KR20060051423A - Complex functional film for plasma display panel - Google Patents

Abstract

The present invention not only makes the thin and thin layer of the plasma display panel possible, but also the handling thereof is good, and it can be directly bonded to the plasma display panel, and maintains optical properties such as antireflection, shielding of near infrared rays and electromagnetic waves, and excellent light transmittance. It provides the composite functional film from which visibility is obtained.

The composite functional film provides a composite functional film for a plasma display panel having an antireflection layer and a near infrared absorbing layer satisfying the following conditions.

(1) The antireflection layer includes a laminate having the following (i) and (ii).

(i) The high refractive index layer containing electroconductive metal oxide particle, 1 or more types chosen from the alkoxy silyl group containing compound, the hydrolyzate, and hydrolysis condensate of this compound.

(ii) A low refractive index layer containing a fluorine-containing olefin polymer having a polysiloxane segment.

(2) The near infrared absorbing layer contains a norbornene-based resin.

Composite function film for plasma display panel, antireflection layer, near infrared absorption layer

Description

Complex Functional Film for Plasma Display Panel

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the form of the composite functional film of this invention.

It is a schematic diagram which shows the form at the time of using the composite functional film of this invention for the board | substrate for PDP.

<Brief description of symbols for the main parts of the drawings>

1 support film

2 shock absorbing layer

3 electromagnetic shielding layer

4 near infrared absorption layer

5 antireflective layer

6 support film

7 hard coating layer

8 anti-reflective layer

9 anti-reflective layer

10 Front panel for PDP

The present invention relates to a composite functional film that can be directly bonded to the front surface of a front plate glass substrate of a plasma display. More specifically, the present invention relates to a composite function film for plasma display panel that can suppress panel damage such as cracks and the like, and can reduce the weight and thickness of the panel without providing voids.

In recent years, a plasma display panel (hereinafter also referred to as "PDP") has attracted attention as a flat fluorescent display.

The display glass used for the PDP tends to be thinner due to the reduction in weight and thickness of the panel itself, and is thus easily broken. For this reason, the examination which installs protective resin layers, such as polycarbonate and an acryl agent, on glass is performed in order to prevent breakage of a glass, and the prevention of glass scattering at the time of breakage. In this case, since multiple reflection images are formed by the reflection of light at the interface between the protective resin layer and the display glass, and a double projection of the image may occur, adverse effects may occur on the device characteristics. It is examined to prevent multiple reflections by providing it.

In addition, in order to shield electromagnetic waves and near infrared rays emitted from the PDP, it is necessary to use an electromagnetic shielding material or a near infrared shielding material.

As an electromagnetic shielding material, the metal mesh which woven the metal wire in grid form is known. In addition, a metal mesh coated with a means such as electroless plating or an ultrafine metal mesh film may be formed on a polyester film.

As the near-infrared shielding material, a near-infrared reflector in which a metal such as silver is deposited on the surface of a transparent substrate such as glass, or a near-infrared absorber in which a near-infrared absorbing dye is added to a transparent resin such as an acrylic resin or a polycarbonate resin is used. .

In this way, it is common in recent years that the functional layer which consists of a multilayer usually exists in the front plate of a PDP.

However, in the PDP, since the transmitted light of the front plate forms an image, when there are a large number of reflective interfaces representing voids on the front plate, there is a problem in that multiple reflective images are formed and the screen is blurred or difficult to see. Moreover, there exists a problem that light transmittance falls by presence of many functional layers. In addition, while weight reduction and thinning are required, there is a problem that the panel becomes heavy.

SUMMARY OF THE INVENTION An object of the present invention is to provide a composite functional film for PDP having excellent functions for providing a PDP front plate, having excellent visibility and light transmittance, excellent transparency, and excellent impact absorption.

The composite functional film for plasma display panel of the present invention (hereinafter also referred to simply as "the composite functional film of the present invention") is characterized by having a near-infrared absorbing layer and an antireflection layer satisfying the following conditions.

(1) The antireflection layer includes a laminate having the following (i) and (ii).

(i) The high refractive index layer containing electroconductive metal oxide particle, 1 or more types chosen from the alkoxy silyl group containing compound, the hydrolyzate, and hydrolysis condensate of this compound.

(ii) A low refractive index layer containing a fluorine-containing olefin polymer having a polysiloxane segment.

(2) The near infrared absorbing layer contains a norbornene-based resin.

It is preferable that the composite function film of this invention has a shock absorbing layer further.

Moreover, it is preferable that the composite function film of this invention has an electromagnetic shielding layer further.

Moreover, it is preferable that the composite function film of this invention is formed by lamination | stacking which has an antireflection layer and a near-infrared absorption layer on a support film.

Best Mode for Carrying Out the Invention

The composite functional film of the present invention has a near infrared absorbing layer and an antireflection layer, and preferably a shock absorbing layer and / or an electromagnetic shielding layer. In particular, it is preferable that these layers were laminated | stacked on the support film, and it is especially preferable that the 2nd support film was superimposed on the formed layer. In order of lamination | stacking of each layer, the order of 1. (support film) / (shock absorbing layer) / (electromagnetic shield layer) / near-infrared absorbing layer / antireflection layer / (support film), or 2. (support film) / (shock absorbing layer) It is preferable to laminate in order of) / near-infrared absorption layer / (electromagnetic shield layer) / reflection prevention layer / (support film), and it is especially preferable to laminate in order of 1.

EMBODIMENT OF THE INVENTION Hereinafter, the member and the manufacturing method which comprise the composite functional film for plasma display panels of this invention are demonstrated in detail.

<Near infrared absorbing layer>

The near-infrared absorption layer which comprises this invention contains a norbornene-type resin, It is characterized by the above-mentioned. Usually, the layer which melt | dissolved and disperse | distributed the near-infrared absorbing dye in norbornene-type resin, or the layer which coated the thin film which has near-infrared absorptivity to the norbornene-type resin layer is used.

The layer containing the norbornene-based resin and the near infrared absorbing dye prepares a composition (hereinafter, also referred to as a "specific composition") in which the norbornene-based resin and the near infrared absorbing dye are dissolved and dispersed in a solvent, and the solvent is removed from the composition. It can be manufactured by manufacturing a near-infrared absorbing layer by the method of melt-molding, or the method of casting (cast molding) the said composition.

[Norbornene-based resin]

Monomer

As norbornene-type resin used for this invention, resin obtained by (co) polymerizing the monomer containing the 1 or more types of norbornene-type compound (Hereinafter, also called a "specific monomer") represented by following General formula (1) is mentioned. have. In particular, resin obtained by ring-opening (co) polymerizing the monomer containing the norbornene-based compound and further hydrogenating is preferable.

In the formula, each of R ¹ to R ⁴ independently represents an atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 30 carbon atoms, or another monovalent organic group, and R ¹ to R ⁴ At least one is a monovalent polar group containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, and R ¹ and R ² or R ³ and R ⁴ are bonded to each other to form an alkylidene group May be formed, R ¹ and R ² , R ³ and R ⁴ Alternatively, R ² and R ³ may be bonded to each other to form a carbocyclic ring or a heterocycle (these carbocyclic rings or heterocycles may be monocyclic, or other rings may be condensed to form a polycyclic structure). The summoned or heterocyclic ring may be an aromatic ring or a non-aromatic ring, m is an integer of 0 to 3, and p is 0 or 1.

The specific monomer is a compound having a structure (hereinafter referred to as "polar structure") containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom in its molecule (hereinafter referred to as "polar structure"), Since it is excellent in adhesiveness and adhesiveness with another raw material, it is preferable. As a specific polar structure, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, a cyano group, an alkoxysilyl group, etc. are mentioned, These polar groups may be couple | bonded through coupling groups, such as a methylene group. .

As a specific example of such a specific monomer, the compound described below can be illustrated, for example, However, this invention is not limited to these specific examples. In addition, the said specific monomer may be used individually by 1 type, and may use 2 or more types together.

5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene,

5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-cyanobicyclo [2.2.1] hept-2-ene,

5-phenylsulfonylbicyclo [2.2.1] hept-2-ene,

5-trimethoxysilylbicyclo [2.2.1] hept-2-ene,

5-triethoxysilylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,

5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,

8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene.

Among the specific monomers, R ¹ and R ^{3 in} Formula 1 are hydrogen atoms or hydrocarbon groups having 1 to 3 carbon atoms, preferably hydrogen atoms or methyl groups, and R ² or R ⁴ Either one is a group having a polar structure, and the other is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, which is preferably low in water absorption (wet) property of the resin.

Moreover, as a polar group, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an allyloxycarbonyl group is preferable, and especially an alkoxycarbonyl group or allyloxycarbonyl group is preferable because there is no excessive interaction with a pigment | dye. That is, in this invention, the compound which has one polar group represented by following General formula (2) as said specific monomer is easy to harmonize with the heat resistance and water absorption (wetness) of resin obtained, and can be used preferably.

-(CH ₂ ) _n COOR

In the formula, R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and n represents 0 or an integer of 1 to 10.

In the above formula (2), a resin having a low water absorption (wet) property is obtained as the n value is larger, but the glass transition temperature of the resin decreases and the heat resistance decreases, so that it is preferably an integer of 0 or 1 to 3, and n is a monomer. Is preferable in that the synthesis is easy. In addition, in the formula (2), R has a tendency to obtain a resin having low water absorption (wet) as the number of carbons increases, but in addition to a tendency to lower the glass transition temperature and lower heat resistance, there is also a tendency to lower the dye dispersibility, A hydrocarbon group of 1 to 12 is preferable, and in particular, a linear or branched alkyl group of 1 to 3 carbon atoms, a cycloalkyl group of 5 or 6 carbon atoms, or an aromatic group of 6 to 12 carbon atoms is preferable.

In the above formula (1), an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, is bonded to the carbon atom to which the group represented by the formula (2) is bonded.

In addition, since the compound which is m = 0 or 1, p = 0 in the said General formula (1) is high in reactivity, resin is obtained by a high yield, polymer hydrogen additive with high heat resistance is obtained, and also industrial availability is easy. It is preferably used.

In the above embodiments, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene or 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] -3-dodecene is particularly preferred as the specific monomer.

In this invention, the compound copolymerizable with this (henceforth a "copolymerizable monomer") can also be used besides the said specific monomer. As such a compound, the norbornene-type compound which does not have polar groups other than the said specific monomer is mentioned, for example. Specifically,

Bicyclo [2.2.1] hept-2-ene,

Tricyclo [4.3.0.1 ^2,5 ] -3-decene,

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5-methylbicyclo [2.2.1] hept-2-ene,

5-ethylbicyclo [2.2.1] hept-2-ene,

5-ethylidenebicyclo [2.2.1] hept-2-ene,

8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5-phenylbicyclo [2.2.1] hept-2-ene,

8-phenyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5-fluorobicyclo [2.2.1] hept-2-ene,

5-fluoromethylbicyclo [2.2.1] hept-2-ene,

5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,

5,5-difluorobicyclo [2.2.1] hept-2-ene,

5,6-difluorobicyclo [2.2.1] hept-2-ene,

5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,

5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,

5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,

5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

8-fluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-fluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-difluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8-difluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-difluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-difluoro-8-heptafluoro-iso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and the like.

In the present invention, cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and dicyclopentadiene may be used as the copolymerizable monomer. As carbon number of a cycloolefin, 4-20 are preferable, More preferably, it is 5-12.

In this invention, these copolymerizable monomers are not limited to the said specific example, You may use individually by 1 type, and may use 2 or more types together.

The preferred ratio of specific monomers to other copolymerizable monomers (specific monomers / other copolymerizable monomers) in the total monomers varies depending on the type of monomer, but is usually 100/0 to 50/50 in weight ratio, more preferably 100 / 0 to 60/40.

Polymerization method

About the polymerization method of norbornene-type resin used for this invention, ring-opening polymerization or addition polymerization can be performed. Among these, norbornene-based resin obtained by ring-opening polymerization is preferable, and resin obtained by ring-opening polymerization and further hydrogenation is particularly preferable.

The ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. This metathesis catalyst,

(A) at least one compound selected from compounds having W, Mo and Re (hereinafter referred to as compound (A)),

(B) Periodic Table of Deming Group IA elements (e.g., Li, Na, K, etc.), Group IIA elements (e.g., Mg, Ca, etc.), Group IIB elements (e.g., Zn, Cd, Hg, etc.) , Group IIIA elements (e.g., B, Al, etc.), group IVA elements (e.g., Si, Sn, Pb, etc.), or compounds having group IVB elements (e.g., Ti, Zr, etc.), A catalyst comprising a combination of one or more compounds selected from compounds having at least one bond of this element with carbon or at least one bond of this element with hydrogen (hereinafter referred to as compound (B)). In addition, the following additive (C) may be further added to increase the activity of the catalyst.

Examples of the compound (A) include halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyl complexes, acetonitrile complexes, hydride complexes of W, Mo or Re, and Although derivatives thereof or combinations thereof can be mentioned, compounds of W and Mo, particularly halides, oxyhalides and alkoxy halides thereof, are preferable in terms of polymerization activity and practicality. Moreover, the mixture of 2 or more types of compounds which produce the compound mentioned above by reaction can also be used. In addition, these compounds may be complexed with a suitable complexing agent, for example, P (C ₆ H ₅ ) ₅ , C ₅ H ₅ N, or the like.

Specific examples of the compound (A) include WCl ₆ , WCl ₅ , WCl ₄ , WBr ₆ , WF ₆ , WI ₆ , MoCl ₅ , MoCl ₄ , MoCl ₃ , ReCl ₃ , WOCl ₄ , MoOCl ₃ , ReOCl ₃ , ReOBr ₃ , W (OC ₆ H ₅ ) ₆ , WCl ₂ (OC ₆ H ₅ ) ₄ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , Mo (OC ₂ H ₅ ) ₅ , Mo0 ₂ (acac) ₂ , W (OCOR _{) 5, W (OC 2 H} 5) 2 Cl 3, W (CO) 6, Mo (CO) 6, Re 2 (CO) 10, ReOBr 3 · P (C 6 H 5) 3, WCl 5 · P ( C ₆ H _5), and the like _{3, WCl 6 · C 5 H} 5 N, W (CO) 5 · P (C 6 H 5) 3, W (CO) 3 · (CH 3 CN) 3. Among these, particularly preferred compounds include MoCl ₅ , Mo (OC ₂ H ₅ ) ₂ Cl ₃ , WCl ₆ , W (OC ₂ H ₅ ) ₂ Cl ₃ , and the like.

Specific examples of compound (B) include nC ₄ H ₅ Li, nC ₅ H ₁₁ Na, C ₅ H ₅ Na, CH ₃ MgI, C ₂ H ₅ MgBr, CH ₃ MgBr, nC ₃ H ₇ MgCl, (C ₆ H ₅ ) ₃ Al, tC ₄ H ₉ MgCl, CH ₂ = CHCH ₂ MgCl, (C ₂ H ₅ ) ₂ Zn, (C ₂ H ₅ ) ₂ Cd, CaZn (C ₂ H ₅ ) ₄ , (CH ₃ ) ₃ B, (C ₂ H ₅ ) ₃ B, (nC ₄ H ₉ ) ₃ B, (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, LiAl (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₃ Al-O (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ AlCl, C ₂ H ₅ AlCl ₂ , (C ₂ H ₅ ) ₂ AlH, (iso-C ₄ H ₉ ) ₂ AlH, (C ₂ H ₅ ) ₂ AlOC ₂ H ₅ , (iso-C ₄ H ₉ ) ₃ Al, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ , (CH ₃ ) ₄ Ga, (CH ₃ ) ₄ Sn, (nC ₄ H ₉ ) ₄ Sn, (C ₂ H ₅ ) ₃ SiH, (nC ₆ H ₁₃ ) ₃ Al, (nC ₄ H _17), and the like _{3 Al, LiH, NaH, B} 2 H 6, NaBH 4, AlH 3, LiAlH 4, BiH 4 and TiH _4. Moreover, the mixture of 2 or more types of compounds which generate these compounds by reaction can also be used. Preferred examples of them include (CH ₃ ) ₃ Al, (CH ₃ ) ₂ AlCl, (CH ₃ ) ₃ Al ₂ Cl ₃ , CH ₃ AlCl ₂ , (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) _{2 AlCl, (C 2 H 5} ) 1.5 AlCl 1 .5, C 2 H 5 AlCl 2, (C 2 H 5) 2 AlH, (C 2 H 5) 2 AlOC 2 H 5, (C 2 H 5) 2 AlCN, (C ₃ H ₇ ) ₃ Al, (iso-C ₄ H ₉ ) ₃ Al, (iso-C ₄ H ₉ ) ₂ AlH, (C ₆ H ₁₃ ) ₃ Al, (C ₈ H ₁₇ ) ₃ Al , (C ₆ H ₅ ) ₅ Al, and the like.

As the additive (C) which can be used together with the compound (A) and the compound (B), alcohols, aldehydes, ketones, amines and the like can be preferably used, for example, the following (1) to (9) Can be illustrated.

(1) Inorganic metal compounds of boron such as boron, BF ₃ , BCl ₃ , B (OnC ₄ H ₉ ) ₃ , (C ₂ H ₅ 0 ₃ ) ₂ , BF, B ₂ 0 ₃ , H ₃ BO ₃ Inorganic metal compounds of silicon such as Si (OC ₂ H ₅ ) ₄ and the like;

(2) alcohols, hydroperoxides and peroxides;

(3) water;

(4) oxygen;

(5) carbonyl compounds such as aldehydes and ketones and polymers thereof;

(6) cyclic ethers such as ethylene oxide, epicrohydrin and oxetane;

(7) amides such as N, N-diethylformamide and N, N-dimethylacetamide, amines such as aniline, morpholine and piperidine, and azo compounds such as azobenzene;

(8) N-nitroso compounds such as N-nitrosodimethylamine and N-nitrosodiphenylamine;

(9) A compound containing an S-Cl or N-Cl group, such as trichloromelamine, N-chlorosuccinimide, or phenylsulphenyl chloride.

The amount of metathesis catalyst to be used is preferably such that the molar ratio of the compound (A) and the total monomers provided for the polymerization (compound: total monomers) is usually 1: 500 to 1: 50,000, preferably 1: 1,000 to 1: 10,000. Do.

The ratio (compound (A): compound (B)) of the compound (A) and the compound (B) is preferably 1: 1 to 1:50, preferably 1: 2 to 1:30, in a metal atomic ratio.

The ratio (compound (C): compound (A)) of the compound (A) and the compound (C) is preferably 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1 in molar ratio.

The solvent used in the ring-opening polymerization reaction is not particularly limited as long as the monomer or catalyst provided for the polymerization is dissolved, and the catalyst is not deactivated, and the produced ring-opening polymer is dissolved. For example, pentane, hexane, heptane, Alkanes such as octane, nonane and decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene bromide, chloroform and tetrachloroethylene; Aryl halide compounds such as chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate and dimethoxyethane; Ethers such as dibutyl ether, tetrahydrofuran, dimethoxyethane and the like. These can be used individually or in mixture of 2 or more types. Such solvents are used as solvents for constituting the molecular weight modifier solution, the specific monomers, copolymerizable monomers and / or metathesis catalysts.

The amount of the solvent used is preferably an amount such that the weight ratio (solvent: total monomers) of the solvent and the monomers provided for the polymerization is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1.

Although the molecular weight of the ring-opened polymer obtained can also be adjusted with polymerization temperature, the kind of catalyst, and the kind of solvent, it can also adjust by coexisting a molecular weight modifier in a reaction system.

Preferable molecular weight modifiers include, for example, olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and styrene. Among these, 1-butene and 1-hexene are especially preferable. These molecular weight modifiers can be used individually or in mixture of 2 or more types.

The use amount of the molecular weight modifier is usually 0.005 to 0.6 mol, preferably 0.01 to 0.5 mol, based on 1 mol of the monomers provided in the ring-opening polymerization reaction.

The ring-opening polymer may be obtained by ring-opening polymerization of a specific monomer alone or a copolymerizable monomer different from a specific monomer, but a conjugated diene compound such as polybutadiene and polyisoprene, a styrene-butadiene copolymer, an ethylene-nonconjugated diene copolymer, The monomer can also be ring-opened-polymerized in the presence of an unsaturated hydrocarbon-based polymer including two or more carbon-carbon double bonds in the main chain such as polynorbornene.

A known ring-opening polymerization reaction for norbornene can be used in the production method of the ring-opening polymer, and a specific monomer and another copolymerizable monomer can be used in the presence of the catalyst for ring-opening polymerization, a solvent for polymerization reaction, and if necessary, the molecular weight regulator. The ring-opening polymer can be produced by ring-opening polymerization.

Since the ring-opening polymer obtained by the said method has an olefinic unsaturated bond in the molecule | numerator, and when used as it is, such an olefinic unsaturated bond may cause deterioration, such as coloring and gelatinization, over time, and therefore, this invention In hydrogen, it is preferable to perform hydrogenation which converts such an olefinic unsaturated bond into a saturated bond.

The hydrogenation reaction is a conventional method, i.e., a known hydrogenation catalyst is added to a solution of a ring-opening polymer, and hydrogen gas at atmospheric pressure to 300 atm, preferably 3 to 200 atm is 0 to 200 캜, preferably 20 It can carry out by making it act at 180 degreeC.

The hydrogenation rate of the hydrogenated polymer is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly preferably 98% or more, most preferably at 500 MHz and ¹ H-NMR. Preferably 99% or more. The higher the hydrogenation rate, the better the stability against heat and light, and when used as a molded body, it is preferable because stable properties can be obtained over a long period of time.

In addition, when the ring-opening polymer obtained by the above method has an aromatic group in the molecule, such an aromatic group does not cause deterioration such as coloration or gelation with time, but rather has a beneficial effect on mechanical or optical properties. In addition, it is not necessary to hydrogenate this aromatic group necessarily.

As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. As this hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are mentioned.

As a heterogeneous catalyst, the solid catalyst which carried noble metal catalyst substances, such as palladium, platinum, nickel, rhodium, ruthenium, on support | carriers, such as carbon, a silica, alumina, titania, is mentioned. Examples of homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octate / n-butyllithium, titanocenedichloride / diethylaluminum monochloride, rhodium acetate and chlorotris (triphenyl Phosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or particulate.

These hydrogenated catalysts are used in a ratio such that the weight ratio of the ring-opening polymer to the hydrogenated catalyst (opening-opening polymer: hydrogenated catalyst) is from 1: 1 × 10 ⁻⁶ to 1: 2.

The norbornene-based resin used in the present invention has an intrinsic viscosity [η] _inh of 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g, and gel permeation chromatography. The polystyrene reduced number average molecular weight (Mn), as measured by GPC, is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw) is 20,000 to 300,000, further Preferably it is 30,000-250,000, Especially preferably, it is 40,000-200,000. When the intrinsic viscosity [η] _inh , the number average molecular weight and the weight average molecular weight are in the above ranges, the norbornene-based resin is excellent in heat resistance, water resistance (wetting), chemical resistance and mechanical properties, and a molded article excellent in durability and mechanical strength. Obtained.

The glass transition temperature (Tg) of the norbornene-based resin is usually 100 to 350 ° C, preferably 120 to 300 ° C, more preferably 130 to 250 ° C. When Tg is less than 100 degreeC, heat resistance may run short and a restriction | limiting may arise in the use environment of a molded object. Moreover, when Tg exceeds 350 degreeC, melt molding may become difficult and the means for obtaining a molded object may be restrict | limited.

The saturated water absorption at 23 ° C. of the norbornene-based resin used in the present invention is preferably 0.1 to 1% by weight, particularly preferably 0.1 to 0.6% by weight. By setting the saturated water absorption as the above value, unintended interaction such as alteration of the dye can be avoided while maintaining the dye dispersibility satisfactorily. That is, when a saturated water absorption is less than 0.1 weight%, pigment dispersibility is inadequate, when a molded object is formed, a "color nonuniformity" and turbidity may arise, or the added pigment may bleed on the surface of a molded object. On the other hand, when the saturated water absorption exceeds 1% by weight, deterioration of the dye occurs and the desired properties are not obtained, or when the liquid composition is formed, the absorption (wet) deformation is not only reduced significantly due to gelation or the like. Problems may occur in the durability of the molded product, such as the occurrence and the desired function cannot be obtained.

In addition, said saturated water absorption is a value obtained by immersing in 23 degreeC water for 1 week according to ASTMD570, and measuring an increase weight.

[Near Infrared Absorption Pigment]

Although the near-infrared absorber used by this invention will not be specifically limited if it is the near-infrared absorber generally added to transparent resin, and is used, It is a near-infrared wavelength of 600-2500 nm with respect to the solution which melt | dissolved 0.1 weight part of this near-infrared absorber with respect to 100 weight part of good solvents. The compound whose light transmittance which made the said good solvent into a control part in a part or all area | region is 50% or less and 30% or less is preferable.

Specifically, the near-infrared absorber whose structural formula is disclosed by Unexamined-Japanese-Patent No. 6-200113, etc., Unexamined-Japanese-Patent No. 8-225752, Unexamined-Japanese-Patent No. 8-253693, Japan Japanese Patent Laid-Open No. 9-1111138, Japanese Patent Laid-Open No. 9-157536, Japanese Patent Laid-Open No. 9-176501, Japanese Patent Laid-Open No. 9-263658, and Japanese Patent Laid-Open The phthalocyanine type compound, the naphthalocyanine type compound, and the dithiol metal complex type compound whose structure and manufacturing method are disclosed by Unexamined-Japanese-Patent No. 2000-212546, Unexamined-Japanese-Patent No. 2002-200711, etc. are mentioned. Moreover, for example, the near-infrared absorber of a commercial item, SIR-103, SIR-114, SIR-128, SIR-130, SIR-132, SIR-152, SIR-159, SIR-162, PA-1001, PA-1005 ( Mitsui Chemicals, Kayasorb IR-750, Kayasorb IRG-002, Kayasorb IRG-003, IR-820B, Kayasorb IRG-022, Kayasorb IRG-023, Kayasorb CY-2, Kayasorb CY-4, Kayasorb CY -9 (above, Nippon Kayaku Co., Ltd.), CIR-1080, CIR-1081 (above, Nippon Karize), YKR-3080, YKR-3081 (above, Yamamoto Kasei), Ixcara IR-10, IR- 12, IR-14 (above, made by Nippon Shokubai), etc. can also be used.

In the present invention, the amount of the near-infrared absorbing dye is appropriately selected according to the desired characteristics, but is usually 10 ^-6 to 30 parts by weight, preferably 10 ^-5 to 10 parts by weight, based on 100 parts by weight of the norbornene-based resin according to the present invention. Parts, more preferably 10 ^-4 to 5 parts by weight. If the amount is less than 10 ^-6 parts by weight, the function as a near infrared absorbing layer may not be exhibited. On the other hand, if the amount is more than 30 parts by weight, a problem may occur in moldability.

[solvent]

As a solvent which can be used for manufacture of a specific composition, if the norbornene-type resin mentioned above can be melt | dissolved, it will not specifically limit. As such a solvent, Aromatic solvents, such as benzene, toluene, and xylene; Cellosolve solvents such as methyl cellosolve, ethyl cellosolve and 1-methoxy-2-propanol; Ketone solvents such as diacetone alcohol, acetone, cyclohexanone, methyl ethyl ketone, and 4-methyl-2-pentanone; Ester solvents such as methyl lactate and ethyl lactate; Cycloolefin solvents such as cyclohexanone, ethylcyclohexanone and 1,2-dimethylcyclohexane; Halogen-containing solvents such as 2,2,3,3-tetrafluoro-1-propanol, methylene chloride and chloroform; Ether solvents such as tetrahydrofuran and dioxane; Alcohol solvent, such as 1-pentanol and 1-butanol, etc. are mentioned.

Further, as a solvent other than the above, the solubility parameter (SP value) is preferably from 10 to 30 (MPa ^1/2), more preferably from 10 to 25 (MPa ^1/2), particularly preferably 15 to 25 (MPa ^1/2), using the solvent in the range of from 15 to 20 (MPa ^1/2) and most preferably, it is possible to dissolve the norbornene-based resin of the present invention, it can be used as a solvent.

The said solvent can be used individually or in mixture of multiple pieces. When mixed and used, it is preferable that the SP value of a mixed solvent exists in the said range. The SP value of the mixed solvent can be predicted by the weight ratio of the solvent. For example, when two kinds of solvents (Solvent 1 and Solvent 2) are mixed, the respective weight fractions are W ₁ , W ₂ , and SP _1. , SP ₂ can be calculated by the following equation (1).

SP value = W ₁ SP ₁ + W ₂ SP ₂

In addition, the near-infrared absorbing dye does not necessarily need to be dissolved in a solvent, and even when the norbornene-based resin of the present invention is present even in a suspended state in a solvent, it can be uniformly dispersed or dissolved by interaction to form a molded article. You can get the function you want. Of course, it is obvious that it is preferable to select a solvent having high solubility in the near infrared absorbing dye.

Preparation of Specific Compositions

The specific composition used for formation of a near-infrared absorption layer contains the norbornene-type resin mentioned above, a near-infrared absorbing pigment, and a solvent, The manufacturing method is not specifically limited, Each component is added to a tank etc. suitably at a desired composition ratio, Although it can manufacture by performing stirring etc., heating as needed, When using norbornene-type resin in the form of the solution which melt | dissolved in the solvent previously, since a near-infrared absorbing dye tends to disperse | distribute uniformly in a composition for a short time, it is preferable. . Here, although the solution of the norbornene-based resin may be adjusted by dissolving a solid resin such as particulate or flake in a solvent, it is also possible to use a polymerization reaction solution. In addition, when using a polymerization reaction solution, it is preferable to perform pretreatment, such as removing the remainder or unreacted monomer of a polymerization catalyst and a hydrogenation catalyst beforehand.

In addition, it is preferable to add a near-infrared absorbing dye in the state suspended or dissolved in a solvent previously in many cases, which can shorten time for manufacturing a liquid resin composition. In this case, although the solvent different from the solvent used for manufacture of the said norbornene-type resin solution can be used, it is preferable to select the solvent which can form a uniform phase with a resin solution.

Moreover, in manufacturing a specific composition, after mixing the said norbornene-type resin, a near-infrared absorbing dye, and a solvent, it is preferable to remove an insoluble content in a composition with a filter etc. If such an insoluble content exists, it may become a defect when using a molded object for optical use.

In this invention, additives, such as antioxidant, can be added to norbornene-type resin, a near-infrared absorbing pigment, and a solvent in the range which does not impair the effect of this invention. Specifically, as antioxidant, 2, 6- di-t- butyl- 4-methyl phenol, 2, 2'- dioxy- 3, 3'- di- t- butyl- 5, 5'- Dimethyldiphenylmethane and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane. As a ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, etc. can be added, for example, and the durability of a molded object can be improved further. Moreover, manufacture of a near-infrared absorption layer by the solution casting method mentioned later can be made easy by adding a leveling agent and an antifoamer.

In addition, these additives may be mixed with components, such as norbornene-type resin at the time of manufacturing a specific composition, and may be mix | blended with resin previously by adding at the time of manufacture of norbornene-type resin. In addition, although the addition amount is suitably selected according to a desired characteristic, it is preferable that it is 0.0001-5 weight part normally with respect to 100 weight part of norbornene-type resin, Preferably it is 0.001-3 weight part.

Near infrared  Manufacturing method of absorber layer

The near-infrared absorbing layer can be manufactured by the method of melt-molding by removing a solvent from the specific composition mentioned above, or the method of casting (cast molding) a specific composition.

(1) melt molding

When a near-infrared absorbing film is manufactured by the method of melt-molding by removing a solvent from a specific composition, when a solvent is removed from a specific composition, the thermoplastic resin composition containing the said norbornene-type resin and a near-infrared absorbing dye is obtained. Such a thermoplastic resin composition can apply melt molding, such as injection molding, melt extrusion molding, or blow molding.

The film obtained by such a method has less thermal history, less deterioration of the resin or pigment, less foreign substances due to gel or sintering than a film obtained from the thermoplastic resin composition obtained by melt kneading a norbornene-based resin and a near infrared absorbing dye. It has the characteristics of and has a big advantage in obtaining the film for optical use.

The method of removing a solvent from a specific composition is not specifically limited, A well-known method is applicable in consideration of the characteristic of norbornene-type resin and a near-infrared absorbing pigment in a composition. For example, a method of precipitating and recovering the resin composition by adding a poor solvent of norbornene-based resin, a method of heating under reduced pressure to remove the solvent, a method of blowing steam to remove the solvent, and the like can be applied.

The amount of residual solvent in the thermoplastic resin composition obtained by the said method is good as little as possible, and is 3 weight% or less normally, Preferably it is 1 weight% or less, More preferably, it is 0.5 weight% or less. When the amount of residual solvent exceeds 3% by weight, a large amount of gas is generated during melt molding, which not only causes contamination or failure of the molding equipment, but also causes appearance defects of the molded body such as silver, voids or citron skin. There are many cases.

(2) casting

The near infrared absorbing layer may be prepared by casting a specific composition on a suitable substrate to remove the solvent. For example, a near-infrared absorption layer can be obtained by apply | coating a specific composition on the above-mentioned board | substrate, the below-mentioned shock absorbing layer or electromagnetic wave shield layer formed on the board | substrate, and drying a solvent. Moreover, a near-infrared absorption layer can also be obtained by apply | coating a specific composition on base materials, such as a steel belt, a steel drum, or a polyester film, drying a solvent, and peeling a coating film from a base material. Further, by coating a specific composition on an optical component made of glass, quartz or transparent plastic and drying the solvent, a near-infrared absorbing layer having a near infrared cutting filter function applied to the original optical component can also be obtained.

The amount of residual solvent in the near-infrared absorbing layer obtained by the said method is good as little as possible, and it is 3 weight% or less normally, Preferably it is 1 weight% or less, More preferably, it is 0.5 weight% or less. When the amount of residual solvent exceeds 3% by weight, the molded body may be deformed or the characteristics may change as time passes, so that the desired function may not be exhibited.

Near infrared  Alternative manufacturing method of absorber layer

The near-infrared absorbing layer may be a laminated structure in which a thin film having near-infrared absorbing ability is coated on a norbornene-based resin film.

As a formation method of a norbornene-type resin film, the method according to the above-mentioned melt molding or casting is mentioned.

As a thin film which has near-infrared absorptivity, the thin film containing the above-mentioned near-infrared absorbing dye, a metal, a metal oxide, a metal complex, a metal salt, etc. are mentioned.

<Anti-reflective layer>

The antireflection layer used in the composite functional film of the present invention includes a laminate having a high refractive index layer, a low refractive index layer, and preferably a hard coating layer. Usually, as this embodiment, it is laminated | stacked in order of (hard coating layer) / high refractive index layer / low refractive index layer on a base material (near-infrared absorption layer or an electromagnetic shielding layer, usually a near-infrared absorption layer).

Hereinafter, the formation material and formation method of each layer are demonstrated in detail.

[High refractive index layer]

The high refractive index layer used in the present invention

(i-1) conductive metal oxide particles,

(i-2) It is obtained from the high refractive index material containing 1 or more types (it also calls "alkoxysilyl group containing compound" hereafter) chosen from the alkoxy silyl group containing compound, the hydrolyzate, and hydrolysis-condensation product of this compound. . Preferably, the conductive metal oxide particles and the alkoxysilyl group-containing compound are preferably reacted in advance in an organic solvent. In addition to high refractive index materials,

(i-3) a polyfunctional (meth) acryl compound containing three or more (meth) acryloyl groups in a molecule, and

(i-4) It is preferable that a radiation polymerization initiator is contained.

(i-1) Conductive Metal Oxide Particles

The powder resistance of the electroconductive metal oxide particle used for this invention is 100 ohm * cm or less, Preferably it is 50 ohm * cm or less.

The primary particle diameter of electroconductive metal oxide particle is the value calculated | required by the BET adsorption method of dry powder, and is 0.1 micrometer or less, Preferably it is 0.01 micrometer-0.001 micrometer. When it exceeds 0.1 micrometer, sedimentation will arise in a composition or the smoothness of a coating film will fall.

50-95 weight% is preferable with respect to the total solid in a composition, and, as for the compounding quantity of electroconductive metal oxide particle, 65-95 weight% is more preferable. If it is less than 50 weight%, high refractive index property may become inadequate when a cured film is formed.

The metal oxide of the conductive metal oxide particles may be a single metal oxide or may be a metal oxide containing two or more alloys.

Although these electroconductive metal oxide particles can be used in the state disperse | distributed to powder or an organic solvent, since it is easy to obtain uniform dispersibility, it is preferable to manufacture a composition in the state disperse | distributed in an organic solvent.

Specific metal oxides that can be used as the conductive metal oxide particles include, for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), phosphorus-doped tin oxide (PTO), and antimony. Zinc oxide, indium-doped zinc oxide, ruthenium oxide, rhenium oxide, silver oxide, and at least one particle selected from the group consisting of nickel oxide and copper oxide. Among these, especially ATO is used preferably.

As a commercial item as powder of such electroconductive metal oxide particle, Mitsubishi Material Co., Ltd. brand name: T-1 (ITO), Mitsui Kinzoku Co., Ltd. brand name: Pastran (ITO, ATO), Ishihara Sangyo Co., Ltd. brand name: SN-100P (ATO), CI Kasei Co., Ltd. brand name: Nanotech ITO, Nissan Chemical Co., Ltd. brand name: ATO, FTO, etc. are mentioned.

It is preferable that the conductive metal oxide particles carry silicon oxide on their surface because they react particularly effectively with the alkoxysilyl group-containing compound. As a method of supporting such a silicon oxide, for example, a process of producing a coprecipitation of a tin oxide and an antimony oxide hydrate disclosed in Patent Publication No. 2858271 and then depositing a silicon compound to fractionate and calcinate It can manufacture.

As a commercial item of the electroconductive metal oxide particle formed by carrying the silicon oxide on the surface, Ishihara Sangyo Co., Ltd. brand name: SN-100P (ATO), SNS-10M, FSS-10M, etc. are mentioned, for example.

As a commercial item which disperse | distributed electroconductive metal oxide particle to the organic solvent, For example, Ishihara Sangyo Co., Ltd. brand name: SNS-10M (antimony-doped tin oxide of MEK dispersion), FSS-10M (antimony-doped oxidation of isopropyl alcohol dispersion) Tin), Nissan Chemical Industries, Ltd. brand name: Celax CX-Z401M (antimony zinc oxide of methanol dispersion), Celax CX-Z200IP (antimony acid zinc of isopropyl alcohol dispersion), etc. are mentioned.

As a method of dispersing powdery conductive metal oxide particles in an organic solvent, for example, a dispersant and an organic solvent are added to the conductive metal oxide particles, and beads of zirconia, glass, and alumina are added as a dispersion medium, and a paint shaker or Henkel mixer is used. The method of stirring and dispersing at high speed etc. is mentioned. As for the addition amount of a dispersing agent, 0.1-5 weight% of the whole composition is preferable. As a dispersing agent, the interface of anionic, nonionic, and cationic systems, such as an alkali metal acrylate metal salt, a phosphate ester of a polyether, a polyethylene oxide / polypropylene oxide block polymer, a nonylphenyl polyether, and cetyl ammonium chloride, for example Activators are mentioned.

The blending amount of the organic solvent used as the dispersion solvent for dispersing the conductive metal oxide particles is preferably 20 to 4,000 parts by weight, more preferably 100 to 1,000 parts by weight based on 100 parts by weight of the conductive metal oxide particles. If the amount of the solvent is less than 20 parts by weight, the uniformity may be difficult because of the high viscosity. If the amount of the solvent exceeds 4,000 parts by weight, the applicability may decrease.

As such an organic solvent, the solvent whose boiling point in normal pressure is 200 degrees C or less is mentioned, for example. Specifically, alcohols, ketones, ethers, esters, hydrocarbons and amides are used, and these can be used alone or in combination of two or more thereof. Especially, alcohols, ketones, ethers, and esters are preferable.

Here, as alcohols, methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, phenethyl alcohol Etc. can be mentioned.

As ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. are mentioned, for example.

As ethers, dibutyl ether, propylene glycol monoethyl ether acetate, etc. are mentioned, for example.

As ester, ethyl acetate, butyl acetate, ethyl lactate, etc. are mentioned, for example.

As hydrocarbons, toluene, xylene, etc. are mentioned, for example.

Examples of the amides include formamide, dimethylacetamide, N-methylpyrrolidone, and the like.

Especially, isopropyl alcohol, ethoxy ethanol, butoxy ethanol, diethylene glycol monoethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monoethyl ether acetate, butyl acetate, ethyl lactate, etc. are preferable. Do.

(i-2) Alkoxysilyl group  contain Compounds

The alkoxysilyl group-containing compounds used in the present invention are at least one selected from alkoxysilyl group-containing compounds, hydrolyzates and hydrolysis condensates of these compounds, preferably the alkoxysilyl group-containing compound is the conductive metal described above. Reaction with the oxide particles is present in the high refractive index material. In the high refractive index layer obtained using this high refractive index material, the alkoxysilyl group containing compound may exist as a hydrolyzate or a hydrolysis condensate.

It is preferable that an alkoxy silyl group containing compound has a polymerizable unsaturated group and an alkoxy silyl group in a molecule | numerator. The alkoxysilyl group is a component that bonds with the adsorbed water present on the surface of the metal oxide particles by hydrolysis and condensation reaction, and the polymerizable unsaturated group is a component that crosslinks chemically between molecules through addition polymerization by active radical species.

As a polymerizable unsaturated group, an acryl group, a vinyl group, and a styryl group are mentioned as a preferable thing, for example. Moreover, as an alkoxy silyl group, the group which can hydrolyze in presence of water or a hydrolysis catalyst is preferable.

Further, such alkoxysilyl group-containing compounds may contain at least one bond group selected from the group consisting of ester bonds, ether bonds, urethane bonds, sulfide bonds and thiourethane bonds in the molecule, and particularly, urethane bonds [-OC ( It is preferred to have = O) NH-] and / or thiourethane bond [-SC (= O) NH-]. This bonding group is a structural unit which directly bonds the molecular piece which has these alkoxysilyl groups, and the molecular piece which has a polymerizable unsaturated group through the other or through another molecular piece, generate | occur | produces the appropriate cohesion force by hydrogen bond between molecules, It is thought to give performances, such as excellent mechanical strength, adhesiveness with a base material, heat resistance, etc. to a cargo.

As an especially preferable alkoxy silyl group containing compound used for this invention, the alkoxysilane compound represented by following General formula (3) is mentioned, for example.

Qm (Q ¹ O) _{3- m} Si-XSC (= O) -NH-Y-NH-C (= O) -OZ-[-OC (= O) -CQ ² = CH ² ] _n

In the formula, Q is a methyl group, Q ¹ is an alkyl group having 1 to 6 carbon atoms, m is 1 or 2, X is a divalent alkylene group having 1 to 6 carbon atoms, Y is a chain, cyclic, or branched carbon group having 3 to 3 carbon atoms. 14 is a divalent hydrocarbon group, Z is a divalent hydrocarbon group having 2 to 14 carbon atoms in any one of 2 to 6 valent chain, cyclic, and branched, and may include an ether bond in Z, and Q ² is a hydrogen atom Or a methyl group, n is an integer of 1-5.

The compounding quantity of the alkoxysilyl group containing compound becomes like this. Preferably it is 5 to 50 weight%, More preferably, it is 5 to 35 weight% with respect to the total solid in a composition. When the alkoxysilyl group-containing compound is less than 5% by weight, the transparency of the cured film may decrease, while when the alkoxysilyl group-containing compound exceeds 50% by weight, the high refractive index may be insufficient.

The alkoxysilyl group-containing compound can be produced as a reaction product with mercaptoalkoxysilanes, diisocyanates and hydroxyl-containing (meth) acrylates.

As a preferable manufacturing method, after manufacturing the intermediate couple | bonded with the thiourethane bond by reaction of mercaptoalkoxysilane and diisocyanate, for example, a urethane bond is made by making the remaining isocyanate react with hydroxyl-containing (meth) acrylates. The method of forming the combined product is mentioned.

Although the same product is obtained also by making the intermediate which couple | bonded with the urethane bond initially by reaction of diisocyanate and hydroxyl-containing (meth) acrylate, and reacting remaining isocyanate and mercaptoalkoxysilanes, mercaptoalkoxysilane The addition reaction of the styrene group and the (meth) acryl group occurs together, the purity thereof is low, and a gelled product may be formed, which is not preferable.

As mercaptoalkoxysilanes for obtaining an alkoxysilyl group containing compound, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl tributoxysilane, 3 -Mercaptopropyldimethylmethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc. are mentioned. Especially, 3-mercaptopropyl trimethoxysilane and 3-mercaptopropylmethyldimethoxysilane are preferable.

As a commercial item of a mercaptoalkoxy silane, Toray Dow Corning Co., Ltd. brand name: SH6062 is mentioned, for example.

As diisocyanate, it is 1, 4- butylene diisocyanate, 1, 6- hexylene diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated bisphenol A diisocyanate, 2, 4- toluenedi, for example. Isocyanate, 2, 6-toluene diisocyanate, etc. are mentioned. Especially, 2, 4- toluene diisocyanate, isophorone diisocyanate, and hydrogenated xylene diisocyanate are preferable.

As a commercial item of a polyisocyanate compound, Mitsui Nisso Urethane Co., Ltd. brand name: TDI-80 / 20, TDI-100, MDI-CR100, MDI-CR300, MDI-PH, NDI, Nippon Polyurethane High School (Note) ) Brand Name: Colonate T, Myrionate MT, Myrionate MR, HDI, Takeda Yakuhin Kogyo Co., Ltd. Product name: Takenate 600, etc. are mentioned.

As a compound which forms an unsaturated double bond among the alkoxy silyl group containing compounds, hydroxyl group containing (meth) acrylates are mentioned. As such hydroxyl-containing (meth) acrylates, 2-hydroxyl ethyl acrylate, 2-hydroxyl ethyl methacrylate, 2-hydroxyl propyl acrylate, 2-hydroxyl propyl methacrylate, 4 -Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, trimethylolpropanediacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol Pentaacrylate and dipentaerythritol pentamethacrylate are mentioned. Preferred hydroxyl group-containing (meth) acrylates are hydroxyl group-containing acrylates, more preferably 2-hydroxyethyl acrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

These mercaptoalkoxysilanes, diisocyanates, and hydroxyl-containing (meth) acrylates can be used individually by 1 type or in combination of 2 or more types.

Preferable mercaptoalkoxysilanes, diisocyanates and hydroxyl group-containing (meth) acrylates in the case of producing an alkoxysilyl group-containing compound are preferably molar ratios of diisocyanates to mercaptoalkoxysilanes. It is 0.8-1.5, More preferably, it is 1.0-1.2, As molar ratio of hydroxyl-containing (meth) acrylates with respect to diisocyanate, Preferably it is 1.0-1.5, More preferably, it is 1.0-1.2. When the molar ratio of diisocyanates to mercaptoalkoxysilanes is less than 0.8, the storage stability of the composition may decrease. When it exceeds 1.5, dispersibility may fall.

When the molar ratio of hydroxyl group-containing (meth) acrylates to diisocyanate is less than 1.0, gelation may occur, and when it exceeds 1.5, high refractive index may decrease.

In order to prevent the anaerobic polymerization of an acryl group and to prevent hydrolysis of an alkoxysilane, it is preferable to carry out manufacture of the alkoxy silyl group containing compound normally. The reaction temperature is preferably 0 ° C to 100 ° C, more preferably 20 ° C to 80 ° C.

Known catalysts may be added in the urethane reaction for the purpose of shortening the production time, and such catalysts include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin didi (2-ethylhexanoate), Octyl tin triacetate.

The addition amount of these catalysts is 0.01 weight%-1 weight% with respect to the total amount with diisocyanate.

Moreover, in order to prevent thermal polymerization of an alkoxysilyl group containing compound, a thermal polymerization inhibitor can also be added at the time of manufacture, for example, p-methoxyphenol and hydroquinone are mentioned. The amount of the thermal polymerization inhibitor added is preferably 0.01% by weight to 1% by weight based on the total amount of the hydroxyl group-containing (meth) acrylates.

The production of the alkoxysilyl group-containing compound can also be carried out in a solvent. As a solvent, it does not react with mercaptoalkoxysilanes, diisocyanate, and hydroxyl-containing (meth) acrylate diisocyanate, for example, It can select suitably from the solvent whose boiling point is 200 degrees C or less.

Specific examples of such a solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate and amyl acetate, and hydrocarbons such as toluene and xylene.

With conductive metal oxide particles Alkoxysilyl group  Reaction with containing compounds

The reaction operation of the conductive metal oxide particles and the alkoxysilyl group-containing compound can be performed by hydrolyzing the alkoxysilyl group-containing compound in the presence of the conductive metal oxide particles. The amount of water added in the hydrolysis is preferably 0.5 to 1.5 equivalents based on the total alkoxy equivalents in the alkoxysilyl group-containing compound, and 0.5 to 5.0 wt% is preferably added to 100 parts by weight of the alkoxysilyl group-containing compound. The water to be used is preferably ion exchange water or distilled water.

The hydrolysis reaction can be carried out by heating and stirring for 1 hour to 24 hours at a temperature of 0 ° C to the boiling point of the component, usually 30 ° C to 100 ° C, in the presence of an organic solvent. As an organic solvent, when using the electroconductive metal oxide particle previously disperse | distributed to the organic solvent, it can carry out as it is, but an organic solvent can also be added separately.

In addition, when performing hydrolysis, an acid or a base may be added as a catalyst to promote the reaction.

Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malic acid, tartaric acid, malonic acid, formic acid, oxalic acid, methacrylic acid, acrylic acid, and itaconic acid. Ammonium salts, such as tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride, are mentioned.

Examples of the base include amines such as aqueous ammonia, triethylamine, tributylamine, and triethanolamine, but the preferred catalyst is an acid, and more preferably an organic acid. The addition amount of these catalysts becomes like this. Preferably it is 0.001 weight part-1 weight part, More preferably, 0.01 weight part-0.1 weight part with respect to 100 weight part of alkoxysilyl group containing compounds.

In addition, the hydrolyzate fixation of the alkoxysilyl group-containing compound on the conductive metal oxide particles can be performed more effectively by adding a dehydrating agent at the end of the hydrolysis reaction.

Examples of the dehydrating agent include organic carboxylic acid orthoesters and ketals, and specific examples thereof include ortho formic acid methyl ester, ortho formic acid ethyl ester, orthoacetic acid methyl ester, orthoacetic acid ethyl ester and the like, and acetone dimethyl ketal and diethyl ketone dimethyl ketal. And acetophenone dimethyl ketal, cyclohexanone dimethyl ketal, cyclohexanone diethyl ketal, benzophenone dimethyl ketal and the like. Especially, they are organic carboxylic acid ortho esters, More preferably, they are ortho formic-acid methyl ester and ortho formic-acid ethyl ester.

These dehydrating agents may be added in an amount of at least 10 moles equal to or more than the molar amount contained in the composition, preferably at least 3 moles or less. If it is less than equimolar, the improvement of storage stability may be insufficient. Moreover, it is preferable to add these dehydrating agents after preparation of a composition. This promotes the storage stability of the composition and the formation of chemical bonds between the silanol group and the conductive metal oxide particles in the hydrolyzate of the alkoxysilyl group-containing compound.

(i-3) Multifunctional  ( MET Acrylic Compound

It is preferable that the high refractive index material used by this invention contains the polyfunctional (meth) acryl compound containing three or more (meth) acryloyl groups in a molecule | numerator. The polyfunctional (meth) acryl compound preferably has 3 to 10, more preferably 3 to 8 (meth) acryloyl groups in the molecule. As such a polyfunctional compound, for example, trimethylol propane tri (meth) acrylate, trimethylol propane trioxyethyl (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

As a commercial item of the polyfunctional (meth) acryl compound which contains three or more (meth) acryloyl groups in a molecule | numerator, For example, Kayarrad DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, D -310, D-330, PET-30, GPO-303, TMPTA, THE-330, TPA-330 (above, Nippon Kayaku Co., Ltd.), Aronix M-315, M-325 (above, Doago Ossei Co., Ltd.) etc. are mentioned.

The ratio of the polyfunctional (meth) acrylic compound in the high refractive index material is preferably 1 to 99% by weight, more preferably 10 to 90% by weight, particularly preferably 30 to 70% by weight.

(i-4) radiation polymerization Initiator

It is preferable that the high refractive index material used for this invention contains a radiation polymerization initiator. As a radiation polymerization initiator, what is necessary is just to decompose by radiation irradiation, generate | occur | produce a radical and start superposition | polymerization, and you may use a photosensitizer further as needed. As such a radiation polymerization initiator, any may be used as long as it is decomposed by irradiation with radiation to generate radicals to initiate polymerization. In the present invention, the term "radiation" refers to infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like.

As a specific example of the said radiation polymerization initiator, For example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1-hydroxycyclohexylphenyl ketone, 2, 2- dimethoxy-2-phenyl acetophenone, a xanthone type compound, Triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzo phenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 1,1-dimethoxydioxybenzoin, 3, 3'-dimethyl-4-methoxybenzophenone, thioxanthone type compound, diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 1- (4-dodecylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, triphenylamine, 2,4,6- Trimethylbenzoyldiphenylphosphineoxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine Seed, bisacylphosphine oxide, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoinethyl Ether, benzoinpropylether, benzophenone, mihiraketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 3-methylacetophenone, 3,3 ' And 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB). Moreover, the combination of BTTB and a dye sensitizer, for example, xanthine, thioxanthine, coumarin, ketocoumarin, etc. are mentioned as an example of an initiator.

Among them, in particular benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Pentylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like are preferable.

As a commercial item of a radiation polymerization initiator, Irgacure 184, 651, 500, 907, 369, 784, 2959, Darocure 1116, 1173 (above, Ciba specialty chemicals company make), Lucirin TPO (BASF) (BASF) company), Ubecryl P36 (manufactured by UCB company), Escarcure KIP150, KIP100F (above, the product made by Runvelty company), etc. are mentioned.

As the sensitizer, for example, triethylamine, diethylamine, N-methyl diethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethyl Aminobenzoic acid isoamyl and the like. As a commercial item, uvecryl P102, 103, 104, 105 (above, UCB Corporation) etc. are mentioned.

The proportion of the radiation polymerization initiator in the composition is preferably 0.01 to 10% by weight, more preferably 0.5 to 7% by weight, particularly preferably 1 to 5% by weight. When it exceeds 10 weight%, it may adversely affect the storage stability of a high refractive index material, the physical property of hardened | cured material, etc.

The high refractive index material includes a polymerization inhibitor, a polymerization initiation aid, a leveling agent, a wettability improving agent, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a silane coupling agent, and an inorganic material within a range that does not impair the object or effect of the present invention. You may further contain additives, such as a filler, a pigment, and dye.

High refractive index layer  formation

A high refractive index layer is formed by apply | coating a high refractive index material to a base material (application member), and hardening | curing. There is no restriction | limiting in particular as a coating method of a high refractive index material, Coating property is a solvent, electroconductive metal oxide particle, the kind and manufacturing conditions of an alkoxysilyl group containing compound, the kind of polyfunctional (meth) acrylate to add, and other additives. It can be adjusted extensively. As a coating method that can be applied, known methods such as roll coating, bar coating, spin coating, curtain coating, spray coating, flow coating, dipping, gravure printing, screen printing and inkjet printing can be applied.

In addition, the means for curing the high refractive index material or the low refractive index material is not particularly limited, for example, heating, irradiation or the like is preferable.

In the case of heat-hardening, it is preferable to heat for 1 to 180 minutes at the temperature within the range of 30-200 degreeC. Moreover, when a radiation polymerization initiator is contained in a high refractive index material, it is preferable to irradiate a radiation and harden a coating film. There is no restriction | limiting in particular as a source of the said radiation as long as it can harden | cure in a short time after apply | coating a composition.

The thickness of the high refractive index layer is not particularly limited, but is preferably, for example, a value of 50 to 30,000 nm, preferably 50 to 1,000 nm. When the thickness of the high refractive index layer is less than 50 nm, in combination with the low refractive index film, the antireflection effect and the adhesion to the substrate may decrease. The effect may fall. In order to obtain a higher antireflection property, when a plurality of high refractive index films are provided in a multilayer structure, the total thickness is preferably within a range of 50 to 30,000 nm. In addition, when providing a hard-coat layer between a high refractive index film and a base material, the thickness of a high refractive index film can be made into the value within the range of 50-300 nm.

In the case where the substrate is provided to provide a high refractive index film or a hard coating layer, the kind is not particularly limited, but for example, glass, polycarbonate resin, polyester resin, acrylic resin, triacetyl cellulose resin The base material containing (TAC) etc. can be mentioned.

The refractive index (refractive index of Na-D line | wire, 25 degreeC of measurement temperature) of a high refractive index layer is 1.6 or more, Preferably it is 1.6-2.0. When the refractive index of the high refractive index layer is less than 1.6, the antireflection effect may be remarkably lowered in combination with the low refractive index film.

In the case where a plurality of high refractive index films are provided, at least one of them may have a refractive index value within the above-described range, and thus the other high refractive index films may have a refractive index value of less than 1.6.

The surface resistance value of the high refractive index layer is preferably 10 ¹⁰ Ω / square or less, more preferably 10 ⁸ Ω / square or less. If the surface resistance value is 10 ¹² Ω / □ or more, adhesion of dust or the like may become remarkable.

[Low refractive index layer]

The low refractive index layer used in the present invention,

(ii-1) It is obtained from the low refractive index material containing the fluorine-containing olefin type polymer which has a polysiloxane segment. In addition, the low refractive index material,

(ii-2) thermosetting compounds and

(ii-3) It is preferable that a curing catalyst is further contained.

(ii-1) Fluorine-containing olefin polymer

The fluorine-containing olefin polymer used in the present invention has a polysiloxane segment in the main chain, and preferably contains 10 to 50 mol% of structural units derived from a monomer containing a hydroxyl group.

The proportion of the polysiloxane segment in the fluorine-containing olefin polymer is usually 0.1 to 10 mol%.

In addition, the fluorine-containing olefin polymer preferably has a fluorine content of 30% by mass or more, more preferably 40 to 60% by mass, and preferably a number average molecular weight in terms of polystyrene obtained by gel permeation chromatography. 5,000 or more, more preferably 10,000 to 500,000. The fluorine content is a value measured by the alizarin complexon method and the number average molecular weight is a value when tetrahydrofuran is used as the developing solvent.

The fluorine-containing olefin polymer includes (a) a fluorine-containing olefin compound (hereinafter referred to as "(a) component"), and (b) a monomer compound containing a hydroxyl group copolymerizable with (a) component (hereinafter referred to as "(b) component" ) And (c) azo group-containing polysiloxane compounds (hereinafter referred to as "(c) component") and, if necessary, (d) reactive emulsifiers (hereinafter referred to as "(d) component") and / or (e) It can obtain by making monomer compounds other than the (b) component copolymerizable with the said (a) component react.

Examples of the fluorine-containing olefin compound as the component (a) include compounds having one or more polymerizable unsaturated double bonds and one or more fluorine atoms, and specific examples thereof include (1) tetrafluoro. Fluoroolefins such as ethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; (2) alkylperfluorovinylethers or alkoxyalkylperfluorovinylethers; (3) Perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether), etc. Perfluoro (alkyl vinyl ether) s; (4) perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether); Others can be mentioned. These compounds can be used alone or in combination of two or more. Among them, hexafluoropropylene, perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkylperfluorovinyl ether is particularly preferable, and it is preferable to use these in combination.

As a monomer compound containing the hydroxyl group which is (b) component, it is (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl, for example. Hydroxyl group-containing vinyl ethers such as ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, and 6-hydroxyhexyl vinyl ether; (2) hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether; (3) allyl alcohol; (4) hydroxyethyl (meth) acrylic acid ester; And others. These compounds can be used alone or in combination of two or more.

The azo group-containing polysiloxane compound of the component (c) is a compound having an azo group and a polysiloxane segment that is easily dissociated in heat represented by -N = N-, for example, the method described in JP-A-6-93100. It can be manufactured by. As a specific example of (c) component, the compound represented by following formula (4) is mentioned.

In formula, y = 10-500 and z = 1-50.

Preferred combinations of the above-mentioned (a) component, (b) component, and (c) component are (1) fluoroolefin / hydroxyl-containing alkyl vinyl ether / polydimethylsiloxane unit, (2) fluoroolefin / purple Luoro (alkylvinylether) / hydroxyl group-containing alkylvinylether / polydimethylsiloxane units, (3) fluoroolefins / perfluoro (alkoxyalkyl) vinylether / hydroxyl group-containing alkylvinylether / polydimethylsiloxane units, (4) Fluoroolefin / (perfluoroalkyl) vinylether / hydroxyl group-containing alkylvinylether / polydimethylsiloxane unit, (5) fluoroolefin / (perfluoroalkoxyalkyl) vinylether / hydroxyl group-containing alkylvinylether / polydimethylsiloxane Unit.

In the fluorine-containing olefin polymer used in the present invention, the structural unit derived from the component (a) is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, particularly preferably 30 to 60 mol% to be. Moreover, the structural unit derived from (b) component becomes like this. Preferably it is 10-50 mol%, More preferably, it is 13-45 mol%, Especially preferably, it is 20-35 mol%. The proportion of the structural unit derived from the component (c) is preferably 0.1 to 20 mol%, more preferably 0.1 to 15 mol%, particularly preferably 0.1 to 20 mol% of the polysiloxane segment contained in the component (c). It is the ratio which becomes 10 mol%.

In the present invention, in addition to the components (a) to (c), it is preferable to further use a reactive emulsifier as the monomer component as the component (d). By using this (d) component, when using a fluorine-containing olefin polymer as a coating agent, favorable applicability | paintability and leveling property can be obtained. Especially as this reactive emulsifier, it is preferable to use a nonionic reactive emulsifier.

In the fluorine-containing olefin polymer, the proportion of the structural unit derived from the component (d) is preferably 10 mol% or less, more preferably 0.1 to 5 mol%.

As a monomer compound other than the (b) component copolymerizable with the (a) component which is (e) component, it is (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl Ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, etc. Alkyl vinyl ethers or cycloalkyl vinyl ethers; (2) carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate and vinyl stearate; (3) methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylic acid esters such as (meth) acrylate and 2- (n-propoxy) ethyl (meth) acrylate; (4) Examples of carboxyl group-containing monomer compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, and the like, and those containing no hydroxyl group are mentioned.

In the fluorine-containing olefin polymer, the proportion of the structural unit derived from the component (e) is preferably 70 mol% or less, more preferably 5 to 35 mol%.

In addition, although the above-mentioned (c) component acts as a radical polymerization initiator, As a radical polymerization initiator which can be used together with this, For example, (1) diacyl peroxides, such as acetyl peroxide and benzoyl peroxide; (2) ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; (3) hydroperoxides such as hydrogen peroxide, tert-butylhydroperoxide and cumene hydroperoxide; (4) dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide and dilauroyl peroxide; (5) peroxy esters such as tert-butyl peroxy acetate and tert-butyl peroxy pivalate; (6) azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; (7) Persulfates, such as ammonium persulfate, sodium persulfate, and potassium persulfate, etc. are mentioned.

It is preferable to perform the polymerization reaction for obtaining a fluorine-containing olefin type polymer in the solvent system using a solvent. As a preferable organic solvent here, For example, (1) Ester, such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and a cellosolve; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; (3) cyclic ethers such as tetrahydrofuran and dioxane; (4) amides such as N, N-dimethylformamide and N, N-dimethylacetamide; (5) aromatic hydrocarbons such as toluene and xylene; And others. Moreover, alcohol, aliphatic hydrocarbons, etc. can also be mixed and used as needed.

In the present invention, any of the emulsion polymerization method, suspension polymerization method, block polymerization method or solution polymerization method using a radical polymerization initiator may be used as the polymerization method for producing the fluorine-containing olefin polymer, and also in the polymerization operation. , A batch, semi-continuous or continuous operation can be selected.

(ii-2) thermosetting compounds

As a thermosetting compound, various amino compound, various hydroxyl-containing compounds, such as pentaerythritol, polyphenol, glycol, etc. are mentioned, for example.

The amino compound used as the thermosetting compound is a compound containing two or more of a total of two or more amino groups, for example, hydroxyalkylamino groups and alkoxyalkylamino groups, which can react with hydroxyl groups present in the fluorine-containing olefin polymer, Specifically, a melamine type compound, a urea type compound, a benzoguanamine type compound, a glycoluril type compound, etc. are mentioned, for example.

Melamine-based compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples thereof include melamine, alkylated melamine, methylolmelamine, alkoxylated methylmelamine, and the like. It is preferable to have two or more of any one or both of methyl groups. Specifically, methylolated melamine, alkoxylated methylmelamine, or derivatives thereof obtained by reacting melamine and formaldehyde under basic conditions are preferable, in particular, good storage stability is obtained in the liquid resin composition, and good reactivity is obtained. Alkoxylated methylmelamine is preferred. There is no restriction | limiting in particular in the methylolation melamine and the alkoxylated methylmelamine used as a thermosetting compound, For example, various resinous forms obtained by the method described in the plastic material course [8] free fish melamine resin (Nigan Kogyo Shimbun). Water can also be used.

Examples of the urea-based compound include methyl urea which is a derivative of polymethylolated urea in addition to urea, methylolated uron having a uron ring, methylalurized alkoxide and the like. Moreover, also about compounds, such as a urea derivative, can use the various dendritic materials described in the said document.

The usage-amount of the thermosetting compound with respect to 100 mass parts of fluorine-containing olefin type polymers is 15-80 mass parts normally, Preferably it is 20-70 mass parts, More preferably, it is 30-60 mass parts. When the amount of the thermosetting compound is used too little, the durability of the low refractive index layer to be formed may be insufficient, and when it exceeds 80 parts by mass, it is difficult to avoid gelation in the reaction with the fluorine-containing olefin-based polymer. It does not become a thing of refractive index, and hardened | cured material may become weak.

The reaction between the fluorine-containing olefin polymer and the thermosetting compound may be performed, for example, by adding the thermosetting compound to a solution of an organic solvent in which the fluorine-containing olefin polymer is dissolved, and homogenizing the reaction system by appropriate time heating and stirring. The heating temperature for this reaction is preferably in the range of 30 to 150 ° C, more preferably in the range of 50 to 120 ° C. When this heating temperature is less than 30 degreeC, reaction progress is very slow and when it exceeds 150 degreeC, since crosslinking reaction by reaction of the methylol group and the alkoxylated methyl group among thermosetting compounds other than the target reaction occurs and a gel is formed, it is preferable. Not. The progress of the reaction can be quantitatively confirmed by a method of quantifying a methylol group or an alkoxylated methyl group by infrared spectroscopy or the like, or by recovering the dissolved polymer by reprecipitation and measuring the increase amount.

(ii-3) curing catalyst

As a curing catalyst, a thermal acid generator is mentioned, for example. A thermal acid generator is a substance which can accelerate hardening reaction when the coating film etc. of the said liquid resin composition are heated and hardened | cured, and the substance which can improve the heating conditions to be milder. There is no restriction | limiting in particular as this thermal acid generator, The above-mentioned various acids and its salts used as a hardening | curing agent for general urea resin, melamine resin, etc. can be used. As a specific example, various aliphatic sulphonic acid, its salt, various aliphatic carboxylic acid, such as citric acid, acetic acid, maleic acid, its salt, various aromatic carboxylic acid, such as benzoic acid, phthalic acid, its salt, alkylbenzene sulfonic acid, and its ammonium salt And various metal salts, phosphoric acid and phosphoric acid esters of organic acids.

The usage-amount of the hardening catalyst with respect to 100 mass parts of fluorine-containing olefin type polymers is 5-20 mass parts normally, Preferably it is 8-20 mass parts, More preferably, it is 10-15 mass parts. When the usage-amount of a hardening catalyst is too low, there exists a possibility that sufficient mechanical strength may not be obtained. Moreover, when this ratio becomes excessive, since the storage stability of the low refractive index material deteriorates, or because the catalyst acts as a plasticizer in the cured film, sufficient mechanical strength may not be obtained.

solvent

Usually, a low refractive index material is obtained as a solution by the solvent used for manufacture of a fluorine-containing olefin polymer, or the solvent used for reaction of a fluorine-containing olefin polymer and a thermosetting compound, and therefore contains a solvent as it is.

Moreover, another solvent can be added and mix | blended for the purpose of improving the coating property etc. of a low refractive index material. Preferable solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate. In addition, the low refractive index material can be used together with the solvent which cannot melt | dissolve a fluorine-containing olefin type polymer, for example, poor solvents, such as water, alcohol, and ether, in the range which does not precipitate a fluorine-containing olefin type polymer. As a result, the solution of the fluorine-containing olefin polymer may have good storage properties and preferable coatability. As such a poor solvent, ethyl alcohol, isopropyl alcohol, tert- butyl alcohol, etc. are mentioned.

additive

The low refractive index material includes various monomers, polymers, pigments or the like having, for example, hydroxyl groups such as hydroxymethyl (meth) acrylate, for the purpose of improving the coating properties and the physical properties of the film after curing, the provision of photosensitivity to the coating film, or the like. Various additives, such as coloring agents, such as dye, stabilizer, such as an antioxidant and an ultraviolet absorber, a thermal acid generator, a photosensitive acid generator, surfactant, a polymerization inhibitor, a solvent, can be contained. In particular, for the purpose of improving the hardness and durability of the cured film to be formed, it is preferable to add a thermal acid generator or a photoacid generator, and in particular, it does not lower the transparency after curing, and is selected and used to be uniformly dissolved in the solution. It is preferable.

Low refractive index  formation

The low refractive index layer is formed by applying and curing a low refractive index material on a substrate (high refractive index layer) similarly to the high refractive index layer. There is no restriction | limiting in particular as a coating method and the hardening method of a low refractive index material, The method mentioned above can be applied as a coating method of a high refractive index material.

The thickness of the low refractive index layer is not particularly limited, but is, for example, 50 to 300 nm, preferably 50 to 250 nm, particularly preferably 60 to 200 nm. When the thickness of the low refractive index layer is less than 50 nm, the adhesion to the high refractive index layer may decrease. On the other hand, when the thickness exceeds 300 nm, optical interference does not occur and the antireflection effect may decrease. In addition, in order to make a multilayer structure by providing two or more low refractive index layers in order to obtain higher antireflection property, what is necessary is just to make the total thickness into the value within the range of 50-300 nm.

The lower the refractive index value of the low refractive index layer (refractive index of Na-D line, measuring temperature 25 ° C.), the better the antireflection effect is obtained when combined with the high refractive index film, but specifically 1.6 or less, preferably 1.3 to 1.6, More preferably, it is 1.3-1.5. In addition, when the refractive index of the low refractive index film is less than 1.3, the kind of usable material may be excessively limited.

In the case where a plurality of low refractive index layers are provided, at least one of them may have a refractive index value within the above-described range, and thus the other low refractive index layers may exceed 1.6.

Further, since a better antireflection effect is obtained, the refractive index difference between the low refractive index layer and the high refractive index layer is preferably set to a value of 0.05 or more. More preferably, it is 0.1-0.5, More preferably, it is 0.15-0.5.

[Hard Coating Layer]

It is preferable that the antireflection layer used by this invention has a hard coat layer further. Examples of the hard coating layer include those made of materials such as silicone resins, epoxy resins, acrylic resins, melamine resins, and the like, and are excellent in adhesion to the near-infrared absorbing layer used in the present invention. The hard coat layer obtained is used preferably.

(iii-1) an oxide compound of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium and an organic compound containing a polymerizable unsaturated group Particles (hereinafter also referred to as "crosslinkable particles"), and

(iii-2) Resin composition containing the (meth) acrylic acid ester which has alicyclic structure.

The resin composition is further,

(iii-3) A compound containing two or more polymerizable unsaturated groups in a molecule other than (iii-2);

(iii-4) It is preferable to contain a radiation polymerization initiator.

(iii-1) Crosslinkable  particle

The crosslinkable particles are formed by combining an oxide compound of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium with an organic compound containing a polymerizable unsaturated group. Particles.

Examples of the oxide particles include silica, aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Among them, silica, aluminum oxide, zirconia and antimony oxide are preferred from the viewpoint of high hardness, and silica is particularly preferable. These can be used individually by 1 type or in combination of 2 or more types.

It is preferable that an oxide particle is powder form or a solvent dispersion sol. In the case of a solvent dispersion sol, the dispersion solvent is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. As such an organic solvent, For example, Alcohol, such as methanol, ethanol, isopropanol, butanol, an octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactate and γ-butyrolactone; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides, such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, are mentioned. Especially, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene are preferable.

The number average particle diameter of the oxide particles is preferably 0.001 µm to 2 µm, more preferably 0.001 µm to 0.2 µm, and particularly preferably 0.001 µm to 0.1 µm. Moreover, in order to improve the dispersibility of particle | grains, various surfactant and amines can also be added.

The shape of the oxide particles is spherical, hollow, porous, rod, plate, fibrous, or indefinite, preferably spherical. The specific surface area (value by the BET specific surface area measurement method using nitrogen) of an oxide particle becomes like this. Preferably it is 10-1000 m <2> / g, More preferably, it is 100-500 m <2> / g.

As a commercially available product as a silicon oxide particle (for example, a silica particle), it is colloidal silica, for example, Nissan Chemical Industries, Ltd. brand name: methanol silicazol, IPA-ST, MEK-ST, NBA -ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. have. Moreover, as powder silica, Nippon Aerosil Co., Ltd. brand name: Aerosyl 130, Aerosyl 300, Aerosyl 380, Aerosyl TT600, Aerosyl OX50, Asahi Glass ( Co., Ltd. Product name: Sildex H31, H32, H51, H52, H121, H122, Nippon Silica Co., Ltd. Product name: E220A, E220, Fuji-Silysia Co., Ltd. Product name: SYLYSIA 470, Japanese glass Co., Ltd. A brand name: SG flake etc. are mentioned.

Moreover, as a water dispersion of alumina, Nissan Chemical Industries, Ltd. brand name: Alumina sol-100, -200, -520; As an aqueous product of zinc antimonate powder, Nissan Chemical Industries, Ltd. brand name: Celnax; Examples of powders and solvent dispersions such as alumina, titanium oxide, tin oxide, indium oxide, and zinc oxide include CI Kasei Co., Ltd. product name: Nanotech; As an aqueous dispersion of antimony dope tin oxide, Ishihara Sangyo Co., Ltd. brand name: SN-100D; As an ITO powder, the product of Mitsubishi Material Co., Ltd .; As a cerium oxide aqueous dispersion, Taki Chemical Co., Ltd. brand name: Nydral etc. are mentioned.

As an organic compound containing a polymerizable unsaturated group, the alkoxy silyl group containing compound mentioned above is mentioned as a structural component of a high refractive index material. Moreover, as a manufacturing method of a crosslinkable particle | grain, the method of combining an oxide particle and the organic compound containing a polymerizable unsaturated group by the method similar to reaction of the above-mentioned electroconductive metal oxide particle and an alkoxy silyl group containing compound is mentioned. have.

The compounding quantity of the crosslinkable particle | grains in the resin composition becomes like this. Preferably it is 5-90 weight%, More preferably, it is 10-70 weight%. In addition, the quantity of crosslinkable particle | grains means solid content, and when a crosslinkable particle | grain is used in the form of a solvent dispersion sol, the compounding quantity does not contain the quantity of a solvent.

(iii-2) Alibi  Having a structure ( MET Acrylic Acid Ester

The alicyclic structure-containing (meth) acrylic acid esters to be used in the present invention are not particularly limited as long as they are (meth) acrylic acid esters containing a cyclic structure with a saturated hydrocarbon in an ester substituent. (Meth) acrylic acid esters, (meth) acrylic acid esters having a bicyclo [2.2.1] heptane ring, (meth) acrylic acid esters having a tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [6.2. 1.0 ^2,7 .1 ^3,6 ] (meth) acrylic acid ester which has a dodecane ring, etc. are mentioned. Among these, (meth) acrylic acid esters having a bicyclo [2.2.1] heptane ring, (meth) acrylic acid esters having a tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [6.2.1.0 ^{2, 7} .1 ^3,6] at least one member selected from the group consisting of (meth) acrylic acid esters having a kanhwan dodecyl are preferred. These alicyclic structure containing (meth) acrylic acid esters have the effect of ensuring firm adhesiveness with the surface of norbornene-based resin.

As a specific example of alicyclic structure containing (meth) acrylic acid ester, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, isoboroyl (meth) acrylate, tricyclodecanediyldi (meth) acrylate, tetratricyclodecanediyldimethadi (meth) acrylate And polymerizable monomers such as (meth) acrylate modified with respective ethylene glycol or propylene glycol. Further, oligomers of norbornene-based resins, intermediates or monomers having unsaturated double bonds before hydrogenation thereof are modified by the same synthesis method as those of (meth) acrylic acid esters such as dicyclopentanyl (meth) acrylate (meth) The photopolymerizable oligomer which introduce | transduced the acryloyl group may be sufficient. Preferred among these are dicyclopentanyl (meth) acrylate, tricyclodecanediyldi (meth) acrylate, tetratricyclodecanediyldi (meth) acrylate, and the like.

(iii-3) other Polymerizable Unsaturated groups  Compound containing

Although there is no restriction | limiting in particular as a compound containing 2 or more polymerizable unsaturated groups in molecules other than (iii-2) used for this invention, For example, (meth) acrylic esters and vinyl compounds are mentioned. In this, (meth) acrylic ester is preferable.

For example, as (meth) acrylic ester, a trimethylol propane tri (meth) acrylate, a ditrimethylol propane tetra (meth) acrylate, a pentaerythritol tri (meth) acrylate, and a pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tree (meth) Acrylate, ethylene glycol di (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, neo Pentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanu Rate (Meth) acrylates and poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols, oligoester (meth) acrylates having two or more (meth) acryloyl groups in the molecule , Oligoether (meth) acrylates, oligourethane (meth) acrylates, and oligoepoxy (meth) acrylates.

Among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylol propane tetra (meth) acrylate are preferable.

Examples of the vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and the like.

As a commercial item of the said compound, Toagosei Co., Ltd. brand name: Aronix M-400, M-408, M-450, M-305, M-309, M-310, M-315, M -320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270 , TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1231, TO-902, TO-904, TO-905, TO-1330, Nippon Kayaku Co., Ltd. : KAYARAD DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR- 444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoesha Chemical Co., Ltd. brand name: Lightacrylate PE-4A, DPE-6A, DTMP-4A, etc. are mentioned.

Moreover, in the composition of this invention, you may contain the compound which has one polymerizable unsaturated group in a molecule as needed.

As for the compounding ratio (weight ratio) of the said (iii-2) component and (iii-3) component, (iii-2) :( iii-1) is usually 5: 95-90: 10, Preferably it is 10: 90-80. : 20.

(iii-4) radiation polymerization Initiator

A radiation polymerization initiator can be mix | blended with a resin composition as needed. As the radiation polymerization initiator, the above-mentioned radiation polymerization initiator can be used as a component of the high refractive index material.

The compounding amount of the radiation polymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of (iii-1) to (iii-3).

As needed, a sensitizer, a solvent, oxide particles other than crosslinkable particle | grains, various additives, etc. can be mix | blended with a resin composition. In addition, a resin composition can be diluted and used with a solvent from a viewpoint of workability.

hard  Formation of coating layer

The hard coat layer is formed by applying the above-described resin composition to a substrate (near infrared ray absorbing layer or the like) and curing the same as the high refractive index layer and the low refractive index layer. There is no restriction | limiting in particular as a coating method and the hardening method of a resin composition, The method mentioned above can be applied as a coating method of a high refractive index material.

The thickness of the hard coat layer is not particularly limited, but is, for example, 1 to 50 µm, preferably 2 to 10 µm. If the thickness of the hard coating layer is less than 1 µm, the adhesion of the antireflection film to the substrate may not be improved. On the other hand, if the thickness exceeds 50 µm, it may be difficult to form uniformly.

<Shock absorbing layer>

The shock absorbing layer, which preferably constitutes the composite functional film of the present invention, has transparency capable of securing visibility of the display content of the display panel, and can prevent damage caused by indentation or collision of the substrate. Although the component is not specifically limited, It is preferable that it is comprised especially with an elastomer. In addition, the elastomer in the present specification includes a dielectric rubber.

Examples of the elastomer include conjugated diene block (co) polymers, hydrogenated products thereof, ethylene-α-olefin copolymers, polar group-modified olefin copolymers, polar group-modified olefin copolymers, metal ions, and / or metal compounds. Nitrile rubber, such as elastomer, acrylonitrile butadiene rubber, butyl rubber, acrylic rubber, thermoplastic polyolefin elastomer (TPO), thermoplastic polyurethane elastomer (TPU), thermoplastic polyester elastomer (TPEE), polyamide elastomer (TPAE) ), Thermoplastic elastomers such as diene elastomers (such as 1,2-polybutadiene), silicone elastomers, fluorine elastomers, and the like. Among these, conjugated diene block (co) polymers and hydrogenated products thereof are preferable, and hydrogenated products of conjugated diene block (co) polymers are particularly preferable. The conjugated diene-based block (co) polymer and its hydrogenated substance include a block (co) polymer of conjugated diene and an aromatic vinyl compound and its hydrogenated substance.

Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene And 4,5-diethyl-1,3-octadiene, chloroprene and the like. Among them, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene and isoprene are particularly preferable. In addition, the compound illustrated above can be used individually by 1 type or in combination of 2 or more types. As a block (co) polymer which uses this conjugated diene, butadiene block copolymer, butadiene-isoprene-butadiene block copolymer, etc. are mentioned.

Examples of the aromatic vinyl compound include styrene, t-butyl styrene, α-methylstyrene, α-chlorostyrene, p-methylstyrene, divinylbenzene, N, N-diethyl-p-aminostyrene, and the like. The compound illustrated above can be used individually by 1 type or in combination of 2 or more types. As a block copolymer which uses this aromatic vinyl compound and conjugated diene, a styrene butadiene styrene block copolymer (SBS), a styrene- isoprene-styrene block copolymer, etc. are mentioned.

In addition, although the hydrogenated substance is obtained by hydrogenating the said block copolymer, as a block polymer used, butadiene polymer block (I) which has a vinyl bond content of less than 25% especially, and a conjugated diene unit / other monomeric unit (mass ratio) = Conjugated diene-based block copolymers having one or more polymer blocks (II) in the molecule of (100 to 50) / (0 to 50) and having a vinyl bond content of 25 to 95% (hereinafter, "polymer (P)") Also referred to).

The content of vinyl bonds (1,2-bonds) in the butadiene polymer block is preferably less than 25%, more preferably 5 to 20%, even more preferably 7 to 19%. Therefore, the butadiene polymer block (I) becomes a crystalline block having a structure similar to that of the ethylene butene copolymer by hydrogenation. By carrying out a vinyl bond content in the said range, the mechanical property and shape retention of a molded object can be improved.

As said polymer (P), when butadiene polymer block (I) is set to "A ¹ " and polymer block (II) is set to "B ¹ ", (A ¹ -B ¹ ) _m1 , (A ¹ -B ¹ ) _m2 -A ¹ , (B ¹ -A ¹ ) _m3 -B ¹ and the like can be used. In each of the above formulas, m1 to m3 represent an integer of 1 or more.

Moreover, if the said polymer (P) is a copolymer which has a block of 3 or more blocks, when the hydrogenated substance is formed, the molded object excellent in shape retention property and mechanical properties can be obtained further. Therefore, m1 in the above formula is preferably an integer of 2 or more.

Further, the polymer (P) is (A ¹ -B ¹ ) _n X, (B ¹ -A ¹ ) _n X, (A ¹ -B ¹ -A ¹ ) _n X, (B ¹ -A ¹ -B ¹ ) The polymer molecular chain may be extended or branched through the coupling agent residue X, such as _n X. In each formula, n represents an integer of 2 or more. Moreover, in each said chemical formula, when n is three or more, when the hydrogenated substance is formed, the molded object excellent in shape retention property, hot melt spot, and adhesiveness can be obtained.

Examples of the coupling agent include 1,2-dibromoethane, methyldichlorosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, tetramethoxysilane, divinylbenzene, diethyl adipate and dioctyl adipic acid. , Benzene-1,2,4-triisocyanate, tolylene diisocyanate, epoxidized 1,2-polybutadiene, epoxidized linseed oil, tetrachlorogermanium, tetrachlorotin, butyltrichlorotin, butyltrichlorosilane, dimethylchloro Silane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, etc. are mentioned.

Hydrogenation of the said polymer (P) is performed with respect to the olefinic unsaturated bond in a block, Hydrogen obtained by making a hydrogenation rate preferably 80% or more, More preferably, 85% or more, Especially preferably, 90% or more The shape retention property and the mechanical property at the time of forming a molded object with an additive can be improved. In addition, the hydrogenation of the said polymer (P) is performed by the method etc. which were disclosed by Unexamined-Japanese-Patent No. 2-133406, Unexamined-Japanese-Patent No. 3-128957, Unexamined-Japanese-Patent No. 5-170844, etc. I can do it.

The shock absorbing layer may be composed of an uncrosslinked elastomer, or may be composed of an elastomer at least partially crosslinked. When at least one part is comprised by the crosslinked elastomer, the heat resistance of a molded object can be improved.

There is no restriction | limiting in particular about the method of bridge | crosslinking the said elastomer, For example, the means chosen from the method of using electron beam irradiation, ultraviolet irradiation, and a crosslinking agent (for example, organic peroxide etc.) is mentioned.

When performing the said bridge | crosslinking by electron beam irradiation, bridge | crosslinking can be formed by irradiating an electron beam with an electron beam irradiation apparatus with respect to the obtained molded object. In addition, in the case of ultraviolet irradiation, crosslinking can be formed by the effect of the photosensitizer mix | blended as needed by irradiating an ultraviolet-ray with an ultraviolet irradiation apparatus with respect to the obtained molded object. In addition, in the case of the method using a crosslinking agent, the obtained molded object is normally heated in atmosphere which does not exist, such as nitrogen atmosphere, and can form bridge | crosslinking by the effect of crosslinking agents, such as an organic peroxide mixed as needed, and a crosslinking adjuvant. Can be.

In the shock absorbing layer, the elastomer may contain a liquid material at room temperature such as various lubricants for plastic and rubber, plasticizers, softeners and liquid oligomers. In this case, a shock absorbing multilayer body for plasma display panel having more flexibility can be manufactured.

Specifically, examples of the lubricant include paraffin lubricants, hydrocarbon lubricants, metal soaps, and the like. Examples of the plasticizer include one or two or more kinds of fatty acid derivatives such as phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives, sebacic acid derivatives, fumaric acid derivatives and citric acid derivatives. Examples of the softener include one or two or more of petroleum softeners such as paraffinic process oils, mineral oil softeners such as ethylene-α-olefin-based oligomers and gilsonite, and fatty acids such as oleic acid and ricinolic acid. have. Moreover, 1 type (s) or 2 or more types, such as polyisobutylene and silicone oil, are mentioned as a liquid oligomer. In particular, when used in a plasma display panel used outdoors, such as a mobile phone, as a liquid material, a component having a double bond or an oil without a double bond, such as paraffin-based process oil, paraffin-based synthetic oil, hydrogenated paraffin-based oil, etc. Use of one kind or two or more kinds of these small (specifically 20 mass% or less, or 10 mass% or less) oils is preferred because an impact absorbing layer excellent in weather resistance can be formed.

The amount used when the liquid material is used is preferably 50 to 5000 parts by mass, more preferably 50 to 3000 parts by mass, particularly preferably when the total amount of the polymer contained in the elastomer is 100 parts by mass. Is 50 to 2000 parts by mass.

The transparency of the shock absorbing layer can be arbitrarily selected according to the position where it is arranged. However, when disposed on the display surface side of the display, when the thickness is 0.5 mm, the total light transmittance is 90% or more, particularly 91% or more, and 92% or more. It is preferable. ·

The thickness of the shock absorbing layer can be arbitrarily selected, and can be, for example, 2.0 mm or less (preferably 1.2 mm or less, more preferably 1.0 mm or less). In addition, the number of layers of the shock absorbing layer arrange | positioned may be one layer, or multiple layers may be sufficient as it.

The method of joining the shock absorbing layer to a substrate or the like is not particularly limited as long as it is a method in which the layers to be bonded are in close contact with each other. For example, it can bond by bonding at predetermined temperature (for example, room temperature etc.), or can adhere using an adhesive agent (or adhesive). Moreover, it can also form directly in a predetermined | prescribed place by hot press, cold press, etc.

<Electromagnetic Shield Layer>

As the electromagnetic shielding layer, which preferably constitutes the composite functional film of the present invention, generally a metal mesh is preferably used. Examples of the metal mesh include a wire mesh and a metal pattern, and a metal pattern is particularly preferable.

As a metal material, metals, such as copper, iron, nickel, aluminum, gold, silver, platinum, tungsten, chromium, titanium, its oxide, and the alloy which combined 2 or more types of these metals can be used. Moreover, the thing which plated the surface as needed, such as oxidation prevention, can be used suitably. Among these metals, particularly preferably copper, aluminum and nickel are suitable in view of thinning processability, conductivity and price, and metals formed by vacuuming such as metal foil having a thickness of 0.5 to 50 µm, plating metal, and vapor deposition are used.

As a method of forming a metal pattern in the present invention, for example, a plurality of holes are produced by punching a metal thin film or a metal foil, or a plurality of holes are subjected to an etching process using a photoresist method to the same metal thin film or a metal foil, for example. A hole may be manufactured or an ultrafine metal mesh film may be formed.

<Manufacturing method of a composite function film>

The composite functional film of the present invention is preferably formed by forming a laminate including each of the above-described layers on a support film, and superposing a second support film on the laminate as necessary. In addition, the composite functional film of the present invention can be preferably formed by a method of forming a partial layer of lamination on a supporting film, forming another layer on the second supporting film, and then overlapping and compressing both.

It is preferable that the said support film is a transparent resin film which has heat resistance and solvent resistance, and has flexibility. As resin which comprises a support film, fluorine-containing resin, such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, nylon, cellulose, for example Etc. can be mentioned. The thickness of a support film is 20-100 micrometers, for example.

Moreover, it is preferable that a mold release process is given to the surface of a support film. Thereby, peeling operation of a support film can be performed easily in the transfer process mentioned later.

It is preferable to use this composite function film by peeling the support film provided as needed and transferring it to the front surface (viewing side) of the front plate for PDPs. An example of the transfer process is as follows. After peeling off a support film, the film is superposed so that the surface (preferably the surface of an impact absorption layer) of a composite functional film may contact the surface of a board | substrate, and this composite functional film is preferably thermocompression-bonded with a heating roller etc., Peeling removal of the 2nd support film provided as needed is carried out. Thereby, lamination | stacking is transcribe | transferred and adhered to the surface of a glass substrate.

The substrate used as the front plate for the PDP described above is a transparent substrate constituting the plasma display unit.

As a board | substrate material, plate-shaped member containing insulating materials, such as glass, silicone, polycarbonate, polyester, aromatic amide, polyamideimide, polyimide, is mentioned, for example. About the surface of this plate-shaped member, Chemical treatment with a silane coupling agent etc. as needed; Plasma treatment; Appropriate pretreatment such as thin film formation by ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like may be performed.

Among these substrate materials, glass plates are preferred. As glass, borosilicate glass, aluminosilicate glass, alumino borosilicate glass, etc. are mentioned, for example. Moreover, the low alkali glass, the alkali free glass, etc. of these glass are mentioned. Moreover, silica glass, soda-lime glass, etc. are mentioned. Among these, borosilicate glass, aluminosilicate glass, aluminoborosilicate glass, and low alkali glass thereof are preferable, and these alkali free glass is preferable.

<Example>

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to this.

1, the cross section of the plasma display composite functional film of this invention is shown typically. First, as the support film 1, a shock absorbing layer 2 having a thickness of 0.8 mm is formed on a polyester film having a thickness of 50 µm, and an electromagnetic wave shield layer 3 having a thickness of 15 µm is formed on the surface thereof. The near-infrared absorption layer 4 of thickness 100micrometer was formed, and the anti-reflective layer 5 was laminated on it. On the antireflection layer 5, a 38-micrometer-thick polyester film was laminated | stacked as the 2nd support film 6. In addition, the antireflection layer was formed of a laminate including a hard coating film 7 having a thickness of 3 μm, a high refractive index film 8 having a thickness of 0.1 μm, and a low refractive index film 9 having a thickness of 0.1 μm, as shown in FIG. 1. .

The supporting film 1 of the composite functional film thus obtained was peeled off and transferred to the visual side of the front plate 10 for a PDP as shown in FIG. 2. After the transfer, the second support film 6 was peeled off.

(Production of Shock Absorbing Layer)

Cyclohexane (25 kg), tetrahydrofuran (1.25 g), butadiene (1500 g), and n-butyllithium (4.5 g) are added to a nitrogen-substituted internal volume 50 l reaction vessel and heat-insulated at 70 ° C. The polymerization was carried out. After completion of the reaction, the temperature was 15 ° C, and tetrahydrofuran (350 g) and 1,3-butadiene (3500 g) were added to perform adiabatic polymerization. After 30 minutes, methyldichlorosilane (3.23 g) was added, and reaction was performed for 15 minutes. After the reaction was completed, 2 g of n-butyllithium and hydrogen gas were supplied at a pressure of 0.4 MPa-G, and stirred for 20 minutes to make the living anion lithium hydride. The reaction solution was 90 degreeC, and the hydrogenation reaction was performed using the titanocene compound of Unexamined-Japanese-Patent No. 2000-37632. When the absorption of hydrogen is complete, the reaction solution is returned to normal temperature and atmospheric pressure, taken out from the reaction vessel, and then the reaction solution is stirred and added in water to remove the solvent by steam distillation, thereby adding hydrogen as a hydrogenated diene polymer. Block polymer 1 was obtained. The hydrogenation rate of the obtained hydrogenated block polymer 1 was 98%, the weight average molecular weight was 280,000, and the vinyl-bond content of the polybutadiene block of the first stage of the polymer before hydrogenation was 14%, and the polybutadiene block of the second stage of the polymer before hydrogenation was 14%. The vinyl bond content of was 80%. Thereafter, the hydrogenated block polymer 1 and the mineral oil-based softener (Idemitsu Kosan Co., Ltd. make, product name "PW-90") were mixed in the ratio of 100: 800 (weight ratio), the resin composition was produced, and this was apply | coated To prepare a shock absorbing layer having a thickness of 0.8 mm.

(Production of Electromagnetic Shield Layer)

The electrolytic copper foil of 15 micrometers in thickness which roughened both surfaces was etched by lattice form, the copper mesh of 20 micrometers of line widths, and 300 micrometers of line pitches was produced, and it was set as the electromagnetic shielding layer.

(Production of Near Infrared Absorption Layer)

(1) Synthesis of Norbornene-Based Resin

175 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (specific monomers), tricyclo [4.3.0.1 ^2,5 ] -3- 75 parts of decene (copolymerizable monomer), 41 parts of 1-hexene (molecular weight regulator) and 750 parts of toluene (solvent for ring-opening polymerization reaction) were placed in a reaction vessel substituted with nitrogen, and the solution was heated to 60 ° C. Then, tungsten chloride (t-butanol: methanol: tungsten = 0.35 mol: 0.3 mol: 1) modified with 0.62 parts of toluene solution of triethylaluminum (1.5 mol / l) and t-butanol / methanol in the solution in the reaction vessel. 3.7 parts of toluene solution (concentration 0.05 mol / L) was added, and the ring-opening polymerization reaction was performed by heating and stirring this system at 80 degreeC for 3 hours, and the ring-opening polymer solution was obtained. The polymerization conversion ratio in this polymerization reaction was 97%.

4,000 parts of the ring-opening polymer solution thus obtained were put in an autoclave, and 0.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution, and the hydrogen gas pressure was 100 kg / cm 2 and the reaction temperature was 165 ° C. The hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of. The obtained reaction solution (hydrogenated polymer solution) was cooled to discharge hydrogen gas, and then a large amount of methanol was added to precipitate and recover the hydrogenated polymer.

Thus, the hydrogenation rate of the obtained hydrogenated polymer (henceforth "norbornene-type resin A") was 100% substantially.

Mw of norbornene-type resin A was 68,000, Mn was 22,000, and glass transition temperature was 146 degreeC. In addition, the saturated water absorption was 0.32%. In addition, the measuring method and evaluation method of each physical property value are as follows.

Molecular weight: Standard polystyrene conversion under conditions of o-dichlorobenzene solvent, 120 ° C using a gel permeation chromatography (GPC) device (150 C type) manufactured by WATERS, Inc. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of were measured.

Hydrogenation rate: It measured using 500 MHz ¹ H-NMR (AVANCE 500) by the Brooker company.

Glass transition temperature (Tg): The temperature increase rate: It measured under nitrogen stream at 20 degreeC every minute using the differential scanning calorimeter (DSC 6200) by Seiko Instruments.

Saturated water absorption: In accordance with ASTM D570, after immersing the test piece in water at 23 ° C. for 1 week, the water absorption was measured from the weight change of the test piece.

(2) Preparation of Specific Compositions

40 g of norbornene-based resin A obtained in (1) was dissolved in 60 g of toluene to obtain a toluene solution of norbornene-based resin A. Subsequently, 100 g of a 0.4% toluene solution of the phthalocyanine-based pigment SIR-159 (manufactured by Mitsui Chemical Industries, Inc.) was added to the toluene solution of the norbornene-based resin A, followed by stirring and mixing, and a fluorine resin filter (pore size: 1 Filtered) and degassed to give specific composition A.

The storage stability was evaluated for the specific composition A as follows.

80 ml of the composition was put and sealed in the inner pressure-resistant container of 100 ml of volume, and it preserve | saved for one week in the hot-air oven of 100 degreeC. Thereafter, the mixture was taken out from the oven, cooled to room temperature, the contents were taken out, the appearance was observed, and the spectral transmittance was measured and compared with the initial value. As a result, both the appearance and the spectral transmittance were unchanged from the initial values, and the storage stability was good.

(3) Preparation of the thermoplastic resin composition

A large amount of methanol was added to the specific composition A to precipitate and recover the thermoplastic resin composition. The recovered thermoplastic resin composition was heated to 120 ° C. in a reduced pressure drier and dried for 24 hours. The thermoplastic resin composition thus obtained is referred to as thermoplastic resin composition A.

As a result of analyzing the amount of toluene and methanol in the thermoplastic resin composition A by gas chromatography, all were 0.1% or less.

(4) Production of molded article

Specific composition A was applied using an applicator bar on a polyester film such that the dry film thickness was 100 μm, followed by drying at 80 ° C. for 8 hours and at 100 ° C. in a reduced pressure dryer for 24 hours. Then, it took out from the dryer, cooled to normal temperature, peeled the polyester film, and obtained film-form molded object A1. Although the external appearance of the obtained molded object A1 was observed, color nonuniformity and a bleeding object were not recognized. Moreover, as a result of analyzing the molded object A1 by gas chromatography, the amount of residual toluene was 0.3%.

The total light transmittance and the spectral transmittance of the molded article A1 were measured. The total light transmittance was 61%, the spectral transmittance was 0% at 800 nm, 4% at 900 nm, and 68% at 1000 nm. Furthermore, after putting molded object A1 in the hot air oven at 100 degreeC for 24 hours, it was taken out, the external appearance observation, total light transmittance, and spectral transmittance were measured, and durability was evaluated by measuring the change with the initial stage. As a result, there was no change in appearance, and both the total light transmittance and the spectral transmittance were less than 5% from the initial value, and no abnormality was recognized.

In addition, the total light transmittance was measured using the haze meter (HGM-2DP type | mold) manufactured by Suga Shikiki Corp., and the spectral transmittance was measured using the spectrophotometer (U-3410) of the Hitachi Seisakusho company.

(Manufacture of antireflection layer)

(1) Formation of Hard Coating Layer

To a solution containing 7.8 parts of mercaptopropyltrimethoxysilane and 0.2 part of dibutyltin dilaurate in dry air, 20.6 parts of isophorone diisocyanate was added dropwise at 50 ° C over 1 hour with stirring, followed by 3 at 60 ° C. Stir for hours. After dropping 71.4 parts of pentaerythritol triacrylate over 1 hour at 30 degreeC to this, the silane compound which has a polymeric unsaturated group and an alkoxysilane group in 1 molecule by heat-stirring at 60 degreeC for 3 hours (henceforth a "silane compound ( A) "also called). Analysis of the amount of residual isocyanate in the product showed 0.1% or less, indicating that the reaction was almost quantitatively terminated.

8.7 parts of a silane compound (A) and a methyl ethyl ketone silicazol (made by Nissan Chemical Industries, Ltd., brand name: MEK-ST (number average particle diameter 0.022 micrometer, silica concentration 30%)) under nitrogen stream 91.3 parts (solid content 27.4 parts) ), A mixture of 0.2 parts of isopropanol and 0.1 parts of ion-exchanged water was stirred at 80 ° C. for 3 hours, and then 1.4 parts of methyl orthoformate ester were added, followed by heating and stirring at the same temperature for 1 hour to obtain a colorless transparent crosslinkable particle dispersion. Got it. 2 g of the dispersion was weighed into an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to obtain a solid content of 35%.

In the container which shielded ultraviolet-ray under the dry air stream, the said crosslinkable particle dispersion was made into 70 parts (24.5 parts of solid content), 20 parts of dipentaerythritol hexaacrylates, 10 parts of tricyclodecanediyl dimethylene diacrylates, and 1-hydride. The resin composition for hard-coat layer formation was obtained by stirring 1.5 parts of oxycyclohexyl phenyl ketones and 1.5 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propanone-1 for 30 minutes at room temperature.

After apply | coating the obtained resin composition using bar coating, it dried for 3 minutes in 80 degreeC hot air dryer, and irradiated with the light amount of 1 J / cm <2> using a conveyor mercury lamp, and formed the hard-coat layer.

(2) Formation of High Refractive Index Layer

The mixed liquid of 8.1 parts of the silane compound (A) obtained in (1), 90.5 parts of methyl ethyl ketone solvent zirconia sol (average particle diameter 0.01-0.05 micrometer, zirconia concentration 30%) and 0.1 parts of ion-exchange water was stirred at 60 degreeC for 3 hours. Thereafter, 1.3 parts of ortho formic acid methyl ester and 41.2 parts of methyl ethyl ketone are added, and the reaction obtained by reacting a compound having a polymerizable unsaturated group and an alkoxysilane group in one molecule with particles of zirconium by heating and stirring at the same temperature for 1 hour. A dispersion of the product was obtained.

92 parts of said dispersion liquid, 8 parts of dipentaerythritol hexaacrylates, 1.2 parts of 1-hydroxycyclohexyl phenyl ketones, and 2-methyl-1- [4- (methylthio) phenyl] which were prepared in the container which shielded the ultraviolet-ray. A high refractive index material was prepared as a uniform solution by stirring 0.8 part of -2-morpholinopropane-1-one at room temperature for 30 minutes.

The obtained high refractive index material was applied using a wire bar coating (N0.10), left in a 40 ° C. infrared drying furnace for 1 minute, and then irradiated and cured with ultraviolet rays of 0.3 J / cm 2 under an air atmosphere to obtain a high refractive index layer. Formed.

(3) Formation of Low Refractive Index Layer

After fully replacing the autoclave made of stainless steel with an internal volume 1.5 L electronic stirrer with nitrogen gas, 500 g of ethyl acetate, 75.4 g of perfluoro (propyl vinyl ether), 34 g of ethyl vinyl ether, and hydroxyethyl vinyl ether 41.6 g, 50 g of "Adecaliia NE-30" (made by Asahi Denka Kogyo Co., Ltd.) as a nonionic reactive emulsifier, "VPS-1001" (made by Wako Pure Chemical Co., Ltd.) 7.5 as azo-group containing polydimethylsiloxane. g and lauroyl peroxide 1.25 g were added, and after cooling to dry-methanol to -50 degreeC, oxygen in a system was removed again with nitrogen gas.

Then, 99.1 g of hexafluoropropylene was added to start the temperature increase. The pressure at the point where the temperature in the autoclave reached 60 ° C. showed 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued under stirring at 70 ° C. for 20 hours, and the autoclave was water-cooled to stop the reaction at the time when the pressure dropped to 1.7 × 10 ⁵ Pa. After reaching room temperature, the unreacted monomer was discharged, the autoclave was opened, and the polymer solution of 31% of solid content concentration was obtained. The obtained polymer solution was poured into a mixed solvent of methanol and water to precipitate a polymer, and then washed with methanol, and dried in vacuo at 50 ° C to obtain 220 g of a fluorine-containing olefin polymer.

10 g of the obtained fluorine-containing olefin-based polymer, 3.2 g of methoxylated methyl melamine "cymel 303" (manufactured by Mitsui Cytec Co., Ltd.) and a curing catalyst, "Caterist 4050" (manufactured by Mitsui Cytec Co., Ltd., aromatic sulfonic acid) A low refractive index material was obtained by dissolving 3.13 g of the compound active ingredient concentration (32%) in 340 g of methyl ethyl ketone of the solvent. Solid content concentration of this low refractive index material was 4.0 mass%.

The obtained low refractive index material was applied using a wire bar coating (# 3), and air dried at room temperature for 5 minutes to form a coating film. The applicability was good. Subsequently, it heated for 2 minutes at 140 degreeC using oven, and formed the low refractive index layer.

(4) Evaluation of antireflection layer

The antireflection property of the obtained anti-reflection layer with a hard coating layer was determined by a spectroscopic reflectance measuring device (magnetic spectrophotometer U-3410, manufactured by Hitachi Seisakusho Co., Ltd.) incorporating a large sample chamber integrating sphere accessory 150-09090. The reflectance was measured and evaluated in the range of wavelength 340-700 nm. That is, as a result of measuring the reflectance of the antireflection layer at each wavelength based on the reflectance of the aluminum deposited film as a reference (100%), the reflectance of light at a wavelength of 550 nm was 1% or less, and was excellent in antireflection. When the light transmittance (T%) having a wavelength of 550 nm was measured using a spectrophotometer, the light transmittance was 95% or more, and the turbidity (haze value) was measured using a haze meter. Excellent.

Further, a high refractive index layer and a low refractive index layer were laminated on the quartz plate in order to prepare an antireflection layer (without a hard coating layer) for hardness measurement. As a result of measuring the pencil hardness in the obtained antireflection layer based on JISK5400, it had sufficient hardness in 3H.

In addition, a hard coating layer, a high refractive index layer, and a low refractive index layer were sequentially laminated on the near-infrared absorbing layer to prepare an antireflection layer. As a result of performing a lattice test in accordance with JIS K5400, peeling was not observed in 100 lattice substrates. Excellent.

According to the composite functional film of the present invention, the thin layer can be made thin, which enables not only the thin and thin layer of the plasma display panel, but also the handleability thereof is good and can be directly bonded to the plasma display panel. Further, optical properties such as antireflection, shielding properties of near infrared rays and electromagnetic waves are maintained, and excellent light transmittance and visibility are obtained.

Claims (7)

(1) antireflection layer (i) a high refractive index layer containing conductive metal oxide particles, at least one selected from an alkoxysilyl group-containing compound, a hydrolyzate and a hydrolysis condensate of the compound, and (ii) a laminate having a low refractive index layer containing a fluorine-containing olefinic polymer having a polysiloxane segment, (2) The composite functional film for plasma display panels, wherein the near infrared absorbing layer has an antireflection layer and a near infrared absorbing layer that satisfy the conditions containing the norbornene-based resin. The composite function film for plasma display panel according to claim 1, further comprising a shock absorbing layer. The composite function film for plasma display panel according to claim 2, wherein the impact absorbing layer is a layer containing an elastomer. The composite function film for plasma display panel according to claim 1, further comprising an electromagnetic shielding layer. The complex function for a plasma display panel according to claim 1, wherein the norbornene-based resin constituting the near-infrared absorbing layer is a resin obtained by ring-opening polymerization of a monomer containing at least one compound represented by the following formula (1) and further hydrogenated. film. <Formula 1>

In the formula, each of R ¹ to R ⁴ independently represents an atom or group selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and R ¹ to R ⁴ At least one is a monovalent polar group containing at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, and R ¹ and R ² or R ³ and R ⁴ are bonded to each other to form an alkylidene group May be formed, R ¹ and R ² , R ³ and R ⁴ Alternatively, R ² and R ³ may be bonded to each other to form a carbocyclic ring or a heterocycle (these carbocyclic rings or heterocycles may be monocyclic, or other rings may be condensed to form a polycyclic structure). The summoned or heterocyclic ring may be an aromatic ring or a non-aromatic ring, m is an integer of 0 to 3, and p is 0 or 1. The composite function film for plasma display panel according to claim 1, wherein the antireflection layer further comprises a laminate having a hard coating layer. The composite function film for plasma display panel according to claim 1, wherein a laminate having an antireflection layer and a near infrared absorbing layer is formed on the support film.

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