JP2006235561A - Laminate having optical interference layer and antireflection film including the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which has high transparency, has a small reflectance amplitude, as a result, can prevent interference fringes on coated film appearance, is excellent in interlayer adhesiveness and, moreover, is excellent in scratch resistance. <P>SOLUTION: The laminate is provided with: an optical interference layer having a refractive index of 1.40 to 1.60 and a film thickness in the range of 70 to 200 nm; and a hard coat layer having a refractive index of 1.40 to 1.70 which is larger than that of the optical interference layer, in this order on a substrate made of polyethylene terephthalate resin. The antireflection film using the laminate has a small reflectance amplitude and, as a result, the interference fringes on coated film appearance are prevented. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminate having an optical interference layer, and in particular, a laminate having excellent adhesion between layers and having a small reflectance amplitude and, as a result, preventing interference fringes on the appearance of the laminate, and a reflection including the laminate. It relates to a prevention film.

  Currently, with the development of multimedia, various developments have been seen in various display devices (display devices). Among various types of display devices, especially those used outdoors, mainly for portable use, the improvement in visibility has become increasingly important, and even in large display devices, it is easier to see. This is a technical issue as it is required by consumers.

  Conventionally, as one means for improving the visibility of a display device, an antireflection film made of a low refractive index material is coated on a substrate of the display device, and a method of forming the antireflection film For example, a method of forming a fluorine compound thin film by a vapor deposition method is known. However, in recent years, there has been a demand for a technique capable of forming an antireflection film for a large display device at a low cost centering on a liquid crystal display device. However, in the case of the vapor deposition method, it is difficult to form a high-efficiency and uniform antireflection film on a large-area substrate, and a vacuum apparatus is required, so that the cost can be reduced. Have difficulty.

  Under such circumstances, a method of forming an antireflection film by preparing a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent and applying it to the surface of a substrate has been studied. Yes. For example, it has been proposed to apply a fluorinated alkylsilane to the surface of a substrate (see, for example, Patent Document 1 and Patent Document 2). In addition, a method of applying a fluorine-based polymer having a specific structure has been proposed (see, for example, Patent Document 3).

  In the polyester film generally used as a base material, for example, the adhesiveness to a prism lens or a hard coat mainly composed of an acrylic resin is poor, and various easy-adhesion layers are applied to the base material in order to improve the adhesiveness. Has been proposed (for example, Patent Document 4). In addition, transparent films generally have interference fringes caused by the optical path difference between the light reflected on the film surface and the light reflected on the back side of the film, and the interference fringes have a problem that they appear clearer as the transparency of the film increases. An optically easy-to-adhere film having excellent quality with no noticeable stripes has been proposed (for example, Patent Document 5).

JP 61-40845 A Japanese Examined Patent Publication No. 6-98703 Japanese Patent Application Laid-Open No. 6-1115023 JP 2001-129948 A JP 2001-71439 A

However, the conventional antireflection film made of a fluorine-based material is not sufficiently adhered to the base material, and particularly when repeatedly scratched, the antireflection film layer is peeled off. There is a problem in that dust and dust in the air adhere to the surface of the prevention film, thereby reducing visibility.
Further, the conventional antireflection film has a problem that the reflectance amplitude is large and the appearance of the coating film is glaring due to the difference in refractive index between the base material, the easy adhesion treatment layer and the hard coat layer.

The present invention has been made against the background of the above situation, and its purpose is high transparency, low reflectance amplitude, and as a result, interference fringes on the appearance of the coating can be prevented, and adhesion between layers can be prevented. Another object of the present invention is to provide a laminate having excellent scratch resistance.
Another object of the present invention includes a laminate having high transparency, low reflectance amplitude, and consequently preventing interference fringes on the appearance of the coating film, excellent adhesion between layers, and excellent scratch resistance. An object is to provide an antireflection film.

  In order to achieve the above object, the present inventors have conducted intensive research and used polyethylene terephthalate (PET) having a refractive index of 1.655 as a base material, and a hard material formed from this base material and a specific curable composition. A laminate obtained by providing a layer having a refractive index lower than that of the hard coat layer (hereinafter referred to as “optical interference layer”) formed from a specific liquid resin composition between the coat layer and the coat layer. It was found that the reflectance amplitude of the film was suppressed and interference fringes on the appearance of the coating film could be prevented, and the present invention was completed.

That is, the present invention provides the following laminate and antireflection film.
[1] On a base material made of polyethylene terephthalate resin, an optical interference layer having a refractive index of 1.40 to 1.60 and a film thickness of 70 to 200 nm, and a refractive index of 1.40 to 1 70, a hard coat layer having a refractive index larger than that of the optical interference layer in this order.
[2] A fluorine-containing olefin polymer in which the optical interference layer contains 10 mol% to 50 mol% of a structural unit derived from a monomer containing the following component (A-1) hydroxyl group:
(A-2) curable compound,
(A-3) A cured layer obtained from a liquid resin composition containing a curing catalyst and / or a radical polymerization initiator, and (A-4) a solvent. .
[3] The hard coat layer has the following component (B-1) oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. B-2) Curable compound (B-3) Radical polymerization initiator (B-4) A cured layer obtained from a liquid curable composition characterized by containing a solvent [1] ] Or the laminate according to [2].
[4] An antireflection film comprising the laminate according to any one of [1] to [3].

The laminate of the present invention has a small reflectance amplitude, and as a result, interference fringes on the appearance of the coating film are prevented, and an optical member or device using this has excellent visibility.
The laminate of the present invention has high transparency, excellent adhesion between layers, and excellent scratch resistance. Therefore, the laminate of the present invention can be advantageously used as an optical material such as an antireflection film and an optical fiber sheath material, and can be suitably used as a coating material and the like. In addition, the laminate is excellent in adhesion between layers, has high scratch resistance, and imparts a good antireflection effect, so it is extremely useful as an antireflection film, and by being applied to various display devices, The visibility can be improved.

Hereinafter, the present invention will be described in detail.
The laminate of the present invention has an optical interference layer having a refractive index of 1.40 to 1.60 and a film thickness of 10 to 400 nm on a substrate made of polyethylene terephthalate resin, and a refractive index of 1 The hard coat layer of .4 to 1.7 is provided in this order.

The structure of the laminate of the present invention will be described with reference to the drawings.
FIG. 1 shows the basic structure of the laminate of the present invention. An optical interference layer 3 is laminated on a substrate 2 made of polyethylene terephthalate resin, and a hard coat layer is further laminated thereon.
FIG. 2 shows the structure of a preferred embodiment of the laminate of the present invention. An easy adhesion layer 5 is provided on the substrate 2, and an optical interference layer 3 and a hard coat layer 4 are sequentially laminated thereon. By providing the easy-adhesion layer 5, the adhesiveness between the base material 2 and the optical interference layer becomes better.

  The refractive index of the polyethylene terephthalate resin constituting the base material 2 used in the present invention is very high as about 1.655, whereas the refractive index of the material constituting the hard coat layer 4 is generally as low as about 1.5, Due to this difference in refractive index, the amplitude of the reflectance increases, and interference fringes appear in the appearance of the laminate, impairing visibility. In the present invention, a material having a refractive index of 1.40 to 1.60 is used between the substrate 2 and the hard coat layer 4, and the optical interference layer 3 having a film thickness in the range of 10 to 400 nm is provided. Thereby, since the amplitude of the reflectance at the center wavelength (400 to 550 nm) in the visible region is suppressed, interference fringes can be prevented. A graph showing the relationship between the reflectance amplitude and the wavelength when the refractive index and film thickness of the optical interference layer 4 are varied is shown in FIG. From the graph of FIG. 3, it can be seen that the amplitude of the reflectance is small at the center wavelength in the visible region.

Next, the material of each member which comprises the laminated body of this invention is demonstrated in detail.
I. Base material The thickness of the base material formed from polyethylene terephthalate resin is usually in the range of 50 to 250 μm, preferably 80 to 190 μm. If the thickness of the substrate is too thick, there is a disadvantage that optical characteristics such as a decrease in light transmittance are impaired, and conversely, if it is too thin, there is a disadvantage that the shape cannot be maintained.

  It is preferable that an easy-adhesion layer is provided on at least the side on which the optical interference layer is laminated of the base material made of polyethylene terephthalate resin used in the present invention. By providing the easy-adhesion layer, the adhesion between the substrate and the optical interference layer becomes better.

(2) Resin composition for forming an easy-adhesion layer Examples of materials constituting the easy-adhesion layer include polyester resins and polyurethane resins.
The easy-adhesion layer may be provided by applying a resin composition for forming an easy-adhesion layer on a substrate, but a commercially available product in which the easy-adhesion layer is formed in advance can also be used. Specific examples of such commercially available products include, for example, single-sided easily-adhesive polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., film thickness: 188 μm), O300E (manufactured by Mitsubishi Polyester Resin Co., Ltd., 188 μm).

II. Optical interference layer (1) Liquid resin composition for forming optical interference layer The optical interference layer in the laminate of the present invention has curability, (A-1) a fluorine-containing olefin polymer, (A-2) It is a cured film formed by curing a liquid resin composition containing a) curable compound, (A-3) a curing catalyst and / or a radical polymerization initiator, and (A-4) a solvent.
The optical interference layer may have the function of an easy adhesion layer, that is, the function of improving the adhesion between the base material and the hard coat layer.

Hereinafter, each component of the liquid resin composition for forming an optical interference layer will be described.
(A-1) Fluorine-containing olefin polymer The fluorine-containing olefin polymer used in the present invention contains 10 mol% to 50 mol% of a structural unit derived from a monomer containing a hydroxyl group. The fluorine-containing olefin polymer preferably has a fluorine content of 30% by mass or more and a number average molecular weight in terms of polystyrene of 5000 or more.

  Further, the fluorine-containing olefin polymer preferably has a fluorine content of 30% by mass or more, more preferably 40 to 60% by mass, and the number average molecular weight in terms of polystyrene obtained by gel permeation chromatography, Preferably it is 5000 or more, More preferably, it is 10000-500000. Here, the fluorine content is a value measured by the alizarin complexone method, and the number average molecular weight is a value when tetrahydrofuran is used as a developing solvent.

  The (A-1) fluorine-containing olefin polymer in the present invention comprises (a) a fluorine-containing olefin compound (hereinafter referred to as “(a) component”), (b) a hydroxyl group copolymerizable with this (a) component. A monomer compound (hereinafter referred to as “component (b)”), and (d) a reactive emulsifier (hereinafter referred to as “component (d)”), and / or (e) It can be obtained by reacting a monomer compound other than the component (b) copolymerizable with the component (a).

  Examples of the fluorine-containing olefin compound as component (a) include compounds having at least one polymerizable unsaturated double bond and at least one fluorine atom. Specific examples thereof include, for example, (1) Fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene; (2) alkyl perfluoro vinyl ethers or alkoxyalkyl perfluoro vinyl ethers; (3) perfluoro (methyl vinyl ether) Perfluoro (alkyl vinyl ethers) such as perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); (4) perfluoro (propoxypropyl vinyl ether) ) Perfluoro (alkoxyalkyl vinyl ether) such as; other can be exemplified. These compounds can be used alone or in combination of two or more. Among these, hexafluoropropylene, perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether is particularly preferable, and a combination thereof is preferably used.

  Examples of the monomer compound containing a hydroxyl group as component (b) include (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl. Hydroxyl group-containing vinyl ethers such as 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) acrylate; These compounds can be used alone or in combination of two or more.

  Preferred combinations of the above components (a) and (b) are, for example, (1) fluoroolefin / hydroxyl group-containing alkyl vinyl ether (2) fluoroolefin / perfluoro (alkyl vinyl ether) / hydroxyl group-containing alkyl vinyl ether (3) fluoroolefin / Perfluoro (alkoxyalkyl) vinyl ether / hydroxyl group-containing alkyl vinyl ether (4) fluoroolefin / (perfluoroalkyl) vinyl ether / hydroxyl group-containing alkyl vinyl ether (5) fluoroolefin / (perfluoroalkoxyalkyl) vinyl ether / hydroxyl group-containing alkyl vinyl ether.

  In the fluorine-containing olefin polymer, the structural unit derived from the component (a) is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, and particularly preferably 30 to 60 mol%. When the proportion of the structural unit derived from the component (a) is less than 20 mol%, the fluorine content in the resulting fluorine-containing olefin polymer tends to be excessive, and the cured product of the resulting liquid resin composition has a sufficient refractive index. It is hard to be low. On the other hand, when the proportion of the structural unit derived from the component (a) exceeds 70 mol%, the solubility of the resulting fluorine-containing olefin polymer in the organic solvent is significantly reduced, and the resulting liquid resin composition is: The transparency and adhesion to the substrate are small.

  In the fluorine-containing olefin polymer, the structural unit derived from the component (b) is 10 to 50 mol%. Preferably it is 13 mol% or more, More preferably, it exceeds 20 mol% and is 21 mol% or more, Preferably it is 45 mol% or less, More preferably, it is 35 mol% or less. By constituting the liquid resin composition using such a fluorine-containing olefin polymer containing a predetermined amount of the component (b), it is possible to realize good scratch resistance and dust wiping in the cured product. it can. On the other hand, when the proportion of the structural unit derived from the component (b) is less than 10 mol%, the fluorine-containing olefin polymer has poor solubility in an organic solvent, and when it exceeds 50 mol%, the liquid resin composition The cured product of the product has deteriorated optical properties such as transparency and low reflectance.

  In the present invention, in addition to the components (a) and (b), it is preferable to use a reactive emulsifier as a monomer component as the component (d). By using this component (d), good coating properties and leveling properties can be obtained when using a fluorine-containing olefin polymer as a coating agent. As the reactive emulsifier, it is particularly preferable to use a nonionic reactive emulsifier. Specific examples of the nonionic reactive emulsifier include compounds represented by the following general formula (3) or general formula (4).

式中、ｎ、ｍ及びｓは、繰り返し単位を示し、ｎ＝１〜２０、ｍ＝０〜４、ｓ＝３〜５０である。

In formula, n, m, and s show a repeating unit, and are n = 1-20, m = 0-4, s = 3-50.

式中、ｍ及びｓは、一般式（３）と同様である。Ｒ^３は、直鎖状でも分岐状でもよいアルキル基であり、好ましくは炭素数１〜４０のアルキル基である。

In the formula, m and s are the same as those in the general formula (3). R ³ is an alkyl group which may be linear or branched, and is preferably an alkyl group having 1 to 40 carbon atoms.

  In the fluorine-containing olefin polymer, the proportion of the structural unit derived from the component (d) is preferably 0 to 10 mol%, more preferably 0.1 to 5 mol%. When this ratio exceeds 10 mol%, the liquid resin composition obtained becomes sticky, making it difficult to handle, and when used as a coating agent, the moisture resistance decreases.

(D) The preferable combination in the case of containing a component is as follows.
(1) fluoroolefin / alkyl vinyl ether / hydroxyl group-containing vinyl ether // nonionic reactive emulsifier, (2) fluoroolefin / perfluoro (alkyl vinyl ether) / alkyl vinyl ether / hydroxyl group-containing vinyl ether // nonionic reactive emulsifier, (3) fluoro Olefin / perfluoro (alkoxyalkyl) vinyl ether / alkyl vinyl ether / hydroxyl group-containing vinyl ether / nonionic reactive emulsifier, (4) fluoroolefin / (perfluoroalkyl) vinyl ether / alkyl vinyl ether / hydroxyl group-containing vinyl ether / nonionic reactive emulsifier, (5 ) Fluoroolefin / (perfluoroalkoxyalkyl) vinyl ether / alkyl vinyl ether / hydroxyl group-containing vinyl ether / nonionic reactive emulsifier.

  As a polymerization mode for producing the fluorine-containing olefin polymer used in the present invention, any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method using a radical polymerization initiator may be used. As the polymerization operation, an appropriate one can be selected from batch operation, semi-continuous operation or continuous operation.

  (E) As a monomer compound other than the component (b) that can be copolymerized with the component (a), (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, Alkyl vinyl ethers or cycloalkyl vinyl ethers such as 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; (2) vinyl acetate , Vinyl carboxylates such as vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl stearate; ) Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n- (Meth) acrylic acid esters such as propoxy) ethyl (meth) acrylate; (4) carboxyl group-containing monomer compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. The thing which does not contain a hydroxyl group can be mentioned.

  In the fluorine-containing olefin polymer, the proportion of the structural unit derived from the component (e) is preferably 0 to 70 mol%, more preferably 5 to 35 mol%. When this ratio exceeds 70 mol%, the resulting liquid resin composition becomes sticky, so that handling becomes difficult, and moisture resistance decreases when used as a coating agent.

  Examples of the radical polymerization initiator include (1) diacyl peroxides such as acetyl peroxide and benzoyl peroxide; (2) ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; (3) hydrogen peroxide, hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide; (4) dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide and dilauroyl peroxide; (5) tert- Peroxyesters such as butyl peroxyacetate and tert-butylperoxypivalate; (6) Azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile; (7) ammonium persulfate , Sodium persulfate, persulfates such as potassium persulfate; Other can be exemplified.

  Specific examples other than the above radical polymerization initiator include, for example, perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (Perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro 2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane And iodine-containing fluorine compounds. The iodine-containing fluorine compound can be used alone or in combination with the organic peroxide, azo compound or persulfate.

  The polymerization reaction for obtaining the fluorine-containing olefin polymer is preferably performed in a solvent system using a solvent. Examples of preferable organic solvents include (1) esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and 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; be able to. Further, if necessary, alcohols, aliphatic hydrocarbons and the like can be mixed and used.

  The fluorine-containing olefin polymer obtained as described above may be able to use the reaction solution obtained by the polymerization reaction as it is as a liquid resin composition, but it is suitable for the polymerization reaction solution. Post-processing is also free. As this post-treatment, for example, a general method represented by a purification method in which a polymerization reaction solution is added dropwise to an insolubilizing solvent for the fluorine-containing olefin polymer made of alcohol or the like to solidify the fluorine-containing olefin polymer. Reprecipitation treatment can be performed, and then the solution of the fluorine-containing olefin polymer can be prepared by dissolving the obtained solid copolymer in a solvent. Moreover, what removed the residual monomer from the polymerization reaction solution can also be used as a solution of a fluorine-containing olefin polymer as it is.

(A-2) Curable compound The curable compound used in the present invention may be either thermosetting or active energy ray curable. Examples of the thermosetting compound used in the present invention include various amino compounds, various hydroxyl-containing compounds such as pentaerythritol, polyphenol, and glycol, and others.

  The amino compound used as the thermosetting compound is an amino group capable of reacting with a hydroxyl group present in the fluorine-containing olefin polymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total 2 More specifically, examples of the compound include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine obtained by reacting melamine and formaldehyde under basic conditions, alkoxylated methylmelamine, or a derivative thereof is preferable, and particularly, good storage stability can be obtained in a liquid resin composition. In view of the point and good reactivity, alkoxylated methylmelamine is preferable. There are no particular limitations on the methylolated melamine and the alkoxylated methylmelamine used as the thermosetting compound. For example, the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun) It is also possible to use various resinous materials obtained.

  In addition to urea, examples of the urea compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, and alkoxylated methyluron. And also about compounds, such as a urea derivative, the use of the various resinous materials described in said literature is possible.

  Specific examples of the active energy ray-curable compound that can be used in the present invention are listed. Examples of the hydroxyl group-containing (meth) acrylic esters include hydroxyl group-containing monofunctional (meth) acrylic esters and hydroxyl group-containing polyfunctional (meth) acrylic esters. Specific examples of the hydroxyl group-containing monofunctional (meth) acrylic esters include hydroxyalkyl (meth) acrylates having 2 to 12 carbon atoms such as hydroxyethyl (meth) acrylate, ethylene glycol mono (meth) acrylate, neopentyl glycol mono ( (Meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, bis (2-hydroxyethyl) isocyanurate mono (meth) acrylate, and starting alcohols thereof Mono (meth) acrylates to which (poly) ethylene oxide or (poly) propylene oxide having 2 to 10 carbon atoms is added, and (poly) ethylene having 2 to 10 carbon atoms per amide bond of isocyanuric acid Oxide or (poly) mono (meth) acrylates of propylene oxide are added and the like.

  As polyfunctional (meth) acrylates, pentaerythritol tri (meth) acrylate, pentaerythritol monoethylene oxide or tripropylene oxide adduct tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) (Poly) ethylene oxide having 2 to 8 carbon atoms per hydroxyl group of acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, glycerin di (meth) acrylate, and these starting alcohols or ( Poly (meth) acrylates to which poly) propylene oxide is added, (poly) ethylene oxide or (poly) propyleneoxy having 2 to 4 carbon atoms per amide bond of isocyanuric acid There may be mentioned di (meth) acrylates, and oligo epoxy (meth) acrylates obtained by adding.

  Among these hydroxyl group-containing (meth) acrylic esters, those having a hydroxyl value of 110 mgKOH / g or more, for example, pentaerythritol tri (meth) acrylate, regardless of monofunctional or polyfunctional, are used from the viewpoint of scratch resistance. preferable.

  (A-1) The usage-amount of the (A-2) curable compound with respect to 100 mass parts of fluorine-containing olefin type polymers needs to be 15-300 mass parts, Preferably it is 20-250 mass parts. . (A-2) If the amount of the curable compound used is too small, the durability of the thin film formed by the resulting liquid resin composition may be insufficient. If the amount exceeds 300 parts by mass, the cured product will be It may be brittle.

(A-1) Reaction of fluorine-containing olefin polymer and (A-2) thermosetting compound is, for example, (A-2) thermosetting in a solution of an organic solvent in which fluorine-containing olefin polymer is dissolved. It may be carried out while adding a functional compound and homogenizing the reaction system by heating, stirring or the like for an appropriate time. 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. If the heating temperature is less than 30 ° C, the reaction proceeds very slowly. If the heating temperature exceeds 150 ° C, in addition to the intended reaction, a crosslinking reaction is caused by the reaction between methylol groups and alkoxylated methyl groups in the thermosetting compound. Is generated and a gel is formed, which is not preferable. The progress of the reaction is quantitative by measuring the amount of methylol group or alkoxylated methyl group by infrared spectroscopic analysis or by collecting the dissolved polymer by reprecipitation method and measuring the increase. Can be confirmed.

(A-3) Curing catalyst and / or radical polymerization initiator (i) Curing catalyst Examples of the curing catalyst used in the present invention include a thermal acid generator or a photosensitive acid generator. The thermal acid generator is a substance that can accelerate the curing reaction when the coating film or the like of the liquid resin composition is heated and cured, and the heating condition is improved to a milder one. It is a substance that can There is no restriction | limiting in particular as this thermal acid generator, The above-mentioned various acids currently used as a hardening | curing agent for general urea resin, melamine resin, etc., and its salts can be utilized. Specific examples include, for example, various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid, and maleic acid, various aromatic carboxylic acids and salts thereof such as benzoic acid and phthalic acid, Examples thereof include alkylbenzenesulfonic acid and its ammonium salt, various metal salts, phosphoric acid and phosphoric acid esters of organic acids.

  The photosensitive acid generator used in the present invention imparts photosensitivity to the coating film of the liquid resin composition, and allows the coating film to be photocured by, for example, irradiation with radiation such as light. It is a substance. Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt; (2) β-ketoester, β-sulfonylsulfone and these Sulfone compounds such as α-diazo compounds of (3); sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfones represented by the following general formula (1) Imide compounds; (5) Diazomethane compounds represented by the following general formula (6);

式中、Ａは、アルキレン基、アリレーン基、アルコキシレン基等の２価の基を示し、Ｒ^４は、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In the formula, A represents a divalent group such as an alkylene group, an arylene group, or an alkoxylen group, and R ⁴ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. Show.

式中、Ｒ^１及びＲ^２は、互いに同一でも異なってもよく、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In the formula, R ¹ and R ² may be the same as or different from each other, and represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

  The photosensitive acid generator can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generator. The use ratio of the photosensitive acid generator is preferably 0 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the fluorine-containing olefin polymer in the liquid resin composition. When this ratio is excessive, the strength of the cured film becomes inferior and the transparency is also lowered, which is not preferable.

  (A-3) The blending amount of the curing catalyst 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 composition excluding the organic solvent. . An excessive amount of the curing catalyst agent is not preferable because sufficient mechanical strength cannot be obtained. If this ratio is excessive, the storage stability of the liquid resin composition is inferior, and the catalyst acts as a plasticizer in the cured film, so that sufficient mechanical strength cannot be obtained, which is not preferable.

(Ii) Radical polymerization initiator Examples of the radical polymerization initiator used in the present invention include a compound that thermally generates active radical species (thermal polymerization initiator), and an active radical species by irradiation with radiation (light). Examples of the compounds to be generated (radiation (light) polymerization initiators) that are widely used can be given.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- ( 1-methylvinyl) phenyl) propanone) and the like.

  As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24- 61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B Etc.

  The amount of the radical polymerization initiator used as necessary in the present invention is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the total composition excluding the organic solvent, 10 parts by weight is more preferable. If it is less than 0.01 part by weight, the hardness when it is a cured product may be insufficient, and if it exceeds 20 parts by weight, the inside (lower layer) may not be cured when it is a cured product.

When hardening the curable composition used by this invention, a photoinitiator and a thermal-polymerization initiator can be used together as needed.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

(A-4) Solvent The liquid resin composition for forming an optical interference layer used in the present invention contains a solvent as an essential component. The solvent of the liquid resin composition is usually a fluorine-containing olefin-based solvent. It is obtained as a solution using the solvent used for the production of the polymer or the solvent used for the reaction between the fluorine-containing olefin polymer and the thermosetting compound, and thus contains the solvent as it is.

  Moreover, a solvent can be separately added and blended for the purpose of improving the coating properties of the liquid resin composition and other purposes. Preferable solvents contained in the liquid resin composition for forming an optical interference layer used in the present invention include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate. Furthermore, in the solution of the liquid resin composition of the present invention, a solvent that cannot dissolve the fluorine-containing olefin polymer, for example, a poor solvent such as water, alcohols, ethers, etc., the fluorine-containing olefin polymer is precipitated. It can be used in combination as long as it is not. Thereby, the solution of the fluorine-containing olefin polymer may have good storage stability and preferable coating properties. Examples of such poor solvents include ethyl alcohol, isopropyl alcohol, tert-butyl alcohol and the like.

  The reaction between (A-1) the fluorine-containing olefin polymer and (A-2) the thermosetting compound is the same as the organic solvent used in the production of the fluorine-containing olefin polymer, for example. It is preferable to use it. In the present invention, the reaction solution obtained by the fluorine-containing olefin polymer and the thermosetting compound thus obtained can be used as a solution for the liquid resin composition as it is, and various additives can be used as necessary. It can also be used after blending.

  The compounding quantity of the (B-4) organic solvent in the composition of this invention is 70-99 mass% normally in all the compositions, and 90-97 mass% is preferable. If it exists in the range of 70-99 mass%, coating property is favorable.

Other additives The liquid resin composition for forming an optical interference layer used in the present invention is intended to improve the coating properties of the liquid resin composition and the properties of the thin film after curing, and to impart photosensitivity to the coating film. For example, various polymers and monomers having a hydroxyl group, colorants such as pigments or dyes, stabilizers such as anti-aging agents and ultraviolet absorbers, thermal acid generators, photosensitive acid generators, surfactants, polymerization Various additives such as an inhibitor and 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, without reducing the transparency after curing of the liquid resin composition. In addition, it is preferable to select and use one that dissolves uniformly in the solution.

(I) Polymer having hydroxyl group Examples of the polymer having a hydroxyl group that can be blended in the liquid resin composition for forming an optical interference layer used in the present invention include a hydroxyl group-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate. Examples of the polymer obtained by copolymerizing a monomer, a novolak resin, or a resole resin include a resin having a known phenol skeleton.

(Ii) Colorant such as pigment or dye Examples of the colorant that can be blended in the liquid resin composition for forming an optical interference layer used in the present invention include (1) alumina white, clay, barium carbonate, barium sulfate. (2) Inorganic pigments such as zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black; (3) Brilliant Carmine 6B, Permanent Red 6B , Permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green and other organic pigments; (4) basic dyes such as magenta and rhodamine; (5) direct dyes such as direct scarlet and direct orange; Acid dyes such as yellow; and the like.

(Iii) Stabilizers such as anti-aging agents and UV absorbers As anti-aging agents and UV absorbers that can be blended in the liquid resin composition for forming an optical interference layer used in the present invention, known ones are used. can do.
Specific examples of the antioxidant include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone Monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl) -4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole, and the like.

  Specific examples of the UV absorber include, for example, salicylic acid UV absorbers represented by phenyl salicylate, benzophenone UV absorbers such as dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and benzotriazole UV absorbers. Ultraviolet absorbers used as additives for various plastics such as cyanoacrylate-based ultraviolet absorbers can be used.

(V) Surfactant In the liquid resin composition for forming an optical interference layer used in the present invention, a surfactant can be blended for the purpose of improving the coating property of the liquid resin composition. As this surfactant, known ones can be used. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used. In particular, a cationic surfactant is preferably used so that the cured film has excellent strength and good optical properties. Furthermore, a quaternary ammonium salt is preferable, and among them, the use of a quaternary polyether ammonium salt is particularly preferable because dust wiping property is further improved. Examples of cationic surfactants that are quaternary polyether ammonium salts include Adekacol CC-15, CC-36, and CC-42 manufactured by Asahi Denka Kogyo Co., Ltd. The use ratio of the surfactant is preferably 5 parts by mass or less with respect to 100 parts by mass of the liquid resin composition.

(Vi) Polymerization inhibitor Examples of the thermal polymerization inhibitor that can be incorporated into the liquid resin composition for forming an optical interference layer used in the present invention include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, and monobenzyl. Ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] Ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and the like. This thermal polymerization inhibitor is preferably used in an amount of 5 parts by mass or less with respect to 100 parts by mass of the liquid resin composition.

(2) Optical interference layer (cured film)
When forming an optical interference layer (cured film) from the liquid resin composition for forming an optical interference layer used in the present invention, it is preferable to coat the base material (applied member). As such a coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, an ink jet method, or the like can be used.

  The means for curing the liquid resin composition for forming an optical interference layer is not particularly limited, but is preferably heated, for example. In this case, it is preferable to heat at 30 to 200 ° C. for 1 to 180 minutes. By heating in this way, a cured film excellent in antireflection properties can be obtained more efficiently without damaging the substrate and the formed cured film. Preferably, the heating is performed at 50 to 180 ° C. for 2 to 120 minutes, more preferably at 80 to 150 ° C. for 2 to 60 minutes.

It can also be cured by irradiation with radiation. In this case, for example, an ultraviolet irradiation device (a metal halide lamp, a high-pressure mercury lamp, or the like) can be used under a light irradiation condition of 0.001 to 10 J / cm ² , but the irradiation condition is not limited to this. . 0.01-5 J / cm ² is more preferable, and 0.1-3 J / cm ² is more preferable.

  The cured film is cured by, for example, (A-2) when a melamine compound is used as the thermosetting compound, or the amount of methylol group or alkoxylated methyl group of the melamine compound is analyzed by infrared spectroscopy, or The gelation rate can be quantitatively confirmed by measuring using a Soxhlet extractor.

  The coating film of the liquid resin composition for forming an optical interference layer formed by coating may give a heat history due to heating, in particular, in order to form a cured film having excellent optical properties and durability. preferable. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time, and the desired cured film is formed. However, in practice, curing by heating is effective in reducing the required time. Is. Moreover, the curing reaction can be further promoted by adding a thermal acid generator as a curing catalyst. The curing catalyst is not particularly limited, and the above-mentioned various acids and salts used as curing agents for general urea resins and melamine resins can be used. In particular, ammonium salts are preferably used. Can do. The heating conditions for the curing reaction can be selected as appropriate, but the heating temperature needs to be equal to or lower than the heat resistant limit temperature of the substrate to be coated.

  The refractive index of the optical interference layer in the laminate of the present invention is in the range of 1.40 to 1.60, preferably 1.40 to 1.55, more preferably 1.42 to 1.50. It is. If it is out of this range, there arises a disadvantage that the interference fringe prevention property does not appear. Further, the refractive index of the optical interference layer must be lower than the refractive index of the hard coat layer in order to exhibit interference fringe prevention properties.

  The thickness of the optical interference layer is in the range of 70 to 200 nm, preferably 100 to 200 nm, and more preferably 120 to 180 nm. If it is out of this range, the reflectance amplitude in the optimum wavelength region cannot be suppressed, and as a result, there arises a disadvantage that the interference fringe prevention property does not appear.

III. Hard coat layer (1) Curable composition for forming hard coat layer The curable composition for forming the hard coat layer constituting the laminate of the present invention comprises (B-1) oxide particles of a specific element ( Hereinafter referred to as “metal oxide particles (B-1)”), (B-2) a curable compound, (B-3) a radical polymerization initiator, and (B-4) a solvent. It is characterized by doing.

  Hereafter, each structural component of the curable composition for hard-coat formation used by this invention is demonstrated concretely.

1. Metal oxide particles (B-1)
From the viewpoint of the colorlessness of the cured film of the resulting curable composition for forming a hard coat layer, the oxide particles (B-1) used in the present invention are silicon, aluminum, zirconium, titanium, zinc, germanium, indium, It is an oxide particle of at least one element selected from the group consisting of tin, antimony and cerium.

  Examples of these metal oxide particles (B-1) include silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. And the like. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These can be used singly or in combination of two or more. Furthermore, it is preferable that oxide particle (B-1) is a powder form or solvent dispersion | distribution sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the metal oxide particles (B-1) 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. If the number average particle diameter exceeds 2 μm, the transparency when cured is reduced, or the surface state when coated is likely to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

As a product marketed as silicon oxide particles (for example, silica particles), for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, 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 and the like can be mentioned. Moreover, as a powder silica, Nippon Aerosil Co., Ltd. product name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product name: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd., trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade name: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd., trade names: SG flakes, and the like.

  Moreover, as an aqueous dispersion product of alumina, product names manufactured by Nissan Chemical Industries, Ltd .: Alumina sol-100, -200, -520; As an isopropanol dispersion product of alumina, product names manufactured by Sumitomo Osaka Cement Co., Ltd .: AS- As a toluene dispersion product of alumina, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: AS-150T; As a zirconia toluene dispersion product, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: HXU-110JC; Product name: Celnax; Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and other powder and solvent dispersion products are manufactured by C-Chemicals Co., Ltd. Name: Nanotech; Antimony-doped tin oxide aqueous dispersion sol manufactured by Ishihara Sangyo Co., Ltd. Product name: SN-100 ; The ITO powder, Mitsubishi Materials Co., Ltd. product; a cerium oxide aqueous dispersion, Taki Chemical Co., trade name: Nidoraru like.

The metal oxide particles (B-1) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape. The specific surface area of the oxide particles (B-1a) (by BET method using nitrogen) is preferably in the 10~1,000m ² / g, more preferably, at 100 to 500 m ² / g is there. These oxide particles (B-1a) can be used in a state of being dispersed in a dry powder, water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, use of a solvent-dispersed sol of an oxide is preferable in applications that require excellent transparency in a cured product.
Further, the metal oxide particles (B-1) used in the present invention are organic compounds (B-1b) containing a polymerizable unsaturated group (preferably, a specific organic further containing a group represented by the formula (7) described later) Reactive particles surface-treated with a compound) may be used.

(2) Organic compound (B-1b)
The organic compound (B-1b) used in the present invention is a compound having a polymerizable unsaturated group, and is preferably an organic compound containing a group represented by the following formula (2). Further, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH—] group. It is preferable that at least 1 of these is included. Moreover, it is preferable that this organic compound (B-1b) is a compound which has a silanol group in a molecule | numerator, or a compound which produces | generates a silanol group by hydrolysis.

［式（２）中、Ｕは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｖは、Ｏ又はＳを示す。］

[In Formula (2), U represents NH, O (oxygen atom) or S (sulfur atom), and V represents O or S. ]

(I) Polymerizable unsaturated group Although there is no restriction | limiting in particular as a polymerizable unsaturated group contained in an organic compound (B-1b), For example, an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a butadienyl group, a styryl group Preferred examples include ethynyl group, cinnamoyl group, maleate group, and acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (2) The group [—UC— (V) —NH—] represented by the formula (2) contained in the organic compound is specifically represented by [—O—C ( = O) -NH-], [-O-C (= S) -NH-], [-S-C (= O) -NH-], [-NH-C (= O) -NH-], Six types of [—NH—C (═S) —NH—] and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [—UC (═V) —NH—] represented by the formula (2) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion and heat resistance to adjacent layers such as materials and high refractive index layers.

(Iii) Silanol group or group that generates a silanol group by hydrolysis The organic compound (B-1b) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. Examples of the compound that generates such a silanol group include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. A compound having a group bonded thereto, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the oxide particles (Aa) by a condensation reaction that occurs following a condensation reaction or hydrolysis.

(Iv) Preferred Embodiment As a preferred specific example of the organic compound (B-1b), for example, a compound represented by the following formula (7) can be mentioned.

In the formula (7), R ⁶ and R ⁷ may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ⁶ O) _j R ⁷ _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ⁸ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
R ⁹ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
R ¹⁰ is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  Specific examples of the compound represented by the formula (7) include compounds represented by the following formulas (8-1) and (8-2).

［式（８−１）及び（８−２）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。「Ｍｅ」は、メチル基を示す。］

[In the formulas (8-1) and (8-2), “Acryl” represents an acryloyl group. “Me” represents a methyl group. ]

  For the synthesis of the organic compound (B-1b) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent.

(3) Reactive Particles An organic compound (B-1b) having a silanol group or a group that generates a silanol group by hydrolysis is mixed with the metal oxide particles (B-1), hydrolyzed, and bonded together. Here, the bond includes not only a covalent bond but also a non-covalent bond such as physical adsorption. The ratio of the organic polymer component, that is, the hydrolyzable silane hydrolyzate and condensate in the obtained reactive particles is usually as a constant value of mass reduction% when the dry powder is completely burned in air. For example, it can be determined by thermal mass spectrometry from room temperature to usually 800 ° C. in air.

  The amount of the organic compound (B-1b) bound to the metal oxide particles (B-1) is 100 masses of reactive particles (the total of the metal oxide particles (B-1) and the organic compound (B-1b)). % Is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 1% by mass or more. When the binding amount of the organic compound (B-1b) bound to the metal oxide particles (B-1) is less than 0.01% by mass, the dispersibility of the reactive particles in the composition is not sufficient, and the resultant is obtained. The cured product may not have sufficient transparency and scratch resistance. Moreover, the compounding ratio of the metal oxide particles (B-1) in the raw material during the production of the reactive particles is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass. The content of the metal oxide particles (B-1) constituting the reactive particles is preferably 65 to 95% by mass of the reactive particles.

  The blending (content) amount of the metal oxide particles (B-1) or reactive particles in the curable composition is preferably 5 to 90% by mass, with the total amount of the composition excluding the organic solvent being 100% by mass, 80% by mass is more preferable. When it is less than 5% by mass, the hardness of the cured film is insufficient, and when it exceeds 80% by mass, the film formability may be insufficient. The amount of the reactive particles means a solid content, and when the reactive particles are used in the form of a dispersion, the amount of the reactive particles does not include the amount of the dispersion medium.

2. Curable compound (B-2)
Component (B-2) used in the present invention is a curable compound. This compound (B-2) is suitably used for increasing the refractive index of the cured product and improving the chemical resistance of the laminate. The curable compound (B-2) may be a thermosetting compound or an active energy ray curable compound.

(I) Thermosetting compound Although it does not specifically limit as a thermosetting compound, The melamine compound which does not have a polymerizable unsaturated group is preferable, and it is preferable that it is a melamine compound specifically shown to following formula (9). .

［式（９）中、Ｘは、それぞれ独立に、水素、又は炭素数１〜１０のアルキル基を示し、Ｙは、それぞれ独立に、水素、炭素数１〜１０のアルキル基、又は下記式（１０）で示す一価の有機基を示し、ｎは、１〜２０の整数である。］

[In Formula (9), each X independently represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and each Y independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or the following formula ( The monovalent organic group shown by 10) is shown, and n is an integer of 1-20. ]

［式（１０）中、Ｘは、それぞれ独立に、水素、又は炭素数１〜１０のアルキル基を示す。］

[In Formula (10), X shows each independently hydrogen or a C1-C10 alkyl group. ]

The alkyl group having 1 to 10 carbon atoms represented by X and Y in the formula (9) and the formula (10) is linear or branched such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an isobutyl group. An alkyl group can be mentioned. Preferably, it is a C1-C5 lower alkyl group.
X in Formula (9) and Formula (10) is preferably a methyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
X in the formula (9) is preferably a methyl group because of excellent curability.
Y in the formula (9) is preferably a methyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, or an organic group of the formula (10).

  As a commercial item of such a thermosetting compound (B-2), Mitsui Cytec Co., Ltd. product name: Cymel 238, XV805, XM2819, Cymel 303; Sanwa Chemical Co., Ltd., Nicarak E-1201, etc. Can be mentioned.

  The number average molecular weight of the thermosetting compound (B-2) used in the present invention is preferably 300 to 20,000. More preferably, it is 300-5,000. If it is less than 500, chemical resistance of the resulting laminate may be insufficient, and if it exceeds 20,000, coatability may be insufficient.

  A thermosetting compound (B-2) may mix and use 2 or more types. In the case where the thermosetting compound (B-2) is a compound represented by the formula (9), two or more types different in X, Y or n may be used.

In particular, in the melamine compound having no polymerizable unsaturated group as the component (B-2), it is preferable that at least 25 mol% of X and Y which is a hydrogen or alkyl group is an isobutyl group. When the content of isobutyl group is 25 mol% or more, the friction resistance is excellent.
More preferably, 40 mol% or more is an isobutyl group.

  The content of the thermosetting compound (B-2) used in the present invention is preferably 0.01 to 50% by weight, more preferably 1 to 40% based on 100% by mass of the total composition excluding the organic solvent. % By weight. If it is less than 0.01% by weight, the chemical resistance of the laminate may be inferior, and if it exceeds 50% by weight, the hardness of the cured product may be insufficient.

(Ii) Active energy ray-curable compound The active energy ray-curable compound (B-2) used in the present invention is a compound having a polymerizable unsaturated group. This compound is suitably used for enhancing the film formability of the composition and improving the scratch resistance of the cured product of the curable composition for forming a hard coat layer used in the present invention. Examples of the active energy ray-curable compound include a hydroxyl group-containing melamine acrylate, a hydroxyl group-containing (meth) acrylic ester, and a hydroxyl group-containing vinyl compound. In order to improve scratch resistance, a hydroxyl group-containing compound can be used. (Meth) acrylic esters are preferred.

Hereinafter, specific examples of the active energy ray-curable compound used in the present invention are listed.
Examples of the hydroxyl group-containing (meth) acrylic esters include hydroxyl group-containing monofunctional (meth) acrylic esters and hydroxyl group-containing polyfunctional (meth) acrylic esters. Specific examples of the hydroxyl group-containing monofunctional (meth) acrylic esters include hydroxyalkyl (meth) acrylates having 2 to 12 carbon atoms such as hydroxyethyl (meth) acrylate, ethylene glycol mono (meth) acrylate, neopentyl glycol mono ( (Meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, bis (2-hydroxyethyl) isocyanurate mono (meth) acrylate, and starting alcohols thereof Mono (meth) acrylates to which (poly) ethylene oxide or (poly) propylene oxide having 2 to 10 carbon atoms is added, and (poly) ethylene having 2 to 10 carbon atoms per amide bond of isocyanuric acid Oxide or (poly) mono (meth) acrylates of propylene oxide are added and the like.
As polyfunctional (meth) acrylates, pentaerythritol tri (meth) acrylate, pentaerythritol monoethylene oxide or tripropylene oxide adduct tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) (Poly) ethylene oxide having 2 to 8 carbon atoms per hydroxyl group of acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, glycerin di (meth) acrylate, and these starting alcohols or ( Poly (meth) acrylates to which poly) propylene oxide is added, (poly) ethylene oxide or (poly) propyleneoxy having 2 to 4 carbon atoms per amide bond of isocyanuric acid There may be mentioned di (meth) acrylates, and oligo epoxy (meth) acrylates obtained by adding.
Among these hydroxyl group-containing (meth) acrylic esters, those having a hydroxyl value of 110 mgKOH / g or more, for example, pentaerythritol tri (meth) acrylate, regardless of monofunctional or polyfunctional, are used from the viewpoint of scratch resistance. preferable.

As a commercial item of hydroxyl-containing (meth) acrylic esters, for example, Toagosei Co., Ltd. product name: Aronix M-400, M-305, M-215, Nippon Kayaku Co., Ltd. product name: PET- 30 (PET-30 is a mixture of pentaerythritol triacrylate as component (C) and pentaerythritol tetraacrylate as component (F) described later in a weight ratio of 60:40), manufactured by Kyoeisha Chemical Co., Ltd. Product names: Light acrylate PE-3A, epoxy ester M-600A, 40EM, 70PA, 200PA, 1600A, 80MFA, 3002M, 3002A, 3000M, 3000A, 200EA, 400EA, and the like.

  Examples of the hydroxyl group-containing vinyl compounds include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, Examples thereof include hydroxyl group-containing vinyl ethers such as diethylene glycol monovinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like. Examples of commercially available hydroxyl group-containing vinyl compounds include HEVE, HBVE, Maruzen Petrochemical Co., Ltd. HEVE, HBVE, and DEGV manufactured by Nippon Carbide Industries.

［式（５）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］ Moreover, oligomers, such as urethane (meth) acrylate, can also be used as an active energy ray hardening compound. Such urethane (meth) acrylate is not particularly limited, and examples thereof include a compound represented by the following formula (5).

[In the formula (5), “Acryl” represents an acryloyl group. ]

  The compounding (content) amount of the active energy ray-curable compound used in the present invention is preferably 5 to 80% by weight, more preferably 10 to 60% by weight, with the total amount of the composition excluding the organic solvent being 100% by mass. preferable. If it is less than 5% by weight or more than 80% by weight, it may not be possible to obtain a high hardness when it is a cured product.

3. (B-3) Radical polymerization initiator Examples of the radical polymerization initiator include a compound that thermally generates active radical species (thermal polymerization initiator) and a compound that generates active radical species by radiation (light) irradiation. And the like (radiation (light) polymerization initiator) and the like can be used.

  The radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy Roxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- ( 1-methylvinyl) phenyl) propanone) and the like.

  As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24- 61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B Etc.

  The blending amount of the radical polymerization initiator used in the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight based on 100% by mass of the total composition excluding the organic solvent. . If it is less than 0.01 part by weight, the hardness when it is a cured product may be insufficient, and if it exceeds 20 parts by weight, the inside (lower layer) may not be cured when it is a cured product.

When hardening the curable composition for hard-coat layer formation used by this invention, a photoinitiator and a thermal-polymerization initiator can be used together as needed.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds. Specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

4). Organic solvent (B-4)
In order to adjust the thickness of the coating film, the composition of the present invention can be used after being diluted with (B-4) an organic solvent. For example, the viscosity of the composition when used as an antireflection film or a coating material is usually 0.1 to 50,000 mPa · sec / 25 ° C., preferably 0.5 to 10,000 mPa · sec / 25 ° C. is there.

  (B-4) Specific examples of the organic solvent include, but are not limited to, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, acetic acid Esters such as butyl, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; 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. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The compounding quantity of the (B-4) organic solvent in the composition of this invention is 30-80 mass% in a whole composition normally, and 40-60 mass% is preferable. If it exists in the range of 30-80 mass%, coating property is favorable.

5. Curing catalyst A curing catalyst can be mix | blended with the composition for hard-coats used by this invention as needed. As the curing catalyst, the same one as the curing catalyst (A-3) used for the optical interference layer composition can be used.

  The blending amount of the curing catalyst used as necessary in the present invention is preferably 0.01 to 20 parts by weight, based on 100% by mass of the total composition excluding the organic solvent, and 0.1 to 10 parts by weight. Further preferred. If it is less than 0.01 part by weight, the film formability may be insufficient, and if it exceeds 20 parts by weight, a hardened cured product may not be obtained.

6). Other components In the curable composition for forming a hard coat layer used in the present invention, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, A wettability improver, a surfactant, a plasticizer, an ultraviolet absorber, an antioxidant, an antistatic agent, an inorganic filler, a pigment, a dye, and the like can be appropriately blended.

7). Hard coat layer forming curable composition coating (coating) method The hard coat layer forming composition used in the present invention is suitable for use as an antireflection film or a coating material. For example, dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating and the like can be mentioned. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 1 to 200 μm after drying and curing.

8). Hardening method for curable composition for forming hard coat layer The curable composition for forming a hard coat layer used in the present invention can be cured by heat and / or radiation (light). When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. In the case of radiation (light), the radiation source is not particularly limited as long as it can be cured in a short time after coating the composition. For example, as an infrared radiation source, a lamp, a resistance heating plate Commercially available, such as lasers, visible light sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet rays sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from the tungsten filament, the cold cathode method using a high voltage pulse on the metal, and the secondary electrons using secondary electrons generated by collision of ionized gaseous molecules with the metal electrode A method can be mentioned. Examples of the source of alpha rays, beta rays, and gamma rays include fission materials such as ⁶⁰ Co. For gamma rays, a vacuum tube that collides accelerated electrons with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.
The curing reaction of the curable composition for forming a hard coat layer used in the present invention can be performed under an anaerobic condition such as nitrogen in an air atmosphere, and even when cured under an anaerobic condition. The cured product has excellent scratch resistance.

(2) Hard coat layer (cured product)
The hard coat layer (cured product) constituting the laminate of the present invention can be obtained by coating and curing the curable composition on a substrate made of polyethylene terephthalate resin. Specifically, a hard coat layer-forming curable composition is coated on a substrate provided with an optical interference layer, and preferably after drying volatile components at 0 to 200 ° C., the above heat and It can be obtained as a coated molded body by performing a curing treatment with radiation. The preferable curing conditions in the case of heat are 20 to 150 ° C., and are performed within a range of 10 seconds to 24 hours. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, as for the irradiation conditions of a preferable electron beam, a pressurization voltage is 10-300 KV, an electron density is 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount is 1-10 Mrad.

The refractive index of the hard coat layer constituting the laminate of the present invention is in the range of 1.40 to 1.70, preferably 1.45 to 1.60, more preferably 1.49 to 1.55. It is. When the refractive index of the hard coat layer is lower than 1.40 or higher than 1.70, depending on the refractive index of the substrate, the refractive index of the optical interference layer, and the thickness of the optical interference layer, it prevents interference fringes. This causes the inconvenience that sex does not appear.
The film thickness of the hard coat layer is usually in the range of 0.1 to 50 μm, preferably 0.5 to 30 μm, and more preferably 1 to 10 μm. If the film thickness of the hard coat layer is smaller than 1 μm, there is a disadvantage that sufficient mechanical strength is not exhibited, and if it exceeds 10 μm, the film is curled.

IV. Other layers Note that other layers may be interposed between the base material, the easy-adhesion layer, the optical interference layer, and the hard coat layer constituting the laminate of the present invention, depending on the purpose. Layers such as a refractive index layer (refractive index 1.5 to 1.7) and a combination of a low refractive index layer (1.3 to 1.5) and a high refractive index layer (1.6 to 2.2) are provided. be able to. Only one of these layers may be formed, or two or more different layers may be formed.
As a coating method of these layers, a known coating method can be used, and various methods such as a dip method, a coater method, and a printing method can be applied.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following description, “parts” and “%” represent parts by mass and mass%, respectively, unless otherwise specified.

Production Example 1
Production of Fluorine-Containing Olefin Polymer A stainless steel autoclave with an internal volume of 1.5 L with a magnetic stirrer was sufficiently replaced with nitrogen gas. .6 g, 50 g of “ADEKA rear soap NE-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) and 1.25 g of lauroyl peroxide as a nonionic reactive emulsifier, and after cooling to −50 ° C. with dry ice-methanol, The oxygen in the system was removed again with nitrogen gas.
Next, 99.1 g of hexafluoropropylene was added, and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, the unreacted monomer was released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 31%. The obtained polymer solution was put into a mixed solvent of methanol and water to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 210 g of a fluorine-containing olefin polymer.
The solid content concentration was measured as follows. Hereinafter, the solid content concentration was measured in the same manner. That is, 1 to 1.5 g of a sample was put in an aluminum pan weighed in advance, dried on a hot plate at 150 ° C. for 5 minutes, and then the residue was weighed to measure the solid content concentration.

Using a 0.5% solution prepared by dissolving this fluorine-containing polymer in tetrahydrofuran (THF), the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography and found to be 46000. Furthermore, the glass transition temperature (Tg) by the differential thermal analysis method (DSC) and the fluorine content by the alizarin complexone method were measured. ^Further, both the NMR analysis of ^{1 H-NMR, 13 C-} NMR, performed elemental analysis to determine the proportion of each monomer component constituting the fluorine-containing polymer. The results are shown in Table 1.

Production Example 2: Production of an organic compound containing a polymerizable unsaturated group In a dry air, a solution comprising 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate was stirred at 50 ° C. with 222 parts of isophorone diisocyanate. Was added dropwise over 1 hour, followed by stirring at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of raw material isocyanate compound disappeared, and new urethane A 1660 Kaiser peak characteristic of the bond and the S (C = O) NH- group and a 1720 Kaiser peak characteristic of the acryloxy group are observed, with an acryloxy group as the polymerizable unsaturated group It was shown that -S (C = O) NH- and an acryloxy group-modified alkoxysilane having both urethane bonds were formed. As a result, a total of 773 parts of the compound (Ab) represented by the formulas (8-1) and (8-2) was obtained, and 220 parts of pentaerythritol tetraacrylate that was not involved in the reaction was mixed. .

Production Example 3 Production of Curable Compound (B-2) NK Ester A-manufactured by Shin-Nakamura Chemical Co., Ltd. with respect to a solution comprising 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer 93 parts of TMM-3LM-N (only the pentaerythritol triacrylate having a hydroxyl group is involved in the reaction) was added dropwise at 10 ° C. for 1 hour, and then stirred at 60 ° C. for 6 hours. And used as a reaction solution.
The product in this reaction solution, that is, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 1, and was 0.1% by mass or less, confirming that the reaction was carried out almost quantitatively. did. Moreover, it confirmed that a molecule | numerator contained a urethane bond and an acryloyl group (polymerizable unsaturated group) in a molecule | numerator.
From the above, 75 parts of the compound represented by the formula (5) was obtained, and 37 parts of pentaerythritol tetraacrylate that was not involved in the reaction were mixed.

Production Example 4: Production of reactive silica fine powder sol 3.2 parts of an organic compound containing a polymerizable unsaturated group produced in Production Example 2, silica particle sol (dispersion medium: methyl ethyl ketone, MEK-manufactured by Nissan Chemical Industries, Ltd.) ST, number average particle size 0.022 μm, silica concentration 30%) 91.3 parts (27 parts as silica particles) and ion-exchanged water 0.1 part were mixed at 60 ° C. for 3 hours, and then methyl orthoformate 1.4 parts of the ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive particle dispersion. 2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to obtain a solid content of 31%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 89%.

Production Example 5: Preparation of zirconia fine powder sol 300 parts of spherical zirconia fine powder (manufactured by Sumitomo Osaka Cement Co., Ltd., number average primary particle diameter 0.01 μm) is added to 700 parts of methyl ethyl ketone (MEK), and glass beads are used. The dispersion was carried out for 168 hours, and the crow beads were removed to obtain 950 parts of methyl ethyl ketone zirconia sol. 2 g of the dispersed sol was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 30%. Moreover, as a result of observation of this solid matter by an electron microscope, the minor axis average particle diameter was 15 nm, the major axis average particle diameter was 20 nm, and the aspect ratio was 1.3.

Production Example 6: Production of reactive zirconia fine powder sol 1.9 parts of an organic compound containing a polymerizable unsaturated group produced in Production Example 2, 237 parts of methyl ethyl ketone zirconia sol (zirconia concentration 30%) prepared in Production Example 5 A mixture of 0.1 part of ion-exchanged water and 0.03 part of p-hydroxyphenyl monomethyl ether was stirred at 60 ° C. for 3 hours, and then 1.0 part of orthoformate methyl ester was added, and further at the same temperature for 1 hour. A reactive particle dispersion was obtained by heating and stirring. 2 g of this dispersion was weighed on an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to determine the solid content, which was 30%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 97%.

  Hereinafter, preparation examples and lamination examples of the liquid resin composition of the present invention are shown in Examples 1 to 3, and comparative preparation examples and lamination examples are shown in Comparative Examples 1 to 3, respectively.

Example 1
(1) Preparation of liquid resin composition A (hard coat layer composition) 27.4 parts of reactive silica fine powder sol prepared in Production Example 4 (8.5 parts of reactive silica) in a container shielded from ultraviolet rays ), 2 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30), curable compound synthesized in Production Example 3 (compound shown in formula (5)) ) 1.6 parts, 0.5 parts of isobutyl-methyl mixed alkylated melamine compound (trade name: Cymel 238 manufactured by Mitsui Cytec Co., Ltd.), “Catalyst 4050” (manufactured by Mitsui Cytech Co., Ltd., aromatic sulfonic acid compound) Active ingredient concentration 32%) 0.6 part, 1-hydroxycyclohexyl phenyl ketone 0.05 part, 2-methyl-1- [4- (methyl E) phenyl] -2 mol morpholino propane -1 0.05 parts to obtain a composition of a homogeneous solution by stirring for 2 hours at 30 ° C.. When the solid content of this composition was measured in the same manner as in Production Example 4, it was 40%.

(2) Preparation of Liquid Resin Composition D (Optical Interference Layer Composition) 10 g of the fluorine-containing olefin polymer obtained in Production Example 1 and thermosetting compound methoxylated methylmelamine “Cymel 303” (Mitsui Cytec) Liquid resin composition D was obtained by dissolving 2.0 g of a product (made by Co., Ltd.) and 3.13 g of “Catalyst 4050” as a curing catalyst in 310 g of methyl isobutyl ketone as a solvent. The solid content concentration in the liquid resin composition was 4.0% by mass.

(3) Manufacture of Laminate After coating liquid resin composition A on the easy-adhesion treated surface of single-sided easy-adhesive polyethylene terephthalate film A4100 (made by Toyobo Co., Ltd., film thickness 188 μm) with wire bar coater # 8. The film was dried in an oven at 80 ° C. for 1 minute to form a coating film. Subsequently, the coating film was UV-cured under light irradiation conditions of 0.3 J / cm ² using a metal halide lamp in the atmosphere to form a cured film A. When the film thickness and refractive index of this cured film were calculated with a reflection spectrometer, the film thickness was 3 μm and the refractive index was 1.49. Furthermore, after laminating the liquid resin composition D on the cured film A with a wire bar coater # 3, the laminate AD was formed by heating in an oven at 140 ° C. for 2 minutes. When the film thickness and refractive index of the cured film D were calculated with a reflection spectrometer, the film thickness was 130 nm and the refractive index was 1.42.

Example 2
(1) Preparation of liquid resin composition B (hard coat layer composition) 27.3 parts of reactive silica fine powder sol prepared in Production Example 4 (8.5 parts of reactive silica) in a container shielded from ultraviolet rays ), 7 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Nippon Kayaku Co., Ltd., trade name: KAYARAD PET-30), curable compound synthesized in Production Example 3 (compound represented by formula (5) ) 1.6 parts, 2 parts of isobutyl-methyl mixed alkylated melamine compound (trade name: Cymel 238, manufactured by Mitsui Cytec Co., Ltd.), 1.9 parts of “Catalyst 4050”, 0.2 part of 1-hydroxycyclohexyl phenyl ketone , 0.2 part of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 is stirred at 30 ° C. for 2 hours. To obtain a composition of a homogeneous solution by. When the solid content of this composition was measured in the same manner as in Production Example 4, it was 50%.

(2) Preparation of liquid resin composition E (composition for optical interference layer) 10 g of the fluorine-containing olefin polymer obtained in Production Example 1, 3.2 g of “Cymel 303” and 3.13 g of “Catalyst 4050” Was dissolved in 300 g of methyl isobutyl ketone as a solvent to obtain a liquid resin composition E. The solid content concentration in the liquid resin composition was 4.5% by mass.

(3) Manufacture of laminated body After applying liquid resin composition B to the easy-adhesion treated surface of single-sided easy-adhesive polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) with wire bar coater # 6. The film was dried in an oven at 80 ° C. for 1 minute to form a coating film. Subsequently, the coating film was ultraviolet-cured under light irradiation conditions of 0.3 J / cm ² using a metal halide lamp in the atmosphere to form a cured film B. When the film thickness and refractive index were calculated in the same manner as in Example 1, the film thickness was 3 μm and the refractive index was 1.51. Furthermore, after laminating the liquid resin composition E on the cured film B with a wire bar coater # 3, the laminate BE was formed by heating at 140 ° C. for 2 minutes in an oven. When the film thickness and refractive index of the cured film E were calculated in the same manner as in Example 1, the film thickness was 160 nm and the refractive index was 1.43.

Example 3
(1) Preparation of liquid resin composition C (hard coat layer composition) 32.0 parts of reactive zirconia fine powder sol prepared in Production Example 6 (9.6 parts of reactive zirconia) in a container shielded from ultraviolet rays ), A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.), curable compound synthesized in Production Example 3 (compound shown in formula (5)) ) 0.4 parts, 4 parts isobutyl-methyl mixed alkylated melamine compound (trade name: Cymel 238, manufactured by Mitsui Cytec Co., Ltd.), 2.5 parts “Catalyst 4050”, 1.0 part of 1-hydroxycyclohexyl phenyl ketone , 1.1 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 and methyl The Sobuchiruketon 13 parts to obtain a composition of a homogeneous solution by stirring for 2 hours at 30 ° C.. When the solid content of this composition was measured in the same manner as in Production Example 4, it was 50%.

(2) Preparation of liquid resin composition F (composition for optical interference layer) 10 g of the fluorine-containing olefin polymer obtained in Production Example 1, 20 g of “Cymel 303” and 4.7 g of “Catalyst 4050” were used as solvents. Liquid resin composition F was obtained by dissolving in 753 g of methyl ethyl ketone. The solid content concentration in the liquid resin composition was 4.0% by mass.

(3) Manufacture of Laminate After coating liquid resin composition C on the easy-adhesion treated surface of single-sided easy-adhesive polyethylene terephthalate film A4100 (made by Toyobo Co., Ltd., film thickness 188 μm) with wire bar coater # 6. The film was dried in an oven at 80 ° C. for 1 minute to form a coating film. Subsequently, the coating film was UV-cured under light irradiation conditions of 0.3 J / cm ² using a metal halide lamp in the atmosphere to form a cured film C. When the film thickness and refractive index were calculated in the same manner as in Example 1, the film thickness was 3 μm and the refractive index was 1.55. Furthermore, after laminating the liquid resin composition F on the cured film C by the wire bar coater # 3, the laminate CF was formed by heating in an oven at 140 ° C. for 2 minutes. When the film thickness and refractive index of the cured film F were calculated in the same manner as in Example 1, the film thickness was 130 nm and the refractive index was 1.50.

Comparative Example 1
A cured film laminate BD was produced in the same manner as in Example 1 except that the liquid resin composition D was laminated with the wire bar coater # 2 on the cured film B obtained in Example 2. When the film thickness of the cured film layer D was calculated in the same manner as in Example 1, it was 50 nm.

Comparative Example 2
A cured film laminate BF was produced in the same manner as in Example 3 except that the liquid resin composition F was laminated on the cured film B obtained in Example 2 with a wire bar coater # 6. As in Example 1, the thickness of the cured film layer F was calculated to be 250 nm.

Comparative Example 3
On the cured film B obtained in Example 2, nothing was laminated, and a laminate B was obtained.
Tables 2 and 3 show compositions other than the solvents of the compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 3.

<Characteristic evaluation of laminate>
About the laminated body produced in Examples 1-3 and Comparative Examples 1-3, the coating-film external appearance (degree of interference fringe) and adhesiveness were evaluated by the method shown below. Table 4 shows the obtained results.

(1) Appearance of coating film (degree of interference fringes)
The appearance of the coating film was visually evaluated according to the following evaluation criteria under a fluorescent lamp.
Appearance of the coating film ○: Appearance of the coating film with almost no interference fringes even when the viewing angle is changed under the fluorescent lamp Δ: Appearance of the coating film with almost no interference fringes when the viewing angle is not changed under the fluorescent lighting ×: Under the fluorescent lighting Interference fringes even when the viewing angle is not changed

(2) Adhesiveness The adhesiveness of the antistatic layer formed on the substrate is based on the cross cellophane tape peeling test in JIS K5400, and the following standard is the remaining film rate at 100 squares in total of 1 mm square. The adhesion was evaluated.
Adhesiveness ○: Remaining film ratio is 100 to 90%
Adhesiveness △: Remaining film ratio is 90 to 50%
Adhesiveness x: Remaining film ratio is 50 to 0%

The laminate of the present invention reduces the reflectance amplitude by providing an optical interference layer having a specific refractive index and film thickness between a base material made of polyethylene terephthalate resin and a hard coat layer. As described above, the problem that the appearance of the coating film is glaring can be solved, the transparency is excellent, and the appearance is excellent.
Furthermore, the laminate of the present invention is excellent in adhesion between the substrate and the hard coat layer, and is excellent in scratch resistance and dust wiping.
Therefore, the laminate of the present invention can be advantageously used for the formation of optical materials such as an antireflection film and an optical fiber sheath material, and the visibility can be improved by applying to various display devices. it can.

FIG. 1 is a diagram showing a basic configuration of a laminate of the present invention. FIG. 2 is a diagram showing the configuration of another embodiment of the laminate of the present invention. FIG. 3 is a graph showing the relationship between the reflectance amplitude and the wavelength of the laminates of Examples 1 to 3 when the refractive index and film thickness of the optical interference layer are varied. FIG. 4 is a graph showing the relationship between the reflectance amplitude and the wavelength of the laminates of Comparative Examples 1 to 3 when the refractive index and film thickness of the optical interference layer are varied.

Explanation of symbols

1: Laminated body 2: Base material 3: Optical interference layer 4: Hard coat layer 5: Easy adhesion layer

Claims (4)

  An optical interference layer having a refractive index of 1.40 to 1.60 and a film thickness of 70 to 200 nm on a base material made of polyethylene terephthalate resin, and a refractive index of 1.40 to 1.70. A laminate comprising a hard coat layer having a refractive index larger than that of the optical interference layer in this order. A fluorine-containing olefin polymer in which the optical interference layer contains 10 mol% to 50 mol% of a structural unit derived from a monomer containing the following component (A-1) hydroxyl group:
(A-2) curable compound,
The laminate according to claim 1, which is a cured layer obtained from a liquid resin composition containing (A-3) a curing catalyst and / or a radical polymerization initiator, and (A-4) a solvent. The hard coat layer comprises the following component (B-1) oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium (B-2) 3) A curable compound (B-3) a radical polymerization initiator (B-4) a cured layer obtained from a liquid curable composition characterized by containing a solvent. The laminated body of description.   An antireflection film comprising the laminate according to any one of claims 1 to 3.

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