ² are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, and a fluorine atom, and ^{when a plurality of L 1s} are present, a plurality of L 1 and L 2 are divalent linking groups. L ¹ is may be different from each, when L ² there are a plurality may be different plurality of L ^2, respectively,
a10 and a14 are 0 to 10 independently, respectively.
a11 and a15 are independently 0 or 1, respectively.
a12 and a16 are 0 to 9 independently of each other.
a13 is 0 or 1,
a21, a22, and a23 are 0 to 2 independently, respectively.
d11 is 1-9,
d12 is 0-9,
e1, e2, and e3 are 1 to 3 independently of each other.

Further, it is also preferable that the first fluorine compound (A) is represented by the following formula (a2-1).

In the above formula (a2-1),
Rf ^a21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced with fluorine atoms.
Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and a plurality of Rf ^a22s are present. if present may be different plurality of Rf ^a22 respectively, when multiple Rf ^a23 there may be different plurality of Rf ^a23 respectively, when multiple Rf ^a24 exists multiple Rf ^a24 there may also be different, when a plurality of Rf ^a25 there may be different plurality of Rf ^a25 respectively,
R ²⁰ , R ²¹ , R ²² and R ²³ are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and when a plurality of R ^20s are present, the plurality of R ^20s are different from each other. At best, when a plurality of R ²¹ are present or different plural R ²¹ are each, when a plurality of R ²² are present or different plural R ²² are each, a plurality of R ²³ is ^{Multiple R 23s,} if present, may be different
R ²⁴ is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present, the plurality of R ^24s may be different from each other.
M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of M ^1s are present, the plurality of M ^1s may be different from each other.
M ² is a hydrogen atom or a halogen atom,
M ³ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-( R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when a plurality of M ^3s are present, the plurality of M ^3s may be different from each other.
M ⁴ is a hydrolyzable group, and when a plurality of M ^4s are present, the plurality of M ^4s may be different from each other.
f11, f12, f13, f14, and f15 are independently integers of 0 or more and 600 or less, and the total value of f11, f12, f13, f14, and f15 is 13 or more.
f16 is an integer of 1 or more and 20 or less.
f17 is an integer of 0 or more and 2 or less.
g1 is an integer of 1 or more and 3 or less,
Rf ^a21 −, M ² −, f11 − {C (R ²⁰ ) (R ²¹ )} −, f12 − {C (Rf ^a22 ) (Rf ^a23 )} −, f13 − {Si (R) ²² ) (R ²³ )}-, f14-{Si (Rf ^a24 ) (Rf ^a25 )}-, f15 -M ^3- , f16- [CH ₂ C (M ¹ ) {(CH ₂₎ ) _F17 −Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }] are arranged in the order of forming a perfluoropolyether structure at least in part with ^{Rf a21} − and M ^{2 − at the ends, and −O.} As long as − is not continuous with −O− to −F, they are combined side by side in any order.

The second fluorine compound (B) includes a compound in which A ¹ of the above formula (b1) is a fluorine atom and A ² is −SiA ³ _c R ¹⁰ _3-c , or the above formula (b1). It is preferable to contain a compound in which A ¹ and A ^{2 of the above are fluorine atoms.}

It is also preferable that the laminate of the present invention further contains a polyimide resin layer, and the abrasion resistant layer, the hard coat layer, and the polyimide resin layer are in this order from the surface.

It is also preferable that the hard coat layer contains an inorganic filler.

According to the present invention, since the hard coat layer further has a wear-resistant layer containing a condensed structure derived from a specific first fluorine compound and a structure derived from a specific second fluorine compound, a wet environment is provided. It is possible to realize a laminated body with less decrease in wear resistance.

The laminate of the present invention has a hard coat layer and an abrasion resistant layer, and the abrasion resistant layer is provided on the surface side of the laminate. In the present invention, the abrasion resistant layer is derived from the first fluorine compound (A). It is characterized in that it contains a condensed structure of the above, and also contains a structure derived from a specific second fluorine compound (B) different from the first fluorine compound (A). By doing so, it is possible to suppress a decrease in wear resistance in a moist environment. Hereinafter, the details of the abrasion resistant layer and the hard coat layer will be described in order.

(A) Abrasion-resistant layer The abrasion-resistant layer contains a condensed structure derived from the first fluorine compound (A) and has a structure derived from a second fluorine compound (B) different from the first fluorine compound (A). Includes. As will be described later, the first fluorine compound (A) may have a hydrolyzable group, and the second fluorine compound (B) may also have a hydrolyzable group. When the second fluorine compound (B) has a hydrolyzable group, the −SiX ¹ ₂ (OH) group ^{in the first fluorine compound (A) generated by hydrolysis (the X 1} is a hydrolyzable group). (The same shall apply hereinafter), -SiX ¹ (OH) ₂ groups, or -Si (OH) ₃ ^{groups, and the -SiX 2} ₂ (OH) group in the second fluorine compound (B) ^{(the X 2} is hydrolyzed). Degradable groups; the same applies hereinafter), -SiX ² (OH) ₂ groups, -Si (OH) ₃ groups, etc. are dehydrated and condensed to form a first fluorine compound (A) and a second fluorine compound (the same applies hereinafter). A hydrolyzed condensate with B) is formed. Therefore, in such a case, it is said that the wear-resistant layer contains the condensed structure derived from the first fluorine compound (A) and the structure derived from the second fluorine compound (B). ) And the second fluorine compound (B). On the other hand, when the second fluorine compound (B) does not have a hydrolyzable group, the wear-resistant layer has a condensed structure derived from the first fluorine compound (A) and the second fluorine compound (B). The inclusion of the derived structure means that the first fluorine compound (A) contains a condensed structure obtained by dehydration condensation and the second fluorine compound (B).

(A-1) First Fluorine Compound (A)
The first fluorine compound (A) (hereinafter, may be simply referred to as “compound (A)”) contains fluorine and polymerizes with each other or with other monomers (particularly polycondensation). A compound that can form a matrix of an abrasion-resistant layer by binding through (reaction), specifically, a fluorine compound in which a monovalent group having a perfluoropolyether structure and a hydrolyzable group are bonded to a silicon atom. Is.

The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyoxyalkylene group are replaced with fluorine atoms, and can also be called a perfluoropolyoxyalkylene group. The perfluoropolyether structure can impart water repellency to the resulting wear resistant layer. The number of carbon atoms contained in the longest linear portion of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, still more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and may be, for example, about 200.

In compound (A), the monovalent group having the perfluoropolyether structure is bonded to the silicon atom. A suitable linking group may be present on the side where the perfluoropolyether structure is bonded to the silicon atom, or the perfluoropolyether structure may be directly bonded to the silicon atom without the linking group. As the linking group, for example, a hydrocarbon group such as an alkylene group or an aromatic hydrocarbon group, a (poly) oxyalkylene group, a group in which at least a part of these hydrogen atoms are substituted with a fluorine atom, and these are suitable. Examples include groups linked to. The carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 15 or less, and more preferably 2 or more and 10 or less.

A plurality of silicon atoms may be bonded to one linking group, or a plurality of perfluoropolyether structures may be bonded to one linking group. The number of monovalent groups having the perfluoropolyether structure bonded to the silicon atom may be 1 or more, may be 2 or 3, but is preferably 1 or 2. It is particularly preferable to have.

Further, in the compound (A), a hydrolyzable group is bonded to the silicon atom, and the hydrolyzable group is a group of the compounds (A) with each other or with the compound (A) through a hydrolysis / dehydration condensation reaction. It has the function of binding to active hydrogen derived from the hydroxy group on the surface of the material. Examples of such a hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms), an acetoxy group, and a halogen atom (particularly a chlorine atom). Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group and a chlorine atom are particularly preferable.

The number of hydrolyzable groups bonded to the silicon atom may be one or more and may be 2 or 3, but is preferably 2 or 3, and particularly preferably 3. When two or more hydrolyzable groups are bonded to a silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but the same hydrolyzable group may be bonded to the silicon atom. preferable. The total number of monovalent groups having a perfluoropolyether structure and hydrolyzable groups bonded to a silicon atom is usually 4, but may be 2 or 3 (particularly 3). In the case of 3 or less, for example, an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), a hydrogen atom, an isocyanate group, or the like can be bonded to the remaining bonding hands.

The monovalent group having a perfluoropolyether structure of compound (A) may be linear or may have a side chain. Further, the monovalent group having a perfluoropolyether structure may further have a silicon atom and a hydrolyzable group bonded to the silicon atom.

The number average molecular weight of compound (A) is not particularly limited, but is preferably 2,000 or more and 50,000 or less, for example. The lower limit of the number average molecular weight of compound (A) is preferably 4,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, and the upper limit is preferably 40,000 or less, more preferably 20. It is 000 or less, more preferably 15,000 or less.

Compound (A) can be represented by, for example, the following formula (a1).

In the above formula (a1),
Rf ^a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
R ^11, R ^12, and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, if R ¹¹ there are a plurality may be different plural R ¹¹ are each, R ¹² is If there are two or more may be multiple R ¹² are different from each may be the case where R ¹³ there are a plurality of different plural R ¹³ are each,
^{E 1, E 2, E 3} , E 4, and E ⁵ is, independently represents a hydrogen atom or a fluorine atom, if E ¹ there are a plurality may be different plurality of E ^1, respectively, E ² may be the case where there are plural different multiple E ² respectively, when the E ³ there are a plurality may be different plurality of E ³ respectively, the plurality of E if E ⁴ there are a plurality of ⁴ may be different,
G ¹ and G ² are 2 to 10-valent organosiloxane groups each independently having a siloxane bond.
J ¹ , J ² , and J ³ are independently hydrolyzable groups _{or-(CH 2} ) _e6- Si (OR ¹⁴ ) ₃ , e 6 is 1-5, and R ¹⁴ is a methyl group. or an ethyl group, if J ¹ there are a plurality may be different plurality of J ^1, respectively, when J ² there are a plurality may be different plurality of J ^2, respectively, J ³ is more ^{Multiple J 3s} may be different if they exist
L ¹ and L ² are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, and a fluorine atom, and ^{when a plurality of L 1s} are present, a plurality of L 1 and L 2 are divalent linking groups. L ¹ is may be different from each, when L ² there are a plurality may be different plurality of L ^2, respectively,
d11 is 1-9,
d12 is 0-9,
a10 and a14 are 0 to 10 independently, respectively.
a11 and a15 are independently 0 or 1, respectively.
a12 and a16 are 0 to 9 independently of each other.
a13 is 0 or 1,
a21, a22, and a23 are 0 to 2 independently, respectively.
e1, e2, and e3 are 1 to 3 independently of each other.

In the above formula (a1)
Rf ^a1 is preferably −O − (CF ₂ CF ₂ O) _e4 − or −O − (CF ₂ CF ₂ CF ₂ O) _e5 − (e4 is preferably 1 to 85, and e5 is preferably. 25 to 70, more preferably 35 to 50),
R ¹¹ , R ¹² , and R ¹³ are each independently preferably an alkyl group having 1 to 10 carbon atoms.
L ¹ and L ² are preferably divalent linking groups having 1 to 5 carbon atoms containing a fluorine atom, respectively.
G ¹ and G ² are preferably 2 to 5 valent organosiloxane groups having a siloxane bond independently of each other.
J ¹ , J ² , and J ³ are each independently preferably a methoxy group, an ethoxy group, or − (CH ₂ ) _e6- Si (OR ¹⁴ ) ₃ .
a10 is preferably 0 to 5 (more preferably 0 to 3), a11 is preferably 0, a12 is preferably 0 to 7 (more preferably 0 to 5), and a14 is preferably 1 to 6 (more preferably 1). ~ 3), a15 is preferably 0, a16 is preferably 0 to 6, a21 to a23 are all preferably 0 or 1 (more preferably all 0), and d11 is preferably 1 to 5 (more preferably 1). ~ 3), d12 is preferably 0 to 3 (more preferably 0 or 1), and e1 to e3 are all preferably 3.

As the compound (A), Rf ^a1 of the above formula (a1) is −O − (CF ₂ CF ₂ CF ₂ O) _e5 −, e5 is 35 to 50, and both L ¹ and L ² are carbon. It is a perfluoroalkylene group of the number 1 to 3, E ¹ , E ² , and E ³ are all hydrogen atoms, and E ⁴ and E ⁵ are hydrogen atoms or fluorine atoms, and J ¹ , J ² , and J ³ Are all methoxy groups or ethoxy groups (particularly methoxy groups), a10 is 1 to 3, a11 is 0, a12 is 0 to 5, a13 is 1, and a14 is 2 to 5. Yes, a15 is 0, a16 is 0-6, a21 to a23 are independently 0 or 1 (more preferably, a21 to a23 are all 0), d11 is 1, and d12. It is preferable to use a compound in which is 0 or 1 and e1 to e3 are both 3.

When the compound a1 used as the compound (A) in the examples described later is represented by the above formula (a1), Rf ^a1 is −O− (CF ₂ CF ₂ CF ₂ O) ₄₃ −, and L ¹ and L ² is − (CF ₂ ) −, E ¹ , E ² and E ³ are all hydrogen atoms, E ⁵ is a fluorine atom, and J ¹ and J ² are all methoxy groups. a10 is 2, a11 is 0, a12 is 0-5, a13 is 1, a14 is 3, a15 is 0, a16 is 0, a21, a22 are all 0, d11 is 1, d12 is 0, e1, e2 is 3 in each case. Further, the compound in Example 5 to be described later compounds a2 used as (A), is represented by the formula (a1), Rf ^a1 is _{-O- (CF 2 CF 2 CF 2} O) 40 - a and, L ¹ and L ² is − (CF ₂ ) −, E ¹ , E ² and E ³ are all hydrogen atoms, E ⁵ is a fluorine atom, and J ¹ and J ² are all methoxy groups. , A10 is 2, a11 is 0, a12 is 0, a13 is 1, a14 is 3, a15 is 0, a16 is 0, a21, a22 are all 0, d11 is 1, d12 is 0, e1, e2. Are all three.

As the compound (A), Rf ^a1 of the above formula (a1) is −O− (CF ₂ CF ₂ CF ₂ O) _e5 −, e5 is 25 to 40, and L ¹ is a fluorine atom and an oxygen atom. It is a divalent linking group containing 3 to 6 carbon atoms, L ² is a perfluoroalkylene group having 1 to 3 carbon atoms, E ² and E ³ are both hydrogen atoms, and E ⁵ is a fluorine atom. Yes, J ² is − (CH ₂ ) _e6 −Si (OCH ₃ ) ₃ , e6 is 2-4, a10 is 1-3, a11 is 0, a12 is 0, a13. Is 0, a14 is 2-5, a15 is 0, a16 is 0, and a21 to a23 are independently 0 or 1 (more preferably, a21 to a23 are all 0). ), D11 is 1, d12 is 0, and e2 is 3. It is also preferable to use a compound.

In addition, compound (A) can also be represented by the following formula (a2-1).

In the above formula (a2-1),
Rf ^a21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced with fluorine atoms.
Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and a plurality of Rf ^a22s are present. if present may be different plurality of Rf ^a22 respectively, when multiple Rf ^a23 there may be different plurality of Rf ^a23 respectively, when multiple Rf ^a24 exists multiple Rf ^a24 there may also be different, when a plurality of Rf ^a25 there may be different plurality of Rf ^a25 respectively,
R ²⁰ , R ²¹ , R ²² and R ²³ are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and when a plurality of R ^20s are present, the plurality of R ^20s are different from each other. At best, when a plurality of R ²¹ are present or different plural R ²¹ are each, when a plurality of R ²² are present or different plural R ²² are each, a plurality of R ²³ is ^{Multiple R 23s,} if present, may be different
R ²⁴ is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present, the plurality of R ^24s may be different from each other.
M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of M ^1s are present, the plurality of M ^1s may be different from each other.
M ² is a hydrogen atom or a halogen atom,
M ³ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-( R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when a plurality of M ^3s are present, the plurality of M ^3s may be different from each other.
M ⁴ is a hydrolyzable group, and when a plurality of M ^4s are present, the plurality of M ^4s may be different from each other.
f11, f12, f13, f14, and f15 are independently integers of 0 or more and 600 or less, and the total value of f11, f12, f13, f14, and f15 is 13 or more.
f16 is an integer of 1 or more and 20 or less.
f17 is an integer of 0 or more and 2 or less.
g1 is an integer of 1 or more and 3 or less,
Rf ^a21 −, M ² −, f11 − {C (R ²⁰ ) (R ²¹ )} −, f12 − {C (Rf ^a22 ) (Rf ^a23 )} −, f13 − {Si (R) ²² ) (R ²³ )}-, f14-{Si (Rf ^a24 ) (Rf ^a25 )}-, f15 -M ^3- , f16- [CH ₂ C (M ¹ ) {(CH ₂₎ ) _F17 −Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }] − is arranged in the order of forming a perfluoropolyether structure at least in part with ^{Rf a21} − and M ^{2 − at the ends, and −} As long as O-is not continuous with -O- to -F, they are combined side by side in any order.
That is, in the equation (a2-1), f11 − {C (R ²⁰ ) (R ²¹ )} − are necessarily continuous, and f12 − {C (Rf ^a22 ) (Rf ^a23 )} − are continuous. , F13 − {Si (R ²² ) (R ²³ )} − are continuous, f14 − {Si (Rf ^a24 ) (Rf ^a25 )} − are continuous, and f15 −M ³ − are continuous. However, it does not mean that f16- [CH ₂ C (M ¹ ) {(CH ₂ ) _f17-Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }]-are arranged in this order in succession. , -C (R ²⁰ ) (R ²¹ ) -Si (Rf ^a24 ) (Rf ^a25 ) -CH ₂ C (M ¹ ) {(CH ₂ ) _f17-Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 } -C (Rf ^a22 ) (Rf ^a23 ) -M ^3- Si (R ²² ) (R ²³ ) -C (Rf ^a22 ) (Rf ^a23 )-and so on, each can be arranged in any order. is there.

Rf ^a21 is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and further preferably 1 to 10 carbon atoms. It is a perfluoroalkyl group of 5.

Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are preferably independently each of a fluorine atom or an alkyl group having 1 to 2 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, more preferably. Are all fluorine atoms.

R ²⁰ , R ²¹ , R ²² and R ²³ are preferably independent hydrogen atoms or alkyl groups having 1 to 2 carbon atoms, and more preferably all hydrogen atoms.

R ²⁴ is preferably an alkyl group having 1 to 5 carbon atoms.

M ¹ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and more preferably all hydrogen atoms.

M ² is preferably a hydrogen atom.

M ³ is preferably −C (= O) −O−, −O−, −OC (= O) −, and more preferably all −O−.

M ⁴ is preferably an alkoxy group or a halogen atom, and particularly preferably a methoxy group, an ethoxy group or a chlorine atom.

Preferably, f11, f13, and f14 are 1/2 or less of f12, more preferably 1/4 or less, further preferably f13 or f14 is 0, and particularly preferably f13 and f14 are 0.

f15 is preferably 1/5 or more of the total value of f11, f12, f13, and f14, and is less than or equal to the total value of f11, f12, f13, and f14.

f12 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, still more preferably 50 or more and 200 or less (more preferably 30 to 150, particularly 80 to 140). f15 is preferably 4 or more and 600 or less, more preferably 4 or more and 200 or less, still more preferably 10 or more and 200 or less (more preferably 30 to 60). The total value of f11, f12, f13, f14, and f15 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, and further preferably 50 or more and 200 or less.

f16 is preferably 1 or more and 18 or less. More preferably, it is 1 or more and 15 or less, and further preferably 1 or more and 10 or less.

f17 is preferably 0 or more and 1 or less.

g1 is preferably 2 or more and 3 or less, and more preferably 3.

f11-{C (R ²⁰ ) (R ²¹ )}-, f12-{C (Rf ^a22 ) (Rf ^a23 )}-, f13-{Si (R ²² ) (R ²³ )}- , F14 − {Si (Rf ^a24 ) (Rf ^a25 )} −, f15 −M ³ − are arbitrary in the formula as long as they are arranged in the order of forming a perfluoropolyether structure at least in part. ^{However, preferably, the repeating unit (that is,-{C (Rf a22} ) (Rf ^a23 )}-) enclosed in parentheses with f12 on the most fixed end side (the side that bonds with the silicon atom) is It is located on the free end side of the repeating unit (that is,-{C (R ²⁰ ) (R ²¹ )}-) enclosed in parentheses with f11 on the most free end side, and more preferably on the most fixed end side. Repeat units in parentheses with f12 and f14 (ie,-{C (Rf ^a22 ) (Rf ^a23 )}-and-{Si (Rf ^a24 ) (Rf ^a25 )}-) are the most. Repeat units in parentheses with f11 and f13 on the free end side (ie-{C (R ²⁰ ) (R ²¹ )}-and-{Si (R ²² ) (R ²³ )}-) It is located on the free end side.

In the above formula (a2-1), Rf ^a21 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are all fluorine atoms, and M ³ is all −O−. M ⁴ is all a methoxy group, an ethoxy group or a chlorine atom (particularly a methoxy group or an ethoxy group), M ¹ and M ² are both hydrogen atoms, f11 is 0, and f12 is 30 to 150 (from). It is preferable that 80 to 140), f15 is 30 to 60, f13 and f14 are 0, f17 is 0 or more and 1 or less (particularly 0), g1 is 3, and f16 is 1-10.

In the compound a1 used as the compound (A) in the examples described later, when expressed by the above formula (a2-1), Rf ^a21 is C ₃ F ₇ −, and both Rf ^a22 and Rf ^a23 are hydrogen atoms. F11 = f13 = f14 = 0, f12 is 131, f15 is 44, f16 is 1 to 6, f17 is 0, M ¹ and M ² are hydrogen atoms, M ³ is -O-, and M. ⁴ is a methoxy group and g1 is 3.

Further, when the compound a2 used as the first fluorine compound (A) in the examples is represented by the above formula (a2-1), Rf ^a21 is C ₃ F ₇ −, and both Rf ^a22 and Rf ^a23 are fluorine. It is an atom, f11 = f13 = f14 = 0, f12 is 122, f15 is 41, f16 is 1, f17 is 0, M ¹ and M ² are hydrogen atoms, M ³ is -O-, and M ⁴ Is a methoxy group and g1 is 3.

In addition, compound (A) can also be represented by the following formula (a2-2).

In the above formula (a2-2),
Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and a plurality of Rf ^a26s are present. if present may be different plurality of Rf ^a26 respectively, when multiple Rf ^a27 there may be different plurality of Rf ^a27 respectively, when multiple Rf ^a28 exists multiple Rf ^a28 there may also be different, when a plurality of Rf ^a29 there may be different plurality of Rf ^a29 respectively,
R ²⁵ , R ²⁶ , R ²⁷ , and R ²⁸ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of R ^25s are present, the plurality of R ^25s are different from each other. At best, when a plurality of R ²⁶ are present or different plural R ²⁶ are each, when a plurality of R ²⁷ are present or different plural R ²⁷ are each, a plurality of R ^{28 Multiple R 28s,} if present, may be different
R ²⁹ and R ³⁰ are independently alkyl groups having 1 to 20 carbon atoms, and when a plurality of R ^29s are present, the plurality of R ^29s may be different from each other, and a plurality of R ^30s are present. If so, multiple R ^30s may be different.
M ⁷ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-( R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when a plurality of M ^7s are present, the plurality of M ^7s may be different from each other.
M ⁵ and M ⁹ are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and when a plurality of M ^5s are present, the plurality of M ^5s may be different from each other, and a plurality of Ms may be different from each other. ^{If 9} is present, multiple M ^9s may be different.
M ⁶ and M ¹⁰ are independently hydrogen atoms or halogen atoms, respectively.
M ^8, M ¹¹ are each independently a hydrolyzable group, when a plurality of M ⁸ there may be different plurality of M ^8, respectively, when a plurality of M ¹¹ is present more M ¹¹ may be different,
f21, f22, f23, f24, and f25 are independently integers of 0 or more and 600 or less, and the total value of f21, f22, f23, f24, and f25 is 13 or more.
f26 and f28 are independently integers of 1 or more and 20 or less, respectively.
f27 and f29 are independently integers of 0 or more and 2 or less, respectively.
g2 and g3 are independently integers of 1 or more and 3 or less, respectively.
M ¹⁰ −, M ⁶ −, f21 − {C (R ²⁵ ) (R ²⁶ )} −, f22 − {C (R f ^a26 ) (R f ^a27 )} −, f 23 − {Si (R) ^{27) (R 28)} -} , f24 amino ^{- {Si (Rf a28) (} Rf a29)} -, f25 amino -M ⁷ -, f26 amino ^{_{- [CH 2 C (M 5}} ) {(CH 2 ) _F27 −Si (M ⁸ ) _g2 (R ²⁹ ) _3-g2 }], f28 − [CH ₂ C (M ⁹ ) {(CH ₂ ) _f29 −Si (M ¹¹ ) _g3 (R ³⁰ ) _{3- g3} }] is ended with M ¹⁰ − and M ⁶ −, forms a perfluoropolyether structure at least in part, and is bound in any order as long as −O − is not continuous with −O −. The joining in any order is the same as described in the above formula (a2-1), and the repeating units are continuously arranged in the order described in the above formula (a2-2). Not limited to meaning.

In the above formula (a2-2), Rf ^a26 , Rf ^a27 , Rf ^a28 , and Rf ^a29 are all fluorine atoms, M ⁷ are all −O−, and M ⁸ and M ¹¹ are all methoxy groups, ethoxy groups, or Chlorine atom (particularly methoxy group or ethoxy group), M ⁵ , M ⁶ , M ⁹ and M ¹⁰ are all hydrogen atoms, f21 is 0, f22 is 30 to 150 (more preferably 80 to 140), It is preferable that f25 is 30 to 60, f23 and f24 are 0, f27 and f29 are 0 or more and 1 or less (particularly 0), g2 and g3 are 3, and f26 and f28 are 1-10.

More specifically, the compound (A) includes a compound represented by the following formula (a3).

In the above formula (a3), R ³⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, R ³¹ and R ³² are both perfluoroalkylene groups having 2 to 6 carbon atoms, and R ³³ is a carbon. It is a trivalent saturated hydrocarbon group having 2 to 6 ^{carbon atoms, and R 34} is an alkyl group having 1 to 3 carbon atoms. The carbon numbers of R ³⁰ , R ³¹ , R ³² , and R ³³ are preferably 2 to 4 independently, and more preferably 2 to 3 respectively. h1 is 5 to 70, h2 is 1 to 5, and h3 is 1 to 10. h1 is preferably 10 to 60, more preferably 20 to 50, h2 is preferably 1 to 4, more preferably 1 to 3, h3 is preferably 1 to 8, and more preferably 1 to 6.

As the compound (A), a compound represented by the following formula (a4) can also be mentioned.

In the above formula (a4), R ⁴⁰ is a perfluoroalkyl group having 2 to 5 carbon atoms ^{, R 41 is a perfluoroalkylene group having 2 to 5 carbon atoms, and R 42} is a perfluoroalkylene group having 2 to 5 carbon atoms. A part of the hydrogen atom of the alkylene group is a fluoroalkylene group substituted with fluorine, R ⁴³ and R ⁴⁴ are independently alkylene groups having 2 to 5 carbon atoms, and R ⁴⁵ is a methyl group or an ethyl group. is there. k1, k2, and k3 are independently integers of 1 to 5.

(A-2) Second fluorine compound (B)
The second fluorine compound (B) (hereinafter, may be simply referred to as “compound (B)”) is represented by the following formula (b1) and is a compound different from the first fluorine compound (A).

In the above formula (b1),
A ¹ and A ² are independent groups represented by hydrogen atom, fluorine atom, or -SiA ³ _c R ¹⁰ _3-c ^{, A 3} is a hydrolyzable group, and R ¹⁰ has 1 carbon atom. ~ 20 alkyl groups, c is an integer 1-3
Rf ^b11 and Rf ^b12 are independently hydrogen atoms, fluorine atoms, or −CF ₃ , except when − {C (Rf ^b11 ) (Rf ^b12 )} − becomes −CH ₂ −. When ^{there are a plurality of Rf b11} , they may be different from each other, and when there are a plurality of ^{Rf b12, they may be different from each other.}
D represents -O-, -C (= O) -O-, or -OC (= O) -O-, -NR-, -NRCO-, -CONR- (R is a hydrogen atom or the number of carbon atoms). Is an alkyl group of 1 to 4 or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when a plurality of D's are present, they may be different from each other.
b1 is 0 or more and 5 or less, b2 is 4 or more and 220 or less, and b3 is 0 or more and 190 or less.
A ¹ −, A ² −, b 1 − (CH ₂ ) −, b 2 − {C (Rf ^b11 ) (Rf ^b12 )} −, b 3 − (D) − are A ¹ −, A ^{As long as 2−} is the terminal and −O− is not continuous with −O− to −F, they are bonded side by side in any order (usually linearly). That is, in the equation (b1), b1 − (CH ₂ ) − is necessarily continuous, b2 − {C (Rf ^b11 ) (Rf ^b12 )} − are continuous, and b3 − (D) −. ^Does not mean that are continuous and arranged in this order, but each can be arranged in any order, such as _{−CH 2} −C (Rf ^b11 ) (Rf b12) −CH ₂ −D−CH _{2 −.} Is.

Fluorine atom is preferable for A ¹
A ² is preferably a fluorine atom or -Si A ³ _c R ¹⁰ _3-c , and when A ² is -Si ^{A 3} _c R ¹⁰ _3-c , A ³ is a methoxy group or an ethoxy group and c is 3. Preferably
It is preferable that both Rf ^b11 and Rf ^{b12 are fluorine atoms.}
D is preferably —O—
b1 is preferably 0 to 3, more preferably 0 to 2, and is preferably 0 to 2.
b2 is preferably 4 to 6.
b3 is preferably 0 to 4, more preferably 0.

As one of the preferred embodiments of the present invention, the compound (B) is preferably a compound in which A ¹ of the above formula (b1) is a fluorine atom and A ² is −SiA ³ _c R ¹⁰ _3-c. It is more preferable that the compound (B) does not have a perfluoropolyether structure. The compound (B) is, A ¹ is a fluorine atom, and A ² is SiA ^{₃ 3} (A ³ is preferably a methoxy group or an ethoxy group), a compound that does not have a perfluoropolyether structure Is more preferable. In particular, A ¹ is a fluorine atom, A ² is SiA ³ ₃ , A ³ is a methoxy group or an ethoxy group, Rf ^b11 and Rf ^b12 are both fluorine atoms, and b1 is 0 to 3. , B2 is 4 to 8, and b3 is 0. It is preferable to use a compound that satisfies all of the above conditions.

Further, as one of another preferable embodiments, the compound (B) is preferably a compound in which ^{A 1} and A ^{2 of the above formula (b1) are fluorine atoms.} Further, more preferably, ^{it is preferable to use a compound in which A 1} and A ² are fluorine atoms, Rf ^b11 and Rf ^b12 are both fluorine atoms, D is −O−, and b1 is 0 to 3. .. In this case, the number average molecular weight of compound (B) is preferably 8,000 to 15,000, more preferably 9,000 to 13,000, and the values of b2 and b3 are appropriately set according to the molecular weight of the compound. it can.

As the compound (B), only one kind may be used, or two or more kinds may be used in combination.

When FAS13E used as the compound (B) in the examples described later is represented by the above formula (b1), A ¹ is a fluorine atom and A ² is Si (OC ₂ H ₅ ) ₃ (that is, A ^3). Is an ethoxy group, and c = 3), Rf ^b11 , and Rf ^b12 are all fluorine atoms, and b1 = 2, b2 = 6, and b3 = 0. When von Bryn M60 is represented by the above formula (b1), A ¹ and A ² are fluorine atoms, Rf ^b11 and Rf ^b12 are both fluorine atoms, D is −O−, and b1 = 0. , B2 = 2 + 2p + q (ie, 188 to 215), b3 = p + q + 1 (ie, in the range of 106 to 189).

Specific examples of the compound (B) include a compound represented by the following formula (b2).

In the above formula (b2), R ⁶⁰ is a perfluoroalkyl group having 3 to 8 carbon atoms, R ⁶¹ is an alkylene group having 1 to 5 carbon atoms, and R ⁶² is an alkyl group having 1 to 3 carbon atoms. .. As the compound represented by the above formula (b2), it is also preferable to use a compound having a boiling point of 100 ° C. or higher (preferably 300 ° C. or lower).

The compound (B) is, for example, a polyalkylene glycol in which the hydrogen atom of at least one OH group may be substituted with an alkyl group or an alkyl fluoride group, and all the hydrogen atoms of the alkylene group become fluorine atoms. Substituted polyalkylene glycol can be mentioned, and can be expressed by the following formula (b3), for example.

In the above formula (b3), R ⁷⁰ is an alkyl group having 1 to 16 carbon atoms or a hydrogen atom in which ^{one or more hydrogen atoms may be substituted with a fluorine atom, and R 71} is one or more hydrogen atoms. Atoms are alkoxy groups or OH groups having 1 to 16 carbon atoms which may be substituted with hydrogen atoms, and m1 − (OC ₄ F ₈ ) −, m 2 − (OC ₃ F ₆ ) −, m3- (OC ₂ F ₄ )-and m4- (OCF ₂ ) ^{-are arranged in any order as long as R 70} and R ⁷¹ are the ends, and m1 to m4 are compound (B). It is a value determined to be a liquid at normal pressure. The number average molecular weight of such compound (B) is, for example, 8,000 to 15,000, preferably 9,000 to 13,000. In particular, m1 = m2 = 0, R ⁷⁰ is a perfluoroalkyl group having 1 to 3 carbon atoms (particularly a perfluoromethyl group), and R ⁷¹ is a perfluoroalkoxy group having 1 to 3 carbon atoms (particularly perfluoro). Compound (B), which is a methoxy group and has a molecular weight of 9,000 to 13,000, is preferable.

The thickness of the wear-resistant layer is, for example, 3 to 20 nm. The wear-resistant layer has water repellency, and the contact angle measured by the sessile drop method (analysis method: θ / 2 method) at a liquid volume of 3 μL is, for example, about 110 to 125 °. The contact angle hysteresis and slide angle measured by the slide-down method (analysis method: contact method) with a liquid volume of 6.0 μL and a slide-down determination distance: 0.25 mm are about 11 to 20 ° (preferably 11 to 17 °) and 30 respectively. It is about ~ 55 ° (preferably 30 to 50 °). Further, on the wear-resistant layer, a silanol condensation catalyst, an antioxidant, a rust preventive, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, and an antibiotic agent, as long as the effects of the present invention are not impaired. It may contain various additives such as deodorants, pigments, flame retardants, and antistatic agents.

(B) Hard coat layer The hard coat layer is a layer having a surface hardness, and the hardness is, for example, a pencil hardness of 2H or more. The hard coat layer may have a single layer structure or a multi-layer structure. The hard coat layer contains a hard coat layer resin, and examples of the hard coat layer resin include acrylic resin, epoxy resin, urethane resin, benzyl chloride resin, vinyl resin or silicone resin, or a mixture thereof. Examples thereof include ultraviolet curable type, electron beam curable type, and heat curable type resins such as resins. In particular, the hard coat layer preferably contains an acrylic resin in order to exhibit high hardness. It is preferable to contain an epoxy resin because the adhesion to the wear-resistant layer tends to be good.

The hard coat layer may further contain an ultraviolet absorber. As the ultraviolet absorber, a benzophenone-based compound, a salicylate-based compound, a benzotriazole-based compound, a triazine-based compound and the like can be used, and preferably, ultraviolet absorption having a concentration capable of absorbing 95% or more of light having a wavelength of 400 nm or less. It is preferable to disperse the agent. The above-mentioned "system compound" refers to a derivative of the compound to which the "system compound" is attached. For example, the "benzophenone-based compound" refers to a compound having an unsubstituted benzophenone as a basic skeleton and appropriately substituting a hydrogen atom of the benzophenone with a substituent. The same applies to other "system compounds".

The hard coat layer may further contain a metal oxide such as silica and alumina, and an inorganic filler such as polyorganosiloxane. By including such an inorganic filler, the adhesion to the wear-resistant layer can be improved. The thickness of the hard coat layer can be appropriately set according to the application to which the laminate of the present invention is applied, for example, 1 to 100 μm, preferably 3 to 50 μm, and more preferably 5 to 20 μm.

(C) Resin layer The laminate of the present invention preferably further contains a resin layer, and the abrasion-resistant layer, the hard coat layer, and the resin layer are in this order from the surface of the laminate. The resin component of the resin layer is not particularly limited, but is polyacrylate-based resin, polyamide-based resin, polyimide-based resin, polyamideimide-based resin, polyurethane-based resin, polyester-based resin, polycarbonate-based resin, polyether sulfone-based resin, and acetylcellulose-based resin. Resins, cycloolefin resins, polyvinyl alcohol resins and the like are preferable because they can easily improve the adhesion to the hard coat layer, and polyimide resins and polyamideimide resins are particularly preferable. Further, it may be a laminate of a hard coat layer and an antireflection layer, or the hard coat layer may have a function of an antireflection layer.

The polyimide resin layer is a polyimide polymer obtained by polycondensation using diamines and tetracarboxylic acid dianhydride or a dicarboxylic acid compound as a starting material, and at least one of polyimide and polyamide-imide is the main component. Included as.

The diamines are not particularly limited, and aromatic diamines, alicyclic diamines, aliphatic diamines and the like usually used for the synthesis of polyimide can be used. The diamines may be used alone or in combination of two or more.

Further, the tetracarboxylic dianhydride is not particularly limited, and an aromatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, and an aliphatic tetracarboxylic dianhydride can be used. The tetracarboxylic dianhydride may be used alone or in combination of two or more.

Further, the dicarboxylic acid compound is not particularly limited, and aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and aliphatic dicarboxylic acids can be used. The dicarboxylic acid may be used alone or in combination of two or more. Specific examples thereof include terephthalic acid and 2,5-naphthalenedicarboxylic acid.

At least one selected from the group consisting of a fluorine group, a trifluoromethyl group, a hydroxyl group, a sulfone group, a carbonyl group, a heterocycle, a long-chain alkyl group, or the like in at least one of the above diamines and tetracarboxylic acid dianhydride. It may have one or more functional groups of.

Among the raw materials for the above-mentioned polyimide resins, the tetracarboxylic dianhydride is a tetracarboxylic dianhydride having a fluorine substituent or a fat from the viewpoint of transparency, flexibility and solubility in a solvent of the polyimide resin. It is preferable to use a cyclic tetracarboxylic dianhydride, and a tetracarboxylic dianhydride having a fluorine substituent is particularly preferable. Specific examples include 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, cyclohexanecarboxylic dianhydride and the like. , Preferably 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride. As the diamines, it is preferable to use aromatic diamines having a fluorine substituent, and specific examples thereof include 2,2'-bis (trifluoromethyl) benzidine.

The polyimide resin preferably further contains a silicon material containing a silicon atom. Examples of such a silicon material include silicon compounds such as silica particles and quaternary alkoxysilane (tetraethyl orthosilicate (TEOS) and the like). Among these silicon materials, silica particles are preferable from the viewpoint of flexibility of the polyimide resin layer. The average primary particle size of the silica particles is preferably 10 to 100 nm, preferably 20 to 50 nm. It is preferable that the average primary particle size of the silica particles is 100 nm or less because the transparency can be improved and the strength of the resin layer can be improved by setting the silica particles to 10 nm or more. The average primary particle size of the silica particles can be measured by the BET method or observation with a transmission electron microscope (TEM).

The thickness of the resin layer can be appropriately set according to the application to which the laminate of the present invention is applied, for example, preferably 10 to 500 μm, preferably 20 to 300 μm, and more preferably 40 to 100 μm.

A primer layer may be provided between the resin layer and the hard coat layer. Further, a primer layer may be provided between the abrasion resistant layer and the hard coat layer. Examples of the primer agent include a primer agent such as an ultraviolet curable type, a thermosetting type, or a two-component curable type epoxy compound. It is preferable that the compound contained in the primer layer is chemically bonded to the resin component contained in the resin layer or the silicon material contained if necessary. Further, a polyamic acid may be used as the primer agent, and the adhesion between the resin layer and the hard coat layer can be improved. Further, a silane coupling agent may be mentioned as a primer agent, which may be chemically bonded to a silicon material contained in the resin substrate as necessary by a condensation reaction. The silane coupling agent is preferably used when the compounding ratio of the silicon material contained in the resin base material is high. The thickness of the primer layer is, for example, 0.1 to 20 μm.

In the laminated body of the present invention, a resin layer (second resin layer) having a different composition may be laminated on the surface of the resin layer opposite to the surface side of the laminated body. Examples of such a resin include polyacrylate, polyamide, polyimide, polyamideimide, polyurethane, polyester, polycarbonate, and polyether sulfone. The thickness of the second resin layer is, for example, 10 to 100 μm.

(D) Method for Producing Laminated Body Next, the method for producing the laminated body of the present invention will be described including the method for producing the polyimide resin layer which is preferably contained in the present invention.

A polyimide varnish is prepared by dissolving a polyimide resin soluble in a polymer polymerized in a solvent using a known polyimide synthesis method. The solvent may be any solvent that can dissolve the polyimide resin, and for example, DMAc (dimethylacetamide), DMF (dimethylformamide), DMSO (dimethyl sulfoxide), γ-butyrolactone, or a combination thereof can be used.

Next, the silicon material is added to the polyimide varnish as needed, and the mixture is stirred and mixed by a known stirring method to uniformly disperse the silicon material in the polyimide varnish to prepare a dispersion liquid. In the polyimide varnish, the compounding ratio of the polyamide resin and the silicon material is preferably 1: 9 to 9: 1 in terms of mass ratio, and more preferably 3: 7 to 8: 2.

The polyimide varnish preferably further contains a binder that binds the particles of the silicon material to each other. The binder is preferably an alkoxysilane or a metal alkoxide, and more preferably an amino group-containing alkoxysilane such as (3-aminopropyl) triethoxysilane or aminoethylaminopropyltrimethoxysilane or an amino group-containing metal alkoxide.

Next, the above dispersion is applied onto a PET base material, a SUS belt, or a glass base material to form a coating film by a known roll-to-roll or batch method, and the coating film is dried to form a base material. A polyimide resin layer is formed by peeling from. The polyimide resin layer can be produced by appropriately evaporating the solvent at a temperature of 50 to 350 ° C. under an inert atmosphere or under reduced pressure conditions.

Next, a primer agent is applied, dried, and cured on the polyimide resin layer as needed to form a primer layer, and then a composition for forming a hard coat is applied and cured to obtain a hard coat layer. .. The composition for forming a hard coat may contain a resin such as the above-mentioned poly (meth) acrylates, an ultraviolet absorber, a polymerization initiator, a leveling agent, a solvent and the like.

The wear-resistant layer is formed by applying a primer agent on the hard coat layer as needed, drying and curing to form a primer layer, and then the first fluorine compound (A) and the second fluorine compound (the first fluorine compound (A)). It can be formed by applying a composition containing B) and a fluorine-based solvent (composition for coating an abrasion-resistant layer) and drying. Examples of the method for applying the composition containing the first fluorine compound (A) and the second fluorine compound (B) include a dip coating method, a roll coating method, a bar coating method, a spin coating method, a spray coating method, and a die coating method. Examples include the law and the gravure coater method.

When the wear-resistant layer is obtained by spray coating, for example, a spray coater (API-40RD advance) manufactured by Apiros can be used, and preferable conditions are, for example, scanning speed: 500 to 700 mm / sec, pitch: 3 to 7 mm, and the like. Liquid volume: 4 to 8 cc / min, atomizing air: 250 to 450 kPa, gap: 60 to 80 mm. Further, before applying the wear-resistant layer coating composition, the coated surface may be subjected to a hydrophilization treatment such as plasma treatment, corona treatment, or ultraviolet treatment, or may be subjected to primer treatment. By hydrophilizing the coated surface of the wear-resistant layer coating composition, a hydroxy group (especially when the coated surface is a hard coat layer formed of an epoxy resin) or a carboxy group (especially coated) is applied to the surface of the coated surface. A functional group (hydrophilic group) such as (when the surface is a hard coat layer formed of an acrylic resin) can be formed. When the functional group is formed on the surface of the coated surface, the adhesion between the wear-resistant layer and the hard coat layer can be improved. Before applying the wear-resistant layer coating composition, it is preferable to carry out a hydrophilic treatment, and it is more preferable to carry out a plasma treatment.

The conditions after applying the coating composition for an abrasion-resistant layer are not particularly limited, but are allowed to stand at room temperature in the air, and further at a temperature of 50 to 300 ° C., preferably 100 to 200 ° C. for 10 to 60 minutes. It is preferable to heat and dry to some extent.

As the fluorine-based solvent, for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent (particularly a fluorinated aromatic solvent) and the like can be used, and the boiling point is particularly 100 ° C. or higher. Is preferable. As the fluorinated ether solvent, hydrofluoro ethers such as fluoroalkyl (particularly perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (particularly methyl group or ethyl group) ether are preferable, and for example, ethyl nona fluorobutyl ether or ethyl nona. Fluoroisobutyl ether can be mentioned. Examples of the ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (manufactured by 3M, molecular weight of about 264, boiling point 76 ° C.). The fluorinated amine-based solvent is preferably an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group, and a third in which all hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly a perfluoroalkyl group). Primary amines are preferable, and specific examples thereof include tris (heptafluoropropyl) amines, and Florinate (registered trademark) FC-3283 (manufactured by 3M, molecular weight: about 521, boiling point: 128 ° C.) corresponds to this. Examples of the fluorinated hydrocarbon solvent include 1,3-bis (trifluoromethylbenzene) (boiling point: about 116 ° C.).

In addition to the above, the fluorocarbon solvent (C) includes hydrochlorofluorocarbons such as Asahiclean (registered trademark) AK225 (manufactured by Asahi Glass Co., Ltd.) and hydrofluorocarbons such as Asahiclean (registered trademark) AC2000 (manufactured by Asahi Glass Co., Ltd.). Can be used.

The molecular weight of the fluorine-based solvent (C) is preferably 900 or less, more preferably 800 or less, and the lower limit is not particularly limited, but is, for example, about 300.

The total amount of the first fluorine compound (A) and the second fluorine compound (B) with respect to 100% by mass of the composition for coating the wear-resistant layer is preferably 0.05% by mass or more, more preferably 0.10% by mass. It is more than that, and it is preferably 10% by mass or less, and more preferably 5% by mass or less. The mass ratio of the first fluorine compound (A) to the second fluorine compound (B) in the composition for coating the wear-resistant layer is preferably 0.5 or more, more preferably 1.0 or more. Further, 2.5 or less is preferable, and 2.0 or less is more preferable.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by the following examples, and it is of course possible to carry out the invention with appropriate modifications within the range that can be adapted to the above-mentioned purpose, and all of them are technical of the present invention. Included in the range.

Example 1
(1) Preparation of Resin Layer A resin solution of polyimide (KPI-MX300F [100] manufactured by Kawamura Sangyo Co., Ltd.) was formed into a film to prepare a resin layer having a thickness of 80 μm.

(2) Preparation of Hard Coat Layer Next, a solution for forming a hard coat layer is applied onto the resin layer to form a coating film, which is dried and then photocured by UV to obtain an epoxy resin and silica. A hard coat layer having a thickness of 10 μm containing particles was formed to obtain a laminate X0.

(3) Preparation of Wear-Resistant Layer As the first fluorine compound (A), the compound represented by the following formula (1) (hereinafter, compound a1), and as the second fluorine compound (B), FAS13E (C ₆ F _13). -C ₂ H _4- Si (OC ₂ H ₅ ) ₃ , boiling point 220 ° C, manufactured by Tokyo Kasei Kogyo Co., Ltd.), FC-3283 (fluorinert, manufactured by 3M) as the main compound are mixed and stirred at room temperature for a predetermined time. Then, a composition for coating an abrasion-resistant layer was obtained. In the composition, the ratio of compound a1 was 0.08% by mass, and the ratio of FAS13E was 0.05% by mass. The composition is applied onto the pretreated laminate X0 using a spray coater manufactured by Apiros, and further heated and dried at 80 ° C. for 30 minutes to obtain an abrasion resistant layer on the laminate X0. Was obtained to prepare a laminated body X. The layer structure of the laminate X was an abrasion resistant layer / a hard coat layer / a polyimide resin film. In the pretreatment, the surface of the laminate X0 was activated by using an atmospheric pressure plasma apparatus (manufactured by Fuji Machine Manufacturing Co., Ltd.). The conditions for spray coating are scan speed: 600 mm / sec, pitch: 5 mm, liquid volume: 6 cc / min, atomizing air: 350 kPa, and gap: 70 mm.

The compound a1 represented by the above formula (1) was synthesized by the method described in Synthesis Examples 1 and 2 of JP-A-2014-15609, where r is 43 and s is an integer of 1 to 6. The number average molecular weight is about 8000.

Example 2
In the preparation of the resin layer, Neoprim 6A20-G manufactured by Mitsubishi Gas Chemicals Co., Ltd. was used as the polyimide, and a resin solution in which 30 parts by weight of silica particles were added to 70 parts by weight of the polyimide was formed. Examples except that a resin film (resin layer) was obtained and then the polyimide resin film was bonded to a polyethylene terephthalate (PET) film having a thickness of 38 μm, and the thickness of the polyimide resin layer was 55 μm. A laminated body Y was obtained in the same manner as in 1. The layer structure of the laminate Y is an abrasion resistant layer / hard coat layer / polyimide resin film / PET film.

Example 3
As the second fluorine compound (B), 0.05% by mass of von Bryn M60 (registered trademark, manufactured by Solvay, number average molecular weight 12,500) represented by the following formula (2) was added in place of FAS13E. A laminated body Z was obtained in the same manner as in Example 1 except for the above.

Example 4
Instead of the polyimide resin layer and the hard coat layer of Example 1, a cycloolefin polymer (COP) film having a thickness of 23 μm was used, and polyvinyl alcohol (PVA) having a thickness of 12 μm in which iodine was adsorbed and oriented on the cycloolefin polymer was used. A polarizing plate (laminate W0) was used in which films were laminated and a triacetyl cellulose (TAC) film (30 μm) having a hard coat layer (acrylic) was laminated so that the hard coat layer was arranged on the outermost surface. A laminated body W was obtained in the same manner as in Example 1 except for the above. The layer structure of the laminate W was an abrasion resistant layer / hard coat layer / TAC / PVA / COP.

Example 5
As the first fluorine compound (A), compound a2 (number average molecular weight 4000) having an r value of about 40 and an s value of 1 in the above formula (1) was used instead of the compound a1. A laminated body V was obtained in the same manner as in Example 1.

Comparative Example 1
In the preparation of the wear-resistant layer, 0.2% by mass of the compound a2 shown in Example 5 was used instead of the compound a1 as the first fluorine compound (A), and the second fluorine compound (B) was not used. A laminated body S was obtained in the same manner as in Example 1 except for the above.

Comparative Example 2
In the preparation of the wear-resistant layer, the laminate T was prepared in the same manner as in Example 1 except that 0.2% by mass of the first fluorine compound (A) was used and the second fluorine compound (B) was not used. Obtained.

Comparative Example 3
A laminated body U was obtained in the same manner as in Example 1 except that a polyethylene terephthalate film having a thickness of 100 μm was used as the resin layer and a hard coat layer was not provided.

The following measurements were carried out on the laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 3.

(i) Measurement of contact angle Using a contact angle measuring device (DM700 manufactured by Kyowa Interface Science Co., Ltd.), the liquid volume: 3 μL by the sessile drop method (analysis method: θ / 2 method) on the wear-resistant layer side of the laminate. The contact angle of water was measured.

(Ii) Measurement of contact angle hysteresis and sliding angle Using DM700 manufactured by Kyowa Interface Science Co., Ltd., sliding method (analysis method: contact method, water droplet amount: 6.0 μm, inclination method: continuous inclination, slide detection: movement after sliding The contact angle hysteresis and the sliding angle of the wear-resistant layer were measured by the determination: advance angle, sliding determination distance: 0.25 mm).

(iii) Measurement of surface hardness Using a tribo gear reciprocating wear tester (TYPE: 30, manufactured by HEIDON), JIS K5600-5-4: 1999 "General paint test method-Part 5: Mechanical properties of coating film-" The pencil hardness of the surface of the laminate on the wear-resistant layer side was measured according to the pencil hardness test specified in "Section 4: Scratch hardness (pencil method)". The load in the measurement was 1000 g, and the speed was 40 mm / sec.

(Iv) Measurement of wear resistance Using a steel wool testing machine (manufactured by Daiei Seiki Co., Ltd.) equipped with steel wool # 0000 (manufactured by Bonster), the steel wool is in contact with the surface (wear resistant layer) of the laminate. A wear test was carried out by applying a load of 500 g, and the test was repeated until peeling / scratches were confirmed visually, and the wear resistance was evaluated by the number of tests when peeling / scratches were confirmed. The presence or absence of peeling and scratches was confirmed at an illuminance of 1000 lux.

In addition, the abrasion resistance after holding the laminate in a wet environment was measured as follows. After a 9 cm × 9 cm laminate was attached to glass, the periphery was surrounded by fluorine grease (manufactured by Nichias Corporation), and about 10 ml of pure water was dropped. After confirming that the entire surface of the laminate on the wear-resistant layer side was covered with pure water, the laminate was allowed to stand in an atmosphere of a temperature of 25 ° C. and a humidity of 40%. After 15 hours, pure water was removed, and then a steel wool abrasion resistance test was conducted in the same manner as described above.

The wear resistance before and after holding in a moist environment was measured, and the rate of decrease in wear resistance before and after holding in a moist environment was also calculated. The rate of decrease is a value calculated by the following formula.

Decrease rate of wear resistance (%) = (number of times of wear resistance before holding wet environment-number of times of wear resistance after holding wet environment) / (number of times of wear resistance before holding wet environment) x 100

The measurement results of each Example and Comparative Example are shown in Tables 1 and 2.

In Examples 1 to 5 in which the wear-resistant layer of the present invention is laminated on the hard coat layer, the rate of decrease in wear resistance after holding in a moist environment is 10% or less (preferably 9% or less). It is suppressed. On the other hand, in Comparative Examples 1 and 2 in which the wear-resistant layer does not have a structure derived from the second fluorine compound (B), the rate of decrease in wear resistance after holding in a wet environment exceeds 10%. Further, in Comparative Example 3 in which the hard coat layer was not provided, the hardness was low and the wear resistance could not be sufficiently exhibited.

INDUSTRIAL APPLICABILITY The present invention has little decrease in abrasion resistance in a moist environment, and therefore can be suitably used in an environment with high humidity or in a state where hands are wet.

Claims (5)

A laminate including a hard coat layer and an abrasion resistant layer,
The hard coat layer contains an acrylic resin or an epoxy resin, and contains an acrylic resin or an epoxy resin.
The wear-resistant layer has a monovalent group having a perfluoropolyether structure, a condensed structure derived from the first fluorine compound (A) in which a hydrolyzable group is bonded to a silicon atom, and a first fluorine. A layer containing a structure derived from a second fluorine compound (B), which is different from the compound (A).
The first fluorine compound (A) is a compound represented by the following formula (a1).
The second fluorine compound (B) is a compound represented by the following formula (b1) or a compound represented by the following formula (b3) and having a number average molecular weight of 9,000 to 13,000. A laminated body characterized by that.

In the above formula (a1),
Rf ^a1 has a divalent perfluoropolyether structure in which both ends are oxygen atoms.
R ^11, R ^12, and R ¹³ are each independently an alkyl group having 1 to 20 carbon atoms, if R ¹¹ there are a plurality may be different plural R ¹¹ are each, R ¹² is If there are two or more may be multiple R ¹² are different from each may be the case where R ¹³ there are a plurality of different plural R ¹³ are each,
^{E 1, E 2, E 3} , E 4, and E ⁵ is, independently represents a hydrogen atom or a fluorine atom, if E ¹ there are a plurality may be different plurality of E ^1, respectively, E ² may be the case where there are plural different multiple E ² respectively, when the E ³ there are a plurality may be different plurality of E ³ respectively, the plurality of E if E ⁴ there are a plurality of ⁴ may be different,
G ¹ and G ² are 2 to 10-valent organosiloxane groups each independently having a siloxane bond.
J ¹ , J ² , and J ³ are independently hydrolyzable groups _{or-(CH 2} ) _e6- Si (OR ¹⁴ ) ₃ , e 6 is 1-5, and R ¹⁴ is a methyl group. or an ethyl group, if J ¹ there are a plurality may be different plurality of J ^1, respectively, when J ² there are a plurality may be different plurality of J ^2, respectively, J ³ is more ^{Multiple J 3s} may be different if they exist
L ¹ and L ² are divalent linking groups having 1 to 12 carbon atoms which may independently contain an oxygen atom, a nitrogen atom, and a fluorine atom, and ^{when a plurality of L 1s} are present, a plurality of L 1 and L 2 are divalent linking groups. L ¹ is may be different from each, when L ² there are a plurality may be different plurality of L ^2, respectively,
a10 and a14 are 0 to 10 independently, respectively.
a11 and a15 are independently 0 or 1, respectively.
a12 and a16 are 0 to 9 independently of each other.
a13 is 0 or 1,
a21, a22, and a23 are 0 to 2 independently, respectively.
d11 is 1-9,
d12 is 0-9,
e1, e2, and e3 are 1 to 3 independently of each other.

In the above formula (b1),
A ¹ is a fluorine atom
A ² is a group represented by ^{−SiA 3} _c R ¹⁰ _3-c ^{, A 3} is a hydrolyzable group, R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, and c is 1 to 3 It is an integer
Rf ^b11 and Rf ^b12 are independently hydrogen atoms, fluorine atoms, or −CF ₃ , except when − {C (Rf ^b11 ) (Rf ^b12 )} − becomes −CH ₂ −. If Rf ^b11 there are multiple well be different plurality of Rf ^b11 respectively, if Rf ^b12 there are a plurality may be different plurality of Rf ^b12, respectively,
D is -O-, -C (= O) -O-, -OC (= O) -O-, -NR-, -NRCO-, or -CONR- (R is a hydrogen atom, the number of carbon atoms is It represents an alkyl group of 1 to 4 or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when a plurality of Ds are present, the plurality of Ds may be different from each other.
b1 is 0 or more and 5 or less, b2 is 4 or more and 220 or less, and b3 is 0 or more and 190 or less.
A ¹ −, A ² −, b 1 − (CH ₂ ) −, b 2 − {C (Rf ^b11 ) (Rf ^b12 )} −, b 3 − (D) − are A ¹ −, A ^{As long as 2−} is the terminal, does not have a perfluoropolyether structure, and −O− is not continuous with −O− to −F, they are bonded side by side in any order.

In the above formula (b3),
R ⁷⁰ is a perfluoroalkyl group having 1 to 3 carbon atoms.
R ⁷¹ is a perfluoroalkoxy group having 1 to 3 carbon atoms.
m1 = m2 = 0,
m3- (OC ₂ F ₄ )-and m4- (OCF ₂ ) ^{-are arranged in any order as long as R 70} and R ⁷¹ are the ends, and m3 and m4 are compound (B). It is a value determined to be a liquid at normal pressure. The laminate according to claim 1, wherein the first fluorine compound (A) has a number average molecular weight of 2,000 or more and 50,000 or less. The laminate according to claim 1 or 2 , wherein the first fluorine compound (A) is represented by the following formula (a2-1).

In the above formula (a2-1),
Rf ^a21 is an alkyl group having 1 to 20 carbon atoms or a fluorine atom in which one or more hydrogen atoms are replaced with fluorine atoms.
Rf ^a22 , Rf ^a23 , Rf ^a24 , and Rf ^a25 are independently alkyl groups or fluorine atoms having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, and a plurality of Rf ^a22s are present. if present may be different plurality of Rf ^a22 respectively, when multiple Rf ^a23 there may be different plurality of Rf ^a23 respectively, when multiple Rf ^a24 exists multiple Rf ^a24 there may also be different, when a plurality of Rf ^a25 there may be different plurality of Rf ^a25 respectively,
R ²⁰ , R ²¹ , R ²² and R ²³ are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and when a plurality of R ^20s are present, the plurality of R ^20s are different from each other. At best, when a plurality of R ²¹ are present or different plural R ²¹ are each, when a plurality of R ²² are present or different plural R ²² are each, a plurality of R ²³ is ^{Multiple R 23s,} if present, may be different
R ²⁴ is an alkyl group having 1 to 20 carbon atoms, and when a plurality of R ^24s are present, the plurality of R ^24s may be different from each other.
M ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when a plurality of M ^1s are present, the plurality of M ^1s may be different from each other.
M ² is a hydrogen atom or a halogen atom,
M ³ is -O-, -C (= O) -O-, -OC (= O)-, -NR-, -NRC (= O)-, or -C (= O) NR-( R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms), and when a plurality of M ^3s are present, the plurality of M ^3s may be different from each other.
M ⁴ is a hydrolyzable group, and when a plurality of M ^4s are present, the plurality of M ^4s may be different from each other.
f11, f12, f13, f14, and f15 are independently integers of 0 or more and 600 or less, and the total value of f11, f12, f13, f14, and f15 is 13 or more.
f16 is an integer of 1 or more and 20 or less.
f17 is an integer of 0 or more and 2 or less.
g1 is an integer of 1 or more and 3 or less,
Rf ^a21 −, M ² −, f11 − {C (R ²⁰ ) (R ²¹ )} −, f12 − {C (Rf ^a22 ) (Rf ^a23 )} −, f13 − {Si (R) ²² ) (R ²³ )}-, f14-{Si (Rf ^a24 ) (Rf ^a25 )}-, f15 -M ^3- , f16- [CH ₂ C (M ¹ ) {(CH ₂₎ ) _F17 −Si (M ⁴ ) _g1 (R ²⁴ ) _3-g1 }] are arranged in the order of forming a perfluoropolyether structure at least in part with ^{Rf a21} − and M ^{2 − at the ends, and −O.} As long as − is not continuous with −O− to −F, they are combined side by side in any order. The laminate according to any one of claims 1 to 3 , wherein the laminate further contains a polyimide resin layer, and the abrasion resistant layer, the hard coat layer, and the polyimide resin layer are in this order from the surface. The laminate according to any one of claims 1 to 4 , wherein the hard coat layer contains an inorganic filler.