JPWO2017168869A1 - Adhesive composition for optical film and optical film - Google Patents

Abstract

Provided are an optical film pressure-sensitive adhesive composition and an optical film that satisfy excellent reworkability and durability even after being placed in a high temperature environment.
(A) Acrylic block copolymer, (B) Anti-adhesive, (C) Tackifying resin, and after standing at 80 ° C. for 72 hours, in accordance with JIS-K-6854-2, tensile speed 50 mm The pressure-sensitive adhesive composition for an optical film has an adhesion strength of 4.0 N / 25 mm or more after one month has elapsed after being attached to the adherend, measured under the conditions of / min. Moreover, let it be the optical film 10 which has the adhesive layer 22 formed using said adhesive composition for optical films on a film surface.

Description

  The present invention relates to an optical film pressure-sensitive adhesive composition and an optical film, and more specifically, for an optical film suitable for an optical film to be attached to a window made of glass or the like in a building such as a building or a house or a vehicle such as an automobile. The present invention relates to an adhesive composition and an optical film.

  A functional film having a predetermined function such as solar shading may be applied to windows made of glass of buildings such as buildings and houses and windows made of glass of vehicles such as automobiles. The functional film has an adhesive layer for attaching to a window made of glass or the like. The functional film is required to have high adhesion (durability) to the window after construction. It is known that an acrylic block copolymer is used as a material for forming the adhesive layer (Patent Document 1).

JP2015-140379A

  The functional film may be stored in stock until it is sold after being manufactured. Especially in the summer, the product may be placed in a high temperature environment during storage or transportation of the product. The product after being placed in such a high temperature environment may not be able to exhibit the adhesive properties immediately after production.

  The problem to be solved by the present invention is to provide an optical film pressure-sensitive adhesive composition and an optical film which satisfy high adhesion to a window after construction even after being placed in a high temperature environment.

  As a result of intensive studies by the present inventors, the acrylic block copolymer used as the pressure-sensitive adhesive itself has high adhesion and cohesion, and exhibits very high adhesion. Therefore, the pellets adhere to each other at the material supply stage. In order to prevent blocking, some anti-adhesive agents are applied to the pellet surface, and this anti-adhesive agent appears on the surface of the adhesive layer in a high-temperature environment, thereby reducing the adhesive properties of the adhesive. I found out. And based on this knowledge, it came to complete this invention.

  That is, in order to solve the above-mentioned problems, the pressure-sensitive adhesive composition for an optical film according to the present invention contains (A) an acrylic block copolymer, (B) an anti-adhesive, and (C) a tackifier resin at 80 ° C. Adhesion after one month has passed after being pasted on the adherend, measured at a tensile speed of 50 mm / min, in accordance with JIS-K-6854-2, after standing for 72 hours, is 4.0 N / 25 mm or more.

  The pressure-sensitive adhesive composition for an optical film according to the present invention has an initial adhesion measured in accordance with JIS-K-6854-2 after being allowed to stand at 80 ° C. for 72 hours, under a tensile speed of 50 mm / min. It is preferable that it is 0.5 N / 25 mm or less. The (B) anti-adhesive and the (C) tackifying resin are preferably a combination having compatibility. The (C) is preferably a styrene copolymer. The (C) may be a styrene polymer composed of a homopolymer of a styrene monomer. The styrene copolymer is preferably one or more of a copolymer of a styrene monomer and a terpene resin and a copolymer of a styrene monomer and a petroleum resin. The content of (C) is preferably in the range of 3.0 to 7.0 parts by mass with respect to 100 parts by mass of (A).

  The gist of the optical film according to the present invention is that the film surface has a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition for optical films described in any one of the above.

  The optical film according to the present invention may further have a metal layer. The metal of the metal layer is preferably one or more of silver, silver alloy, aluminum, alloy steel (iron alloy), and gold. The optical film according to the present invention may further have a high refractive index layer having a refractive index higher than that of the metal layer. The high refractive index layer is preferably one or more of a metal oxide thin film and an organic thin film. The metal oxide layer is preferably formed by a sol-gel method. The optical film according to the present invention may further have a base film. The thickness of the base film is preferably in the range of 25 to 125 μm. The base polymer of the base film is desirably any one of a polyester resin, a polyolefin resin, an acrylic resin, a polycarbonate resin, and a vinyl chloride resin. The base film is preferably a biaxially stretched polypropylene film. The optical film according to the present invention includes the adhesive layer, the metal layer, the organic thin film as a high refractive index layer having a higher refractive index than the metal layer, and a base film, and includes an adhesive layer / organic thin film / metal layer / They may be laminated in the order of organic thin film / base film.

  According to the pressure-sensitive adhesive composition for an optical film according to the present invention, it contains (C) a tackifying resin together with (A) an acrylic block copolymer and (B) an anti-adhesive agent, and is allowed to stand at 80 ° C. for 72 hours. , In accordance with JIS-K-6854-2, measured at a tensile speed of 50 mm / min, because the adhesive strength after one month has elapsed from pasting to the adherend is 4.0 N / 25 mm or more. Even after being placed in a high temperature environment, it satisfies the high adhesion to the window after construction.

  And the adhesive composition for optical films which concerns on this invention is the initial contact | adhesion measured on condition of 50 mm / min of tensile speeds based on JIS-K-6854-2 after leaving to stand at 80 degreeC for 72 hours. Since the force is 0.5 N / 25 mm or less, excellent reworkability that enables reattachment during construction is maintained even after being placed in a high temperature environment.

  And according to the optical film according to the present invention, since it has a pressure-sensitive adhesive layer formed on the film surface using the pressure-sensitive adhesive composition for optical film according to the present invention, even after being placed in a high-temperature environment, Satisfies high adhesion to windows after construction. Further, even after being placed in a high temperature environment, it is possible to maintain excellent reworkability that enables re-sticking during construction.

It is sectional drawing of the optical film which concerns on one Embodiment of this invention. It is sectional drawing of the other optical film which concerns on one Embodiment of this invention. It is sectional drawing of the other optical film which concerns on one Embodiment of this invention. It is a schematic diagram explaining the affixing method of the optical film to a to-be-adhered body. It is a graph which shows the DSC chart measured about the mixture of an adhesion promoter and tackifying resin.

  Hereinafter, the present invention will be described in detail.

  The pressure-sensitive adhesive composition for optical films according to the present invention (hereinafter sometimes referred to as the present composition) contains (A) an acrylic block copolymer, (B) an anti-adhesive agent, and (C) a tackifier resin. This composition contains these as essential components, and after being allowed to stand at 80 ° C. for 72 hours, is measured on the condition of a tensile speed of 50 mm / min in accordance with JIS-K-6854-2. Adhesive strength after one month has passed after being attached to the surface becomes 4.0 N / 25 mm or more.

  By including an acrylic polymer in the present composition, the composition can be excellent in visible light permeability and optical characteristics with little haze. Moreover, the strong contact | adhesion power which can ensure the scattering prevention of glass can be provided. Among acrylic polymers, acrylic block copolymers have a narrow molecular weight distribution and low low molecular weight components compared to many other acrylic polymers, and phase separation structures due to intramolecular soft blocks and hard blocks. Therefore, it has tackiness and can maintain a high cohesive force.

  Acrylic block copolymer can reduce the low molecular weight components that transfer to the adherend to contaminate the surface or reduce the cohesive force by controlling the molecular weight distribution narrowly, and suppress fluctuations in mechanical properties and adhesion. From the viewpoint of being able to do so, it is preferable that the value of Mw / Mn, which is an index of molecular weight distribution, is in the range of 1.0 to 1.5. More preferably, it exists in the range of 1.0-1.3, More preferably, it exists in the range of 1.0-1.2.

  AB block diblock copolymer comprising two polymer blocks A and B rather than a multiblock copolymer in terms of ease of obtaining a phase separation structure caused by soft blocks and hard blocks in the molecule Also preferred is an ABA or ABA ′ type triblock copolymer comprising three polymer blocks A and B (and A ′). In this case, it is desirable that A and A '(that is, a high Tg polymer) are hard segments, and B (that is, a low Tg polymer) is a soft segment. When the alkyl part is the same, the methacrylic acid alkyl ester has a higher Tg than the acrylic acid alkyl ester, so the high Tg polymer is generally a methacrylic acid alkyl ester polymer, and the low Tg polymer is generally an acrylic acid alkyl ester polymer. is there. That is, if it is a triblock body, it is desirable that they are a methacrylic acid alkylester polymer-acrylic acid alkylester polymer-methacrylic acid alkylester polymer.

  The acrylic block copolymer may be composed of one kind of acrylic block copolymer or may be composed of two or more kinds of acrylic block copolymers. Examples of one type of acrylic block copolymer include one type selected from diblock copolymers and one type selected from triblock copolymers. As two or more types of acrylic block copolymers, two or more types selected from diblock copolymers, two or more types selected from triblock copolymers, one or more types selected from diblock copolymers And one or more selected from triblock copolymers. The diblock copolymer is excellent in flexibility and wettability with the adherend surface, and the triblock copolymer is excellent in cohesive force.

  The polymer block A includes, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 2-methacrylic acid 2- Polymers such as ethylhexyl, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isobornyl methacrylate, etc., and those obtained by substituting some or all of the hydrogen atoms of these monomers with substituents And those obtained by substituting the alkyl or cycloalkyl carbon atom of these monomers with a heteroatom. Among these, those derived from alkyl methacrylates are preferred, alkyl alkyls having 1 to 4 carbon atoms in alkyl are preferred, and ethyl methacrylate or methyl methacrylate is more preferred.

The polymer block B is, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, acrylic acid 2- Polymers such as ethylhexyl, n-octyl acrylate, lauryl acrylate, tridecyl acrylate, and stearyl acrylate, and those obtained by substituting some or all of the hydrogen atoms of these monomers with substituents, these Examples thereof include those obtained by substituting carbon atoms of monomeric alkyl or cycloalkyl with heteroatoms. A larger number of carbon atoms in the alkyl group tends to have a lower Tg and become a soft segment. Among these, those derived from an alkyl acrylate ester are preferable, those derived from an alkyl alkyl ester having 3 to 6 carbon atoms in alkyl are more preferable, and those derived from butyl acrylate are more preferable.

  Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a nitro group, and a cyano group. Among these, a hydroxy group or a carboxy group is preferable. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, and a boron atom.

  Moreover, as an upper limit of the glass transition temperature of the polymer block A, 140 degreeC is preferable and 120 degreeC is more preferable. On the other hand, as a minimum of glass transition temperature of polymer block A, 80 ° C is preferred and 100 ° C is more preferred. As an upper limit of the glass transition temperature of the polymer block B, -20 degreeC is preferable and -40 degreeC is more preferable. On the other hand, the lower limit of the glass transition temperature of the polymer block B is preferably -60 ° C, more preferably -50 ° C.

  When the acrylic block copolymer is composed of one type selected from diblock copolymers and one type selected from triblock copolymers, the diblock copolymer may be methyl methacrylate / acrylic. Examples thereof include butyl acrylate, ethyl methacrylate / butyl acrylate, methyl methacrylate / 2-ethylhexyl acrylate, ethyl methacrylate / 2-ethylhexyl acrylate, and the triblock copolymer includes methyl methacrylate / butyl acrylate / methacrylic acid. And methyl methacrylate, ethyl methacrylate / butyl acrylate / ethyl methacrylate, methyl methacrylate / 2-ethylhexyl acrylate / methyl methacrylate, ethyl methacrylate / 2-ethylhexyl acrylate / ethyl methacrylate, and the like.

  (B) The anti-adhesive agent is a material applied to the surface of the pellets so that the acrylic block copolymer pellets adhere to each other and do not block. Since the acrylic block copolymer itself has high adhesion and cohesion and exhibits very high adhesion, an anti-adhesive agent is applied to the pellet surface to prevent the pellets from sticking to each other and blocking at the material supply stage. Has been. Examples of the anti-blocking agent for the acrylic block copolymer pellet include fatty acid amide, polyalkylene glycol, and saturated fatty acid ester. Examples of fatty acid amides include ethylene bis stearic acid amide and palmitic acid amide. (B) The adhesion amount of the anti-adhesive agent to the pellet is about several hundred ppm. From the viewpoint of preventing blocking of pellets (anti-adhesion effect), the adhesion amount of the anti-adhesive is relatively large. (B) The anti-adhesive agent is dispersed in the present composition after being kneaded. In this state, since the amount appearing on the surface is extremely small (according to surface analysis (TOF-SIMS), it is about the lower limit of detection and about 500), the adhesive property of the composition is not disturbed. Absent. However, when placed in a high-temperature environment (for example, in a summer warehouse (40-60 ° C), when transporting ships, trucks, etc. (-80 ° C)), B) the adhesion agent bleeds out to the surface and the surface sticks. It has been found that the characteristics are degraded. Bleeding out to the surface is confirmed by surface analysis (surface analysis: TOF-SIMS). Although it depends on the kind and blending amount of the adhesion-preventing agent, the detected value is 5000 or more, or 10,000 or more when the adhesion amount is from the viewpoint of preventing blocking of the pellet (anti-adhesion effect).

  (C) Tackifying resin is not only added to improve the tackiness of the present composition, but (B) is blended in order to suppress a decrease in the tackiness characteristics of the present composition due to the anti-adhesive agent. It is. When it is added simply to improve the tackiness of the present composition, a tackifier resin generally having a high compatibility with the (A) acrylic block copolymer is selected. This is because the compatibility is high, and the tackifier resin is uniformly dispersed in the material and exhibits uniform adhesive properties. Moreover, it is because it becomes a composition which is more excellent in light transmittance. Examples of tackifying resins highly compatible with acrylic block copolymers include natural resins such as rosin and terpene resins, and synthetic resins such as petroleum resins, hydrogenated petroleum resins, aromatics, and styrenes. It is done.

  On the other hand, in this composition, what has a comparatively low compatibility with an acrylic block copolymer is used as tackifying resin. Since the compatibility with the acrylic block copolymer is low, it becomes possible to behave in the same manner as the (B) anti-adhesive agent, and it becomes easy to bleed out to the surface like the (B) anti-adhesive agent. It has been confirmed by surface analysis that a tackifying resin having low compatibility with the acrylic block copolymer is bleeding out on the surface (surface analysis: TOF-SIMS). Moreover, it has also confirmed by surface analysis that it is bleeding out on the surface with (B) anti-adhesive agent (surface analysis: TOF-SIMS). As described above, even when the detection value of the anti-adhesive is as high as 5000 or higher, or 10,000 or higher, the tackifier resin bleeds out to the surface (detected value of 10,000 or higher). It is possible to suppress deterioration of characteristics and maintain desired adhesion even after being placed in a high temperature environment. That is, as described above, after being allowed to stand at 80 ° C. for 72 hours, in accordance with JIS-K-6854-2, measured under the condition of a tensile speed of 50 mm / min, 1 after being attached to an adherend. The adhesion strength after a lapse of months can be 4.0 N / 25 mm or more. Thereby, prevention of scattering of glass can be guaranteed.

  (C) As tackifying resin, what has compatibility with (B) adhesion promoter is preferable. (B) Having compatibility with the anti-adhesive agent means that the (B) anti-adhesive agent is affected to the extent that the melting point derived from the (B) anti-adhesive agent is lowered when mixed with the (B) anti-adhesive agent. In particular, (C) refers to one that lowers the melting point derived from the adhesion-preventing agent and shows a single melting point peak due to the influence of the tackifying resin.

  (C) As tackifying resin, aromatic modified terpene resin, aromatic modified hydrogenated terpene resin, aromatic modified petroleum resin, etc. are mentioned. Moreover, the styrene polymer which consists of a homopolymer of a styrene monomer is also mentioned. These may be used individually by 1 type as tackifying resin, and may be used in combination of 2 or more type. Of these, aromatic modified terpene resins or aromatic modified hydrogenated terpene resins are preferred from the viewpoint of stability with an anti-adhesive agent. An aromatic modified hydrogenated terpene resin is more preferable from the viewpoints of excellent light transmittance and suppressing haze-up. The aromatic modified terpene resin is a resin (styrene copolymer) obtained by copolymerizing terpenes such as α-pinene, β-pinene and limonene (dipentene) with a styrene monomer. Terpene resin is a hydrogenated product. The aromatic modified petroleum resin is a copolymer of styrene monomer and petroleum resin (styrene copolymer).

  The content of the (C) tackifying resin is 3.0 parts by mass or more with respect to 100 parts by mass of (A) from the viewpoint of easily maintaining desired adhesion even after being placed in a high temperature environment. Preferably there is. More preferably, it is 4.0 parts by mass or more. Moreover, from the viewpoint of suppressing white turbidity (haze-up) due to a decrease in compatibility with the acrylic block copolymer, the content is preferably 7.0 parts by mass or less with respect to 100 parts by mass of (A). . More preferably, it is 6.0 parts by mass or less.

  As described above, after being allowed to stand at 80 ° C. for 72 hours, measured under conditions of a tensile speed of 50 mm / min in accordance with JIS-K-6854-2. The adhesion force is more preferably 5.0 N / 25 mm or more, 7.0 N / 25 mm or more, and 10.0 N / 25 mm or more. This adhesion force can be increased by increasing the content of (C) the tackifier resin, for example.

  This composition has excellent workability such as water drainage and reworkability by having an appropriate adhesion force, and the film ends off due to its own weight, or the end of the film laminated for film curling From the viewpoint of being able to hold a film that floats on the window, it is preferable to have excellent initial adhesion. The initial adhesiveness is the adhesiveness for 1 hour after construction. Moreover, it is preferable that the adhesive force after 3 to 24 hours is suppressed from a viewpoint of easy position adjustment and re-sticking (excellent reworkability). Furthermore, it is preferable that the adhesive force with the passage of time of 72 hours or more is high from the viewpoint of anti-scattering property that prevents debris from scattering when the window is broken. Here, it refers to the thing before being placed in a high temperature environment. Specifically, the initial adhesion strength (one hour after construction) is preferably 0.05 N / 25 mm or more. Moreover, it is preferable that the adhesive force after 3 hours is less than 4.0 N / 25mm. More preferably, it is 1.0 N / 25 mm or less. Furthermore, it is preferable that the adhesive strength over time of 72 hours or more (for example, after one month) is 4.0 N / 25 mm or more. The adhesion is measured under the condition of a tensile speed of 50 mm / min according to JIS-K-6854-2. The initial and temporal adhesion can be adjusted, for example, by including a plasticizer for adjusting the adhesive strength. The adhesive strength over time can be controlled by selecting an appropriate plasticizer type and amount.

  In addition, even after the composition is placed in a high temperature environment, it is excellent in initial adhesion as well as before being placed in a high temperature environment, and the adhesion force after 3 to 24 hours is suppressed. preferable. Specifically, the initial adhesion strength (one hour after construction) is preferably 0.05 N / 25 mm or more. Moreover, it is preferable that the adhesive force after 3 hours is less than 4.0 N / 25mm. By blending a tackifying resin with low compatibility with the acrylic block copolymer, the initial adhesion strength and the adhesion strength after 3 to 24 hours can be within the above range even after being placed in a high temperature environment. it can.

  It is preferable that this composition contains the plasticizer for adjusting adhesive force. The adhesive strength over time can be controlled by selecting an appropriate plasticizer type and amount. It is desirable that the plasticizer is compatible with the acrylic block copolymer. From this viewpoint, it is preferable that the solubility parameter of the plasticizer (SP value according to the Small method) is in the range of 8.0 to 9.9. When the SP value is within this range, a uniform composition having excellent compatibility between the plasticizer and the acrylic block copolymer and no phase separation can be formed. Thereby, an adhesive surface with less unevenness in terms of adhesion can be formed. The SP value is more preferably in the range of 8.2 to 9.1, and still more preferably in the range of 8.3 to 8.9, from the viewpoints of the above, coating properties, and appearance after coating. From the same viewpoint, the molecular weight is preferably in the range of 300 to 500. When the molecular weight is within this range, the plasticizer and the acrylic block copolymer are excellent in compatibility, and a uniform composition without phase separation can be formed. Thereby, an adhesive surface with less unevenness in terms of adhesion can be formed. The molecular weight of the plasticizer is more preferably in the range of 340 to 430, still more preferably in the range of 350 to 400, from the above viewpoint.

  Examples of the plasticizer include phosphoric acid esters, phthalic acid esters, and adipic acid esters. These may be used alone as a plasticizer or in combination of two or more. Among these, phosphoric acid esters are more preferable from the viewpoints of improving flame retardancy and fire resistance, excellent heat resistance, and suppressing bleed and bloom in a high temperature environment. In addition, when it is a phthalate ester or adipic acid ester, it has excellent compatibility with an acrylic block copolymer, ensures initial adhesion, and an optical film using this composition as a pressure-sensitive adhesive is a window when applied with water. It is suitable because it is easily held.

  Examples of the phosphate ester include tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, and the like. These may be used individually by 1 type as phosphate ester as a plasticizer, and may be used in combination of 2 or more type. Among these, tricresyl phosphate, trixylenyl phosphate, and cresyl diphenyl phosphate are more preferable from the viewpoint of excellent flame retardancy, fire resistance, and heat resistance.

  Examples of the phthalic acid ester include dioctyl phthalate (DOP), bis (2-butoxyethyl phthalate (DBEP)), and diisononyl phthalate (DINP). Examples of adipic acid esters include dioctyl adipate (DOA), diisodecyl adipate (DIDA), and bis (2-butoxyethyl) adipate (DBEA). Among these, excellent initial adhesion, large increase in adhesion over time of 72 hours, excellent compatibility with acrylic block copolymer, forming a uniform composition without phase separation, From the viewpoint of being able to form an adhesive surface with less unevenness in terms of adhesion and available at a relatively low cost, dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA) ) Is preferred. In addition, with respect to the adhesive strength over time, the increase in the adhesive strength after 10 to 24 hours is suppressed, and from the viewpoint of easy position adjustment and reattachment (excellent reworkability), diisononyl phthalate (DINP), Dioctyl adipate (DOA) is more preferred. In addition, with respect to the adhesion strength over time, dioctyl adipate (DOA) is used from the standpoint that the increase in adhesion strength after 3 to 5 hours is suppressed, and position adjustment and reattachment are easy (excellent reworkability). Particularly preferred.

  It is preferable that content of a plasticizer is 1 mass part or more with respect to 100 mass parts of acrylic polymers from a viewpoint of adhesive force. More preferably, it is 3 parts by mass or more. On the other hand, it is preferably 40 parts by mass or less from the viewpoint of maintaining compatibility with the acrylic polymer and preventing bleeding of the adhesion adjusting agent. Moreover, it is preferable that it is 20 mass parts or less from a viewpoint from which the increase in the adhesive force after 3 to 5 hours is suppressed. Furthermore, it is preferable that it is 10 mass parts or less from a viewpoint by which the increase in the adhesive force after 10 to 24 hours is suppressed.

  The present composition may further contain a light stabilizer. Addition of the light stabilizer improves the weather resistance and suppresses the deterioration of the characteristics over time due to light irradiation or the like. Depending on the type, there is also an effect of increasing the adhesive strength over time. Moreover, this composition may contain antioxidant further.

  Examples of the light stabilizer include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, and HALS (hindered amine light stabilizer). Of these, benzotriazole-based ultraviolet absorbers are preferred from the standpoint of excellent effects of increasing the adhesive force over time.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chloro. Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-5′-di-tert-pentyl) ) Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) ) Phenyl, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-cal) Kishifeniru) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol, etc. 2- (2'-hydroxyphenyl) benzotriazole compounds and the like.

  Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid 3 hydrate. 2-hydroxybenzophenones such as 2-hydroxy-4-n-octyloxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).

  Examples of triazine ultraviolet absorbers include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyl). Oxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2 -[2-hydroxy-4- (3-dodecyloxy-2-hydroxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy-4- (3-Tridecyloxy-2-hydroxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2-hydroxy- -[3- (2-Ethylhexyloxy) -2-hydroxypropyloxy] phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) ) -4,6-dibiphenyl-s-triazine, 2- [2-hydroxy-4- [1- (i-octyloxycarbonyl) ethyloxy] phenyl] -4,6-dibiphenyl-s-triazine, 2, 4-bis (2-hydroxy-4-octoxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine, 2,4-bis (4-butoxy-2-hydroxyphenyl) -6- (2 , 4-dibutoxyphenyl) -s-triazine, 2,4,6-tris (2-hydroxy-4-octoxyphenyl) -s-triazine Such as the Jin class, and the like.

  As HALS (hindered amine light stabilizer), 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 1,2,2 , 6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6) -Pentamethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxypentyl) -2-n-butyl malonate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) · di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / succinol Acid diethyl polycondensate, 1 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) Hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6 Tertiary octylamino-s-triazine polycondensate, dimethyl succinate 1- (2hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl-4-piperidine polycondensate, 1,5 , 8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5 , 8,12-Tetraazadode Can, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6 Yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) ) Amino) -s-triazin-6-ylaminoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) ) Amino) -s-triazin-6-ylaminoundecane, 2-decanedioic acid bis (2,2,6,6-tetramethyl-1-octyloxy) -4-piperidinyl) ester and 1,1 dimethylethylhydro Reaction product of polyoxide and octane Such as Ren and the like. Since an ultraviolet absorber and HALS work complementarily, it is preferable to add both. Further, it is preferable to add an ultraviolet absorber in order to prevent the heat shielding layer from being deteriorated by ultraviolet rays.

  The content of the light stabilizer is 1 part by mass or more with respect to 100 parts by mass of the acrylic polymer from the viewpoints of desired weather resistance, deterioration of characteristics over time, and thickness of the pressure-sensitive adhesive layer. Is preferred. More preferably, it is 2 parts by mass or more. Further, if it is excessively added, there are adverse effects such as precipitation, bleeding, and a decrease in adhesion, and therefore it is preferably 6 parts by mass or less. More preferably, it is 4 parts by mass or less.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and the like. In this, a phenolic antioxidant is preferable.

  Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, C2-10 alkylene bis (tert-butylphenol) [for example, 2,2'-methylene bis (4-methyl-6- Tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol)], tris (di-tert-butyl-hydroxybenzyl) benzene [eg 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, etc.], C2-10 alkanediol-bis [(di-tert-butyl-hydroxyphenyl) propionate] [For example, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like], di- or trioxy-C -4 alkanediol-bis (tert-butyl-hydroxyphenyl) propionate [e.g., triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] etc.], C3 -8 alkanetriol-bis [(di-tert-butyl-hydroxyphenyl) propionate], C4-8 alkanetetraol tetrakis [(di-tert-butyl-hydroxyphenyl) propionate] [e.g. pentaerythritol tetrakis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like], long-chain alkyl (di-tert-butylphenyl) propionate [for example, n-octadecyl-3- (4 ′, 5 '-Di-tert-butylphenyl) propionate, stearyl-2- 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, etc.], 2-tert-butyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methyl And phenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), and the like.

  Phosphorus antioxidants include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,4-ditert-butyl-5-methylphenyl) Phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (Decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Ditert-butyl-4-methylphenyl) pentaerythritol Phosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, Tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5- Tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 2'-methylenebis (4,6-tert-butylphenyl) -2-ethyl Silphosphite, 2,2′-methylenebis (4,6-tertiarybutylphenyl) -octadecylphosphite, 2,2′-ethylidenebis (4,6-ditertiarybutylphenyl) fluorophosphite, Tris (2 -[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 2-ethyl-2- Examples thereof include phosphites of butylpropylene glycol and 2,4,6-tritert-butylphenol.

  Sulfur antioxidants include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, pentaerythrityl tetrakis (3-lauryl) Thiopropionate) and sulfur compounds such as 2-mercaptobenzimidazole.

  The content of the antioxidant is 0.01 parts by mass or more with respect to 100 parts by mass of the acrylic polymer from the viewpoints of desired weather resistance, deterioration of characteristics over time, and thickness of the pressure-sensitive adhesive layer. Preferably there is. More preferably, it is 0.05 mass part or more. Further, if it is excessively added, there are adverse effects such as precipitation, bleeding, and a decrease in adhesion, so that the amount is preferably 2.0 parts by mass or less. More preferably, it is 1.0 mass part or less.

  This composition is used as a material for the pressure-sensitive adhesive layer formed on the film surface. Thereby, an adhesive film (optical film) can be constituted. What is necessary is just to adjust the thickness of an adhesive layer suitably in consideration of a use, adhesive force, an optical characteristic, a material type, durability, etc. For example, 10 μm or more is preferable from the viewpoint of adhesion, ultraviolet absorption, and the like. More preferably, it is 20 μm or more. Moreover, 100 micrometers or less are preferable from viewpoints, such as visible-light transmittance, transparency, and economical efficiency. More preferably, it is 50 μm or less. Although it does not specifically limit as a base film of an optical film, A polymer film etc. can be mentioned. The optical film can be suitably used as a film that can be attached to the surface of an adherend such as a window glass of a building such as a building or a house or a window glass of a vehicle such as an automobile.

  If the thickness of the pressure-sensitive adhesive layer is reduced, the adhesive force tends to be reduced. For example, when using a light stabilizer, a UV absorber or the like to improve the adhesion, the amount of these additives may be adjusted according to the thickness of the pressure-sensitive adhesive layer. For example, when the thickness of the pressure-sensitive adhesive layer is reduced, the blending amount of these additives may be increased. For example, when the thickness of the pressure-sensitive adhesive layer is 10 to 25 μm, the content of the light stabilizer or the UV absorber is 3.0 to 10 parts by mass with respect to 100 parts by mass of the (A) acrylic block copolymer. preferable. More preferably, it is 3.5-7.0 mass parts.

  The pressure-sensitive adhesive layer preferably has a high elastic modulus from the viewpoint of excellent drainage during construction. This is because, when the elastic modulus of the pressure-sensitive adhesive layer is high, the force of the squeegee can be easily transmitted to the adherend such as glass and water can be easily pushed out. From the above viewpoint, the elastic modulus of the pressure-sensitive adhesive layer is preferably 15000 Pa or more. More preferably, it is 20000 Pa or more. On the other hand, from the viewpoint of adhesion and the like, the elastic modulus of the pressure-sensitive adhesive layer is preferably 50000 Pa or less. More preferably, it is 40000 Pa or less. The elastic modulus of the pressure-sensitive adhesive layer can be measured by shear rate control (CSR) using a rheometer.

  The base film is preferably a light-transmitting polymer film from the viewpoint of excellent transparency and durability as an optical film (adhesive film for window pasting). Light transmittance means that the transmittance value in the wavelength region of 360 to 830 nm is 50% or more.

  Specific examples of the material (base polymer) for the light-transmitting polymer film include polyester resins such as polyethylene terephthalate (PET), polyethylene naphtholate (PEN), and polybutylene terephthalate (PBT), polyethylene, polypropylene, Polyolefin resin such as cycloolefin polymer, acrylic resin such as polymethyl methacrylate, polycarbonate (polycarbonate resin), polyvinyl chloride (vinyl chloride resin), ethylene-vinyl acetate copolymer, polystyrene, polyamide , Polymer materials such as polyetheretherketone, polyvinylidene chloride, triacetylcellulose, and polyurethane. These may be used alone or in combination of two or more. Among these, polyester resins, polyolefin resins, acrylic resins, polycarbonate resins, and vinyl chloride resins are preferable materials from the viewpoint of excellent transparency, durability, and processability. Further, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyethylene, polypropylene, and cycloolefin polymer are more preferable materials. In addition, polyethylene, polypropylene, and cycloolefin polymers are more preferable materials from the viewpoints of excellent flexibility, good drainage by a squeegee, easy construction, economical efficiency (low cost), and the like.

  The thickness of the base film may be appropriately adjusted in consideration of the application, optical characteristics, material type, durability, and the like. For example, it is preferably 25 μm or more from the viewpoints of being difficult to wrinkle during processing, difficult to break, handling properties when applied as an adhesive film for window pasting, anti-scattering performance and the like. More preferably, it is 38 μm or more. Further, from the viewpoint of flexibility, handleability, economical efficiency, etc., 125 μm or less is preferable. More preferably, it is 100 micrometers or less, More preferably, it is 50 micrometers or less. Moreover, 125 micrometers or less are preferable from a viewpoint of ensuring the outstanding softness | flexibility by setting it as predetermined thickness or less, and being easy to ensure the water draining property by a squeegee. More preferably, it is 100 μm or less. More preferably, it is 50 μm or less.

  The optical film according to the present invention can be suitably used as a film that can be attached to windows such as glass of buildings such as buildings and houses, and windows of vehicles such as automobiles. The optical film according to the present invention preferably has a functional layer for imparting functions such as solar shading to the window. A functional layer may be between a base film and an adhesive layer, and may be on the base film surface opposite to an adhesive layer.

  The optical film according to the present invention may further have a metal layer made of a metal thin film. The metal layer is made of a metal that easily reflects near infrared rays and far infrared rays, and functions as a solar radiation shielding layer that reflects heat rays (sunlight) and as a heat insulation layer that reflects indoor heating heat to ensure heat insulation. . That is, it has heat insulation and heat insulation.

  The optical film according to the present invention may further have a high refractive index layer in addition to the metal layer. The high refractive index layer can exhibit functions such as increasing light transmittance by being laminated together with the metal layer. The high refractive index layer has a higher refractive index than the base film and the metal layer. The refractive index refers to the refractive index for light of 633 nm. Examples of the high refractive index layer include metal oxide thin films and organic thin films.

  In the optical film according to the present invention, the metal layer may be one layer or two or more layers. Further, a metal layer and a high refractive index layer may be formed to overlap each other. The number of metal layers and high refractive index layers and their positions are not particularly limited. From the viewpoint of light transmittance, a configuration in which metal layers and high refractive index layers are alternately arranged is more preferable.

  The total number of layers of the metal layer and the high refractive index layer may be appropriately set according to demands for optical properties such as light transmittance and solar shading. Considering the film thickness, production cost, etc., it is preferably within the range of 1 to 10 layers. In consideration of optical characteristics, odd-numbered layers are more preferable, and 1-layer, 3-layer, 5-layer, 7-layer, and 9-layer are particularly preferable. Moreover, 3 layers are more preferable from the surface of cost.

  Specifically, a particularly preferable configuration is shown as follows: metal layer (one layer), high refractive index layer / metal layer (two layers), metal layer / high refractive index layer (two layers), high refractive index layer / metal layer / high Refractive index layer (3 layers), metal layer / high refractive index layer / metal layer (3 layers), high refractive index layer / metal layer / high refractive index layer / metal layer / high refractive index layer (5 layers), metal layer / High refractive index layer / Metal layer / High refractive index layer / Metal layer (5 layers), High refractive index layer / Metal layer / High refractive index layer / Metal layer / High refractive index layer / Metal layer / High refractive index layer ( 7 layers), metal layer / high refractive index layer / metal layer / high refractive index layer / metal layer / high refractive index layer / metal layer (7 layers), and the like.

  When the high refractive index layer is made of a metal oxide thin film, a barrier thin film may be formed on one side or both sides of the metal layer. The barrier thin film is a thin film accompanying the metal layer, and is counted as one layer together with the metal layer. The barrier thin film suppresses diffusion of elements constituting the metal layer into the metal oxide thin film.

  When two or more high refractive index layers are provided, all the high refractive index layers may be made of the same material, or some of the high refractive index layers are made of a material different from the others. Alternatively, all the high refractive index layers may be made of different materials.

  Next, the optical film which concerns on one Embodiment of this invention is demonstrated using drawing.

  In FIG. 1, the optical film which concerns on one Embodiment of this invention is shown. The optical film 10 has a functional layer 14, an adhesive layer 16, a polyolefin layer 18, and a hard coat layer 20 in this order on one side of the base film 12, and the other side of the base film 12. The adhesive layer 22 and the separator 24 are provided on the top.

  The functional layer 14 is directly formed on one surface of the base film 12. The adhesive layer 16 is a layer that adheres the functional layer 14 and the polyolefin layer 18, and is in contact with both the functional layer 14 and the polyolefin layer 18. The hard coat layer 20 is formed directly on the surface of the polyolefin layer 18. Therefore, the optical film 10 includes the base film 12, the functional layer 14 in contact with the base film 12, the adhesive layer 16 in contact with the functional layer 14, the polyolefin layer 18 in contact with the adhesive layer 16, and the hard in contact with the polyolefin layer 18. The coating layer 20 is provided in this order.

  The pressure-sensitive adhesive layer 22 is for attaching the optical film 10 to a window such as glass. The optical film 10 can be attached to a window via the pressure-sensitive adhesive layer 22 by peeling off the separator 24. The pressure-sensitive adhesive layer 22 becomes the pressure-sensitive adhesive layer according to the present invention described above (consisting of the present composition). The pressure-sensitive adhesive layer 22 is directly formed on the other surface of the base film 12. The separator 24 is made of, for example, a polymer film.

  The functional layer 14 has a metal layer made of a metal thin film and functions as a solar radiation shielding layer. As a structure of the functional layer 14, the thing of the 3 layer structure which consists of a high refractive index layer / metal layer / high refractive index layer is mentioned as a suitable thing from the base film 12 side. As the high refractive index layer, a layer made of a metal oxide thin film is preferable. As a metal of a metal layer, silver and a silver alloy are mentioned as a suitable thing. As a metal oxide of the high refractive index layer, titanium oxide is preferable. A barrier thin film may be formed on one surface or both surfaces of the metal thin film. As the barrier thin film, a metal oxide thin film is preferable. As a metal oxide of the barrier thin film, titanium oxide is preferable.

  As the substrate film 12, a polyethylene terephthalate (PET) film is preferable.

  The polyolefin layer 18 is made of a material containing polyolefin. The polyolefin layer 18 covers the surface of the functional layer 14 and can prevent salt water from entering the metal thin film from the surface of the functional layer 14. The polyolefin layer 18 is preferably formed from a polyolefin film for reasons such as excellent effect of suppressing salt water corrosion from the surface of the functional layer 14. Further, since polyolefin is a relatively flexible material, the polyolefin layer 18 is excellent in flexibility and can relieve squeegee stress when the optical film 10 is applied to a window. The material of the polyolefin layer 18 is not particularly limited as long as it is a polyolefin. Examples of the material of the polyolefin layer 18 include polypropylene and polycycloolefin. The material of the polyolefin layer 18 is preferably polypropylene from the viewpoint of excellent light transmittance. In particular, biaxially oriented polypropylene (OPP) is preferred.

  The thickness of the polyolefin layer 18 is preferably 30 μm or less from the viewpoint of excellent heat insulating properties (suppressing the heat flow rate low). More preferably, it is 24 μm or less. Moreover, it is preferable that it is 10 micrometers or more from a viewpoint of being excellent in the effect which relieve | moderates the squeegee stress at the time of construction. More preferably, it is 13 μm or more.

  The adhesive layer 16 can bond the polyolefin layer 18 on the surface of the functional layer 14. By having the adhesive layer 16 between the functional layer 14 and the polyolefin layer 18, interlayer adhesion between the functional layer 14 and the polyolefin layer 18 can be improved. The adhesive layer 16 contains an adhesive. The pressure-sensitive adhesive is applied by applying pressure using the adhesiveness of the surface, and is distinguished from an adhesive that exhibits a peeling resistance force by solidification as a pressure-sensitive adhesive. Examples of the pressure-sensitive adhesive include acrylic resin-based pressure-sensitive adhesives, silicone resin-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives. Here, the adhesive layer 16 is shown, but an adhesive layer containing an adhesive may be used instead of the adhesive layer 16.

  The thickness of the pressure-sensitive adhesive layer 16 is preferably 22.0 μm or less from the viewpoint of excellent heat insulation (suppressing the heat transmissivity low). More preferably, it is 5.0 micrometers or less, More preferably, it is 2.0 micrometers or less. Moreover, it is preferable that it is 0.3 micrometer or more from a viewpoint of being excellent in adhesiveness with the polyolefin layer 18, etc. More preferably, it is 0.5 micrometer or more, More preferably, it is 1.0 micrometer or more. Moreover, it is preferable that it is 0.3 micrometer or more from a viewpoint of being excellent in a high temperature creep characteristic. More preferably, it is 0.5 micrometer or more, More preferably, it is 1.0 micrometer or more.

  The hard coat 20 covers the surfaces of the functional layer 14 and the polyolefin layer 18 and can suppress the surface from being scratched. The thickness of the hard coat layer 20 is preferably 0.4 μm or more from the viewpoint of excellent scratch resistance. More preferably, it is 0.6 micrometer or more, More preferably, it is 0.8 micrometer or more. On the other hand, it is preferable that it is 2.0 micrometers or less from a viewpoint of being excellent in heat insulation (suppressing heat transmissivity low). More preferably, it is 1.6 micrometers or less, More preferably, it is 1.0 micrometers or less. Suitable examples of the hard coat layer 20 include a layer containing a curable resin and a layer containing an organic-inorganic hybrid material.

  Suitable examples of the curable resin include silicone resins and acrylic resins. The silicone resin and acrylic resin may be thermosetting, photocurable, or water curable. Suitable acrylic resins include acrylic / urethane resins, silicone acrylic resins, acrylic / melamine resins, and the like.

  An organic-inorganic hybrid material is formed of an organic material (raw material of an organic component) and an inorganic material (raw material of an inorganic component), and the organic material and the inorganic material are combined at the nano level or the molecular level. Organic-inorganic hybrid materials are, for example, network-like cross-linked structures in which inorganic materials dispersed in organic materials and organic materials undergo a reaction such as a polymerization reaction, and inorganic components are highly dispersed in organic components through chemical bonds. It is what has. Since the hard coat layer 20 is made of an organic-inorganic hybrid material, the interlayer adhesion between the polyolefin layer 18 and the hard coat layer 20 is improved. This is presumably because hardening shrinkage of the hard coat layer 20 is suppressed by adding an inorganic component to the material forming the hard coat layer 20.

  Examples of the raw material of the organic component forming the organic-inorganic hybrid material include curable resins. Examples of the curable resin include acrylic resin, epoxy resin, and urethane resin. These may be used alone or in combination of two or more. Moreover, a metal compound etc. are mentioned as a raw material of an inorganic component. Examples of the metal compound include a Si compound, a Ti compound, and a Zr compound. These may be used alone or in combination of two or more. The metal compound is a compound containing an inorganic component such as Si, Ti, or Zr, and can be compounded by causing a reaction such as a polymerization reaction with a raw material of the organic component. More specifically, examples of the metal compound include organometallic compounds. Examples of organometallic compounds include silane coupling agents, metal alkoxides, metal acylates, metal chelates, and silazanes.

  Furthermore, the content ratio of the metal component contained in the hard coat layer 20 made of an organic-inorganic hybrid material is preferably 5.9% by mass or more. More preferably, it is 23.7 mass% or more. When the content ratio of the metal component is 5.9% by mass or more, the interlayer adhesion between the polyolefin layer 18 and the hard coat layer 20 is remarkably improved. Further, the content ratio of the metal component contained in the hard coat layer 20 made of an organic-inorganic hybrid material is preferably 41.4% by mass or less. More preferably, it is 35.5 mass% or less. When the content ratio of the metal component is 41.4% by mass or less, the stability of the coating liquid is excellent, and a decrease in light transmittance of the hard coat layer 20 is suppressed.

  The content of the metal component contained in the hard coat layer made of an organic-inorganic hybrid material can be examined using a heating residue analysis, X-ray photoelectron spectroscopy (XPS), or the like.

  The surface of the polyolefin layer 18 that is in contact with the adhesive layer 16 or the surface that is in contact with the hard coat layer 20 may be subjected to surface treatment for the purpose of improving interlayer adhesion, if necessary. Examples of such surface treatment include corona treatment. In addition, an easy adhesion layer may be provided on the surface of the polyolefin layer 18 in contact with the adhesive layer 16 or the surface in contact with the hard coat layer 20 for the purpose of improving interlayer adhesion. Examples of the easy adhesion layer include a modified polyolefin layer having a polar group and an acrylic resin layer. Examples of the polar group include those having a heteroatom such as N, O, and S. Examples of the modified polyolefin include a polypropylene copolymer having a polar group, polyethylene having a polar group, polyisoprene having a polar group, polyisobutylene having a polar group, and the like.

  The optical film 10 can be manufactured as follows, for example. On the base film 12, the functional layers 14 are formed by sequentially stacking the thin films by a predetermined thin film forming method so as to have a predetermined laminated structure. Thereafter, heat treatment such as post-oxidation is performed as necessary. Thereafter, an adhesive is applied to the surface of the functional layer 14 to form the adhesive layer 16. Thereafter, a polyolefin film is placed on the surface of the adhesive layer 16 and pressure is applied to form the polyolefin layer 18. The hard coat layer 20 is formed by applying a curable resin or an organic-inorganic hybrid material on the surface of the polyolefin layer 18 to form a coating film, and performing a curing process on the formed coating film. be able to. In the case where an adhesive is used instead of the adhesive, the adhesive may be cured after coating the surface of the functional layer 14 and disposing a polyolefin film on the coating film. The pressure-sensitive adhesive layer 22 can be formed by applying the present composition (pressure-sensitive adhesive) to the surface of the base film 12 or the surface of the separator 24.

  FIG. 2 shows another optical film according to an embodiment of the present invention. The optical film 30 has the functional layer 14, the pressure-sensitive adhesive layer 22, and the separator 24 in this order on one surface of the base film 12, and the hard coat layer on the other surface of the base film 12. 20. That is, the optical film 30 includes the base film 12, the functional layer 14 in contact with the base film 12, the adhesive layer 22 in contact with the functional layer 14, and the separator 24 in contact with the adhesive layer 22 in this order. doing. The hard coat layer 20 is directly formed on the other surface of the base film 12. The structure of each layer is the same as that of the optical film 10 shown in FIG.

  Still another optical film according to an embodiment of the present invention includes the optical film 40 shown in FIG. The optical film 40 shown in FIG. 3 is a layer in which the base film 12 is made of a polyolefin film and the high refractive index layer of the functional layer 14 is an organic thin film as compared with the optical film 30 shown in FIG. 14 is a three-layer structure consisting of an organic thin film / metal layer / organic thin film from the base film 12 side). Other configurations are the same as those of the optical film 30 shown in FIG.

  Since polyolefin is a relatively flexible material, the polyolefin film is excellent in flexibility and can relieve squeegee stress when the optical film 40 is applied to a window. In addition, since it is flexible, it has good drainage by a squeegee and is easy to install. The film is a thin film, and generally has a thickness of 200 μm or less or 250 μm or less. What is necessary is just to have the softness | flexibility which can be wound in roll shape, and if it is such, it may be 200 micrometers or more or 250 micrometers or more thick. The film is generally delivered as a roll. The polyolefin film is preferably 25 μm or more from the viewpoints of processability, handling properties as an optical film, anti-scattering performance and the like. More preferably, it is 38 μm or more. Moreover, 125 micrometers or less are preferable from a viewpoint of ensuring the outstanding softness | flexibility by setting it as predetermined thickness or less, and being easy to ensure the water draining property by a squeegee. More preferably, it is 100 μm or less. More preferably, it is 50 μm or less.

  Examples of the polyolefin of the polyolefin film include chain polyolefin and cyclic polyolefin. Examples of the chain polyolefin include polyethylene, polypropylene, and ethylene-α olefin copolymer. Examples of the cyclic polyolefin include cycloolefin polymers. As the polyolefin, polypropylene is preferable from the viewpoints of light transmittance, durability, workability, and the like. In particular, from the viewpoint of light transmittance and the like, biaxially oriented polypropylene (OPP) is preferable.

  The polyolefin film may be subjected to surface treatment on one or both surfaces for the purpose of improving interlayer adhesion with the functional layer 14 or the hard coat layer 20 in contact therewith. Further, for the purpose of improving interlayer adhesion, an easy adhesion layer may be provided on one or both surfaces thereof. Further, for the purpose of improving interlayer adhesion, a surface treatment may be performed on one surface, and an easy adhesion layer may be provided on the other surface. Examples of such surface treatment include corona treatment and plasma treatment. Thereby, a hydroxyl group and an oxygen group are formed on the surface of the polyolefin film. Examples of the easy adhesion layer include a modified polyolefin layer having a polar group and an acrylic resin layer. Examples of the polar group include those having a heteroatom such as N, O, and S. Examples of the modified polyolefin include a polypropylene copolymer having a polar group, polyethylene having a polar group, polyisoprene having a polar group, polyisobutylene having a polar group, and the like.

  From the viewpoint of interlayer adhesion, a polyolefin film has a surface treatment applied to one or both surfaces, an easy-adhesion layer is provided on one or both surfaces, or a surface on one surface thereof. It is preferable that the process is performed and the easily bonding layer is provided in the other surface. In particular, it is preferable that one or both surfaces be subjected to surface treatment.

  In the optical film 40, since the base film 12 is made of a polyolefin film, the adhesion with the functional layer 14 tends to be poor as compared with a base film made of PET film. For example, when the optical film 40 attached at the time of replacement is peeled off from the window, it is peeled off between the functional layer 14 and the base film 12 made of polyolefin film to leave glue (the adhesive layer 22 and the functional layer 14 remain in the window). It is preferable to adjust the adhesive force of the pressure-sensitive adhesive layer 22 to the window in consideration of the material of the base film 12 and the like to the extent that does not occur. The adhesion can be adjusted by selecting the material of the pressure-sensitive adhesive layer 22, the type of additive such as a plasticizer, the amount of addition, the surface treatment of the base film 12 with plasma or corona, and the like.

  Moreover, in the optical film 40, since the base film 12 consists of polyolefin films, it exists in the tendency for adhesiveness with the hard-coat layer 20 to be bad compared with the base film which consists of PET films. For this reason, it is preferable that the hard-coat layer 20 is comprised from an organic inorganic hybrid material. When the hard coat layer 20 is composed of an organic-inorganic hybrid material, the interlayer adhesion between the polyolefin film and the hard coat layer 20 is improved. This is presumably because curing shrinkage of the hard coat layer 20 was suppressed by adding an inorganic component to the material forming the hard coat layer 20. That is, it is presumed that the distortion of the optical film 40 is reduced by suppressing the curing shrinkage of the hard coat layer 20, and the stress to be peeled between the polyolefin film and the hard coat layer 20 is reduced.

  Moreover, since the curing shrinkage of the hard coat layer 20 affects the distortion of the optical film 40, the curing shrinkage of the hard coat layer 20 also affects the interlayer adhesion between the polyolefin film included in the optical film 40 and the functional layer 14. give. That is, by suppressing the curing shrinkage of the hard coat layer 20, the distortion of the optical film 40 is reduced, and as a result, the stress to be peeled between the polyolefin film and the functional layer 14 is reduced. Therefore, the hard coat layer 20 made of an organic-inorganic hybrid material suppresses deterioration of interlayer adhesion between the polyolefin film and the functional layer 14 and improves the condition.

  The optical film 10 shown in FIG. 1 is strong because the base film 12 is made of a PET film, and is suitable for window pasting. The PET film easily absorbs infrared rays due to its functional group. However, when the optical film 10 is attached to the indoor side of the window, the PET film is disposed on the outdoor side of the functional layer 14, so that the indoor heating heat is Before being absorbed by the PET film, it is reflected by the metal layer of the functional layer 14 and can have excellent heat insulating properties. Therefore, the optical film 10 is excellent in heat insulation and heat insulation (insulation heat type).

  The optical film 20 shown in FIG. 2 is strong because the base film 12 is made of a PET film, and is suitable for window pasting. When the optical film 20 is affixed to the indoor side of the window, the PET film is disposed on the indoor side of the functional layer 14, so that the heat insulating property is inferior to that of the optical film 10 shown in FIG. However, since there are few layer structures, it is advantageous in terms of cost. Therefore, the optical film 20 is excellent in cost and heat shielding properties (low cost heat shielding type).

  The optical film 30 shown in FIG. 3 has little infrared absorption since the base film 12 is made of a polyolefin film. When the optical film 30 is attached to the indoor side of the window, the polyolefin film is disposed on the indoor side of the functional layer 14. However, since the infrared film absorbs less, reflection by the metal layer of the functional layer 14 is not hindered. For this reason, heat insulation can be made excellent. Moreover, since there are few layer structures, it is advantageous also in terms of cost. Therefore, the optical film 30 is excellent in cost, heat insulation, and heat insulation (low cost insulation heat type).

  The optical film according to the present invention is attached to a window via the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer 22) according to the present invention. At this time, it may be applied to the adherend without using the application liquid, but it is better to apply the application liquid using the application liquid. When the construction liquid is used, it is easy to adjust the sticking position at the time of construction, and it becomes easy to remove bubbles and wrinkles generated between the window and the optical film according to the present invention at the time of construction.

  In the film construction using the construction liquid, for example, after applying the construction liquid to the surface of the adherend or the adhesive surface, the adhesive surface of the optical film (adhesive film) is matched to the surface of the adherend applied with the construction liquid. At this time, the construction position of the optical film is adjusted while sliding the optical film with respect to the adherend using the construction liquid as a medium. In addition, the application liquid is applied from the outside of the optical film, and air bubbles generated between the optical film and the adherend are extruded by a jig such as a squeegee without causing damage to the optical film through the application liquid. The wrinkles generated in the optical film are stretched. At the same time, the construction liquid between the optical film and the adherend and the construction liquid on the outer surface of the optical film are discharged.

  The construction liquid may be a liquid containing an additive that imparts slipperiness such as a surfactant such as a neutral detergent, or water that does not contain an additive that imparts slipperiness such as a surfactant (or water Only). Examples of other additives include alcohols. Construction fluids containing additives that impart slipperiness, such as surfactants, are excellent in terms of adjusting the above-mentioned sticking position and removing bubbles from wrinkles, etc., and are also damaging to optical films during squeegee work. Excellent in that it is difficult to give. However, the construction liquid containing the additive tends to remain at the interface between the optical film and the glass, that is, poor appearance of the window due to poor water drainage.

  A liquid containing an additive imparting slipperiness such as a surfactant such as a neutral detergent as a construction liquid may contain a fatty acid amide as a surfactant. When such a construction liquid is used, adhesion after construction may be lowered. However, according to the present invention, even when such a construction liquid is used, a decrease in adhesion after construction can be suppressed.

  And according to this composition of the above structure and the optical film which concerns on this invention, this composition contains (A) acrylic block copolymer, (B) anti-adhesive agent, and (C) tackifying resin. Adhesive force after one month has elapsed after sticking to the adherend, measured under conditions of a tensile speed of 50 mm / min, after being allowed to stand at 80 ° C. for 72 hours, in accordance with JIS-K-6854-2 Is 4.0 N / 25 mm or more, it satisfies the high adhesion to the window after construction even after being placed in a high temperature environment. Moreover, it can be set as the adhesive film which was excellent in visible light transmission by including an acryl-type polymer, and was excellent in the optical characteristic with few hazes. Moreover, the strong contact | adhesion power which can ensure the scattering prevention of glass can be provided.

  And the optical film which concerns on this composition and this invention after leaving to stand at 80 degreeC for 72 hours is based on JIS-K-6854-2, and the initial stage adhesive force measured on the conditions of 50 mm / min of tensile speeds Is 0.5 N / 25 mm or less, the excellent reworkability enabling re-attachment during construction is maintained even after being placed in a high-temperature environment.

  By blending an appropriate plasticizer, it is possible to appropriately control the change in adhesion with time. By blending a plasticizer, initial adhesion is ensured, and the optical film is easily held in the window at the time of water application, and the workability is excellent. And the anti-scattering property is ensured by the adhesive force increasing with time of 72 hours or more by the plasticizer. Furthermore, reworkability is ensured by suppressing the adhesion force after 3 to 24 hours.

  An optical film having a high refractive index layer made of a metal oxide thin film is formed by a metal oxide thin film formed by a sol-gel method, while water leakage from the surface after water application is hindered by the metal oxide thin film. If so, the water permeability is higher than that of a metal oxide thin film formed by a physical method such as sputtering due to the formation of holes due to curing shrinkage or the like, and the water drainage from the surface after the water application is improved. Therefore, water can be expected to escape from the surface after the water application.

  The optical film 10 shown in FIG. 1 has many layer structures, and has a metal layer and a polyolefin layer. The optical film 30 shown in FIG. 2 has relatively few layer structures. The optical film 40 shown in FIG. 3 has a relatively small layer structure, but has a polyolefin layer. Therefore, among these, regarding the drainage from the surface after the water application, the optical film 30 shown in FIG. 2 is the best, the optical film 40 shown in FIG. 3 is the next best, and the optical film 10 shown in FIG. Not the best.

  Hereinafter, the metal oxide thin film, metal thin film, barrier thin film, and organic thin film of the functional layer 14 will be described in detail.

  As the metal oxide of the functional layer metal oxide thin film, titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, magnesium oxide, aluminum oxidation Products, zirconium oxide, niobium oxide, cerium oxide, and the like. These may be contained alone or in combination of two or more. These metal oxides may be composite oxides in which two or more metal oxides are combined. Among these, titanium oxide, indium and tin oxide, zinc oxide, tin oxide, and the like are preferable from the viewpoint of relatively high refractive index with respect to visible light.

  The metal oxide thin film can be formed by either a vapor phase method or a liquid phase method. The liquid phase method does not need to be evacuated or use a large electric power as compared with the gas phase method. Therefore, it is advantageous in terms of cost, and is excellent in productivity. As the liquid phase method, a sol-gel method can be suitably used from the viewpoint of easily leaving an organic component.

  The metal oxide thin film is mainly composed of the metal oxide described above, but may contain an organic component in addition to the metal oxide. It is because the softness | flexibility of a light transmissive laminated body can be improved more by containing an organic component. Specific examples of this type of organic component include components derived from a material for forming a metal oxide thin film, such as a component derived from a starting material of a sol-gel method.

  More specifically, as the organic component, for example, an organic metal compound (including a decomposition product thereof) such as a metal alkoxide, metal acylate, metal chelate or the like of a metal oxide, or the above organic metal compound Various additives such as an organic compound (described later) that reacts to form an ultraviolet-absorbing chelate can be exemplified. These may be contained alone or in combination of two or more.

  The lower limit of the content of the organic component contained in the metal oxide thin film is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably, from the viewpoint of easily imparting flexibility. It is good that it is 7% by mass or more. On the other hand, the upper limit of the content of the organic component contained in the metal oxide thin film is preferably 30% by mass or less, from the viewpoint of easily ensuring a high refractive index and easily ensuring solvent resistance. More preferably, it is 25 mass% or less, More preferably, it is good in it being 20 mass% or less. The organic content can be examined using X-ray photoelectron spectroscopy (XPS) or the like. Moreover, the kind of said organic content can be investigated using infrared spectroscopy (IR) (infrared absorption analysis) etc.

  More specifically, as the sol-gel method, for example, a coating liquid containing a metal organometallic compound that constitutes a metal oxide is coated in a thin film shape, and this is dried as necessary to obtain a metal oxide. Examples include a method of forming a precursor thin film of a thin film and then hydrolyzing and condensing an organometallic compound in the precursor thin film to synthesize an oxide of a metal constituting the organometallic compound. . According to this, a metal oxide thin film containing a metal oxide as a main component and containing an organic component can be formed. Hereinafter, the above method will be described in detail.

  The coating liquid can be prepared by dissolving the organometallic compound in a suitable solvent. In this case, specific examples of the organometallic compound include organic compounds of metals such as titanium, zinc, indium, tin, magnesium, aluminum, zirconium, niobium, cerium, silicon, hafnium, and lead. Can do. These may be contained alone or in combination of two or more.

  Specific examples of the organometallic compound include metal alkoxides, metal acylates, and metal chelates of the above metals. A metal chelate is preferable from the viewpoint of stability in air.

  As the organic metal compound, in particular, a metal organic compound that can be a metal oxide having a high refractive index can be preferably used. Examples of such organometallic compounds include organic titanium compounds.

  Specific examples of the organic titanium compound include M-O-R bonds such as tetra-n-butoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, and tetramethoxy titanium (R represents an alkyl group). , M represents a titanium atom) and an acylate of titanium having an M—O—CO—R bond (R represents an alkyl group and M represents a titanium atom) such as isopropoxy titanium stearate. Examples thereof include titanium chelates such as diisopropoxy titanium bisacetylacetonate, dihydroxy bis lactato titanium, diisopropoxy bis triethanolaminato titanium, diisopropoxy bis ethyl acetoacetate titanium, and the like. These may be used alone or in combination. These may be either monomers or multimers.

  The content of the organometallic compound in the coating liquid is preferably from 1 to 20% by mass, more preferably from 3 to 20% from the viewpoint of the film thickness uniformity of the coating film and the film thickness that can be applied at one time. It is good if it exists in the range of 15 mass%, More preferably, 5-10 mass%.

  Specific examples of the solvent for dissolving the organometallic compound include alcohols such as methanol, ethanol, propanol, butanol, heptanol and isopropyl alcohol, organic acid esters such as ethyl acetate, acetonitrile, acetone and methyl ethyl ketone. Examples thereof include ketones such as tetrahydrofuran, cycloethers such as dioxane, acid amides such as formamide and N, N-dimethylformamide, hydrocarbons such as hexane, aromatics such as toluene, and the like. These may be used alone or in combination.

  At this time, the amount of the solvent is preferably 5 to 100 times the amount of the solid content mass of the organometallic compound from the viewpoint of the film thickness uniformity of the coating film and the film thickness that can be applied at one time. More preferably, the amount is 7 to 30 times, and further preferably 10 to 20 times.

  When the amount of the solvent is more than 100 times, the film thickness that can be formed by a single coating becomes thin, and a tendency to require many coatings to obtain a desired film thickness is observed. On the other hand, when the amount is less than 5 times, the film thickness becomes too thick, and there is a tendency that the hydrolysis / condensation reaction of the organometallic compound does not proceed sufficiently. Therefore, the amount of the solvent is preferably selected in consideration of these.

  The coating liquid is prepared, for example, by mixing an organometallic compound weighed so as to have a predetermined ratio, an appropriate amount of solvent, and other components added as necessary, with a stirring means such as a stirrer for a predetermined time. It can be prepared by a method such as stirring and mixing. In this case, the components may be mixed at a time or may be mixed in a plurality of times.

  In addition, as a coating method of the coating liquid, from the viewpoint of easy uniform coating, a micro gravure method, a gravure method, a reverse roll coating method, a die coating method, a knife coating method, a dip coating method, a spin coating method, a bar coating method, and the like. Various wet coating methods such as a coating method can be exemplified as suitable ones. These may be appropriately selected and used, and one or more may be used in combination.

  Further, when the coated coating liquid is dried, it may be dried using a known drying apparatus. In this case, as the drying conditions, specifically, for example, a temperature range of 80 ° C to 120 ° C, Examples of the drying time include 0.5 minutes to 5 minutes.

  Specific examples of the means for hydrolyzing and condensing the organometallic compound in the precursor thin film include various means such as irradiation with light energy such as ultraviolet rays, electron beams, and X-rays, and heating. can do. These may be used alone or in combination of two or more. Among these, preferably, irradiation with light energy, particularly ultraviolet irradiation can be suitably used. Compared with other means, it is possible to produce a metal oxide at a low temperature in a short time, and it is difficult to give heat load such as thermal degradation to the light transmissive polymer film (especially in the case of ultraviolet irradiation, This has the advantage of requiring relatively simple equipment.) In addition, there is an advantage that an organic metal compound (including a decomposition product thereof) or the like is easily left as an organic component.

  Furthermore, when a sol-gel method using light energy at the time of sol-gel curing is employed, a rough metal oxide thin film can be obtained as compared with a metal oxide thin film formed by sputtering or the like. Therefore, when water is applied to the window glass of a building, even when water remains between the window glass, good water drainage can be obtained and the water application workability can be improved. Because there is an advantage.

  In this case, specific examples of the ultraviolet irradiator to be used include a mercury lamp, a xenon lamp, a deuterium lamp, an excimer lamp, a metal halide lamp, and the like. These may be used alone or in combination of two or more.

  Further, the amount of light energy to be irradiated can be variously adjusted in consideration of the type of the organometallic compound mainly forming the precursor thin film, the thickness of the precursor thin film, and the like. However, if the amount of light energy to be irradiated is too small, it is difficult to increase the refractive index of the metal oxide thin film. On the other hand, if the amount of light energy to be irradiated is excessively large, the light transmissive polymer film may be deformed by heat generated during the light energy irradiation. Therefore, these should be noted.

When the light energy to irradiate is ultraviolet rays, the amount of light is preferably from 300 to 8000 mJ at a measurement wavelength of 300 to 390 nm from the viewpoint of the refractive index of the metal oxide thin film, damage to the light transmissive polymer film, and the like. / Cm ² , more preferably in the range of 500 to 5000 mJ / cm ² .

  When light energy irradiation is used as a means for hydrolyzing and condensing the organometallic compound in the precursor thin film, it reacts with the organometallic compound in the coating liquid described above to absorb light (for example, absorbs ultraviolet rays). It is preferable to add an additive such as an organic compound that forms a chelate. When the above additives are added to the coating solution as the starting solution, light energy is irradiated where the light-absorbing chelate has been formed in advance, so that the metal oxide thin film is formed at a relatively low temperature. This is because a high refractive index can be easily achieved.

  Specific examples of the additive include additives such as β diketones, alkoxy alcohols, and alkanolamines. More specifically, examples of the β diketones include acetylacetone, benzoylacetone, ethyl acetoacetate, methyl acetoacetate, diethyl malonate, and the like. Examples of the alkoxy alcohols include 2-methoxyethanol, 2-ethoxyethanol, 2-methoxy-2-propanol, and the like. Examples of the alkanolamines include monoethanolamine, diethanolamine, and triethanolamine. These may be used alone or in combination.

  Of these, β diketones are particularly preferred, and acetylacetone can be most preferably used.

  The blending ratio of the additive is preferably 0.1 to 1 mol of the metal atom in the organometallic compound from the viewpoint of easiness in increasing the refractive index and stability in the state of the coating film. It is good that it is in the range of 2 times mole, more preferably 0.5 to 1.5 times mole.

  The film thickness of the metal oxide thin film can be adjusted in consideration of solar shading, visibility, reflection color, and the like. The lower limit value of the thickness of the metal oxide thin film is preferably 10 nm or more, more preferably 15 nm, from the viewpoints of easily suppressing the red and yellow coloring of the reflected color and obtaining high transparency. As described above, more preferably, it is 20 nm or more. On the other hand, the upper limit value of the thickness of the metal oxide thin film is preferably 90 nm or less, more preferably 85 nm, from the viewpoints of easily suppressing the green color of the reflected color and easily obtaining high transparency. Hereinafter, more preferably, it is 80 nm or less.

  Metals of the metal thin film include metals such as silver, gold, platinum, copper, aluminum, chromium, titanium, zinc, tin, nickel, cobalt, niobium, tantalum, tungsten, zirconium, lead, palladium, and indium. An alloy etc. are mentioned. These may be contained alone or in combination of two or more.

  As the metal of the metal thin film, silver or a silver alloy is preferable from the viewpoint of being excellent in visible light transmittance, heat ray reflectivity, conductivity, and the like at the time of lamination. More preferably, from the viewpoint of improving durability against environment such as heat, light, and water vapor, the main component is silver, and at least one metal element such as copper, bismuth, gold, palladium, platinum, and titanium is included. It should be a silver alloy. More preferably, a silver alloy containing copper (Ag—Cu alloy), a silver alloy containing bismuth (Ag—Bi alloy), a silver alloy containing titanium (Ag—Ti alloy), or the like may be used. This is because there are advantages such as a large silver diffusion suppression effect and cost advantage.

  In the case of using a silver alloy containing copper, in addition to silver and copper, for example, other elements and inevitable impurities may be contained as long as they do not adversely affect the aggregation / diffusion suppression effect of silver.

  Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be, Ru, Rh, Os, Ir, Bi, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, etc. in Ag-Cu alloys Element which can be precipitated as a single phase in Y; La, Ce, Nd, Sm, Gd, Tb, Dy, Ti, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

  When using a silver alloy containing copper, the lower limit of the copper content is preferably 1 atomic% or more, more preferably 2 atomic% or more, and even more preferably 3 atomic% or more, from the viewpoint of obtaining the effect of addition. Good to be. On the other hand, the upper limit of the copper content is preferably 20 atomic% or less, more preferably 10 atomic%, from the viewpoint of manufacturability such as easy to ensure high transparency and easy production of a sputtering target. Hereinafter, it is more preferable that it is 5 atomic% or less.

  Further, when using a silver alloy containing bismuth, in addition to silver and bismuth, for example, other elements and inevitable impurities may be included as long as they do not adversely affect the aggregation / diffusion suppression effect of silver. good.

  Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be, Ru, Rh, Os, Ir, Cu, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, etc., in Ag-Bi alloys Element which can be precipitated as a single phase in Y; La, Ce, Nd, Sm, Gd, Tb, Dy, Ti, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

  When using a silver alloy containing bismuth, the lower limit of the bismuth content is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably, from the viewpoint of obtaining the effect of addition. It may be 0.1 atomic% or more. On the other hand, the upper limit of the bismuth content is preferably 5 atomic% or less, more preferably 2 atomic% or less, and still more preferably 1 atomic% from the viewpoint of manufacturability such as easy production of a sputtering target. It is good to be below.

  In addition, when using a silver alloy containing titanium, other than silver and titanium, for example, other elements and inevitable impurities may be included as long as they do not adversely affect the aggregation / diffusion suppression effect of silver. good.

  Specific examples of the other elements include elements that can be dissolved in Ag such as Mg, Pd, Pt, Au, Zn, Al, Ga, In, Sn, Sb, Li, Cd, Hg, and As. ; Be, Ru, Rh, Os, Ir, Cu, Ge, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Si, Tl, Pb, Bi, etc., Ag-Ti system Elements that can be precipitated as a single phase in the alloy; Y, La, Ce, Nd, Sm, Gd, Tb, Dy, Zr, Hf, Na, Ca, Sr, Ba, Sc, Pr, Eu, Ho, Er, Tm Examples include elements capable of precipitating intermetallic compounds with Ag such as Yb, Lu, S, Se, and Te. These may be contained alone or in combination of two or more.

  When using a silver alloy containing titanium, the lower limit value of the titanium content is preferably 0.01 atomic% or more, more preferably 0.05 atomic% or more, and still more preferably, from the viewpoint of obtaining an addition effect. It may be 0.1 atomic% or more. On the other hand, the upper limit of the content of titanium is preferably 2 atomic% or less, more preferably 1.75 atomic% or less, and still more preferably, from the viewpoint that a complete solid solution is easily obtained when it is formed into a film. Is preferably 1.5 atomic% or less.

  Note that the proportion of subelements such as copper, bismuth and titanium can be measured using ICP analysis. Further, the metal (including alloy) constituting the metal thin film may be partially oxidized.

  The lower limit of the thickness of the metal thin film is preferably 3 nm or more, more preferably 5 nm or more, and further preferably 7 nm or more from the viewpoints of stability, heat ray reflectivity, and the like. On the other hand, the upper limit value of the thickness of the metal thin film is preferably 30 nm or less, more preferably 20 nm or less, and further preferably 15 nm or less, from the viewpoint of transparency of visible light, economy, and the like.

  Here, as a method of forming the metal thin film, specifically, for example, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, MBE, laser ablation, thermal CVD, etc. Examples thereof include a vapor phase method such as a chemical vapor deposition method (CVD) such as a plasma CVD method. The metal thin film may be formed using any one of these methods, or may be formed using two or more methods.

  Of these methods, sputtering methods such as a DC magnetron sputtering method and an RF magnetron sputtering method can be preferably used from the viewpoint of obtaining a dense film quality and relatively easy film thickness control.

  In addition, the metal thin film may be oxidized within the range which does not impair the function of a metal thin film by receiving the post-oxidation etc. which are mentioned later.

  The barrier thin film associated with the metal thin film mainly has a barrier function that suppresses diffusion of elements constituting the metal thin film into the metal oxide thin film. Moreover, by interposing between a metal oxide thin film and a metal thin film, it can also contribute to the improvement of adhesiveness of both. The barrier thin film may have discontinuous portions such as floating islands as long as the diffusion can be suppressed.

  Specific examples of the metal oxide constituting the barrier thin film include, for example, titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, and magnesium oxide. And aluminum oxide, zirconium oxide, niobium oxide, cerium oxide, and the like. These may be contained alone or in combination of two or more. Further, these metal oxides may be double oxides in which two or more metal oxides are combined. The barrier thin film may contain inevitable impurities in addition to the metal oxide.

  Here, the barrier thin film is mainly composed of a metal oxide contained in the metal oxide thin film from the viewpoint of excellent diffusion suppression effect of the metal constituting the metal thin film and excellent adhesion. good.

More specifically, for example, when a TiO ₂ thin film is selected as the metal oxide thin film, the barrier thin film is a titanium oxide thin film mainly composed of an oxide of Ti that is a metal contained in the TiO ₂ thin film. Good to have.

  When the barrier thin film is a titanium oxide thin film, the barrier thin film may be a thin film formed as titanium oxide from the beginning, a thin film formed by post-oxidizing a metal Ti thin film, or It may be a thin film formed by post-oxidizing a partially oxidized titanium oxide thin film.

  The barrier thin film is mainly composed of a metal oxide in the same manner as the metal oxide thin film, but is set to be thinner than the metal oxide thin film. This is because the diffusion of the metal constituting the metal thin film occurs at the atomic level, so that it is not necessary to increase the film thickness to a sufficient level to ensure a sufficient refractive index. Further, by forming the thin film, the film formation cost can be reduced correspondingly, and the production cost can be reduced.

  The lower limit value of the thickness of the barrier thin film is preferably 1 nm or more, more preferably 1.5 nm or more, and further preferably 2 nm or more, from the viewpoint of easily ensuring barrier properties. On the other hand, the upper limit value of the thickness of the barrier thin film is preferably 15 nm or less, more preferably 10 nm or less, and still more preferably 8 nm or less, from the viewpoint of economy and the like.

  When the barrier thin film is mainly composed of titanium oxide, the lower limit value of the atomic molar ratio Ti / O of titanium to oxygen in the titanium oxide is 1.0 / 4.0 or more from the viewpoint of barrier properties and the like. Preferably, 1.0 / 3.8 or higher, more preferably 1.0 / 3.5 or higher, even more preferably 1.0 / 3.0 or higher, most preferably 1.0 / 2.8. It is good to be above.

  When the barrier thin film is mainly composed of titanium oxide, the upper limit value of the atomic molar ratio Ti / O of titanium to oxygen in the titanium oxide is preferably 1.0 / 0.5 or less, more preferably 1.0 / 0.7 or less, more preferably 1.0 / 1.0 or less, even more preferably 1.0 / 1.2 or less, most preferably 1 0.0 / 1.5 or less is preferable.

  The Ti / O ratio can be calculated from the composition of the thin film. As a method for analyzing the composition of the thin film, energy dispersive X-ray fluorescence analysis (EDX) can be suitably used from the viewpoint that the composition of an extremely thin film can be analyzed relatively accurately.

  A specific composition analysis method will be described. First, a test piece having a thickness of 100 nm or less in a cross-sectional direction of a functional layer including the thin film to be analyzed is prepared using an ultrathin section method (microtome) or the like. Next, the positions of the functional layer and the thin film are confirmed by a transmission electron microscope (TEM) from the cross-sectional direction. Next, an electron beam is emitted from the electron gun of the EDX apparatus and is incident on the vicinity of the central portion of the thin film to be analyzed. Electrons incident from the surface of the test specimen enter to a certain depth and generate various electron beams and X-rays. By detecting and analyzing characteristic X-rays at this time, the constituent elements of the thin film can be analyzed.

  As the barrier thin film, a vapor phase method can be suitably used from the viewpoint that a dense film can be formed, and a thin film of about several nm to several tens of nm can be formed with a uniform film thickness.

  Specific examples of the vapor phase method include physical vapor deposition methods (PVD) such as vacuum deposition, sputtering, ion plating, MBE, and laser ablation, thermal CVD, and plasma CVD. Examples thereof include chemical vapor deposition (CVD) and the like. As the vapor phase method, a sputtering method such as a DC magnetron sputtering method or an RF magnetron sputtering method is preferable from the viewpoint of excellent adhesion at the film interface as compared with a vacuum deposition method and the like and easy control of the film thickness. Can be used.

  Each barrier thin film included in the functional layer may be formed using any one of these vapor phase methods, or may be formed using two or more methods. May be.

  The barrier thin film may be formed as a metal oxide thin film from the beginning by using the above-described vapor phase method, or a metal thin film or a partially oxidized metal oxide thin film is once formed. Later, it can be formed by oxidizing it afterwards. The partially oxidized metal oxide thin film refers to a metal oxide thin film that has room for further oxidation.

  When forming a metal oxide thin film from the beginning, specifically, for example, a gas containing oxygen as a reactive gas is mixed with an inert gas such as argon or neon as a sputtering gas, and the metal and oxygen are mixed. A thin film may be formed while reacting (reactive sputtering method). For example, when the titanium oxide thin film having the Ti / O ratio is obtained by using the reactive sputtering method, the oxygen concentration in the atmosphere (volume ratio of the gas containing oxygen to the inert gas) is the above-described film thickness range. The optimum ratio may be appropriately selected in consideration of the above.

  On the other hand, when a metal thin film or a partially oxidized metal oxide thin film is formed and then post-oxidized later, specifically, the functional layer is formed on the light-transmitting substrate, and then the function is performed. The metal thin film in the layer or the partially oxidized metal oxide thin film may be post-oxidized. Note that the sputtering method or the like may be used for forming the metal thin film, and the reactive sputtering method or the like described above may be used for forming the partially oxidized metal oxide thin film.

  Examples of the post-oxidation technique include heat treatment, pressure treatment, chemical treatment, and natural oxidation. Of these post-oxidation techniques, heat treatment is preferable from the viewpoint of enabling post-oxidation relatively easily and reliably. Examples of the heat treatment include, for example, a method in which a light transmissive polymer film having the above-described functional layer is present in a heating atmosphere such as a heating furnace, a method of immersing in warm water, a method of microwave heating, Examples thereof include a method of energizing and heating a metal thin film, a partially oxidized metal oxide thin film, and the like. These may be performed in combination of one or two or more.

  As heating conditions at the time of the heat treatment, specifically, for example, preferably 30 ° C. to 60 ° C., more preferably 32 ° C. to 57 ° C., more preferably 35 ° C. to 55 ° C., heating When present in the atmosphere, the heating time is preferably selected from 5 days or longer, more preferably 10 days or longer, and even more preferably 15 days or longer. This is because the post-oxidation effect, the thermal deformation / fusing suppression of the light transmissive polymer film 12 and the like are good within the above heating condition range.

  The heating atmosphere during the heat treatment is preferably an atmosphere containing oxygen or moisture, such as in the air, a high oxygen atmosphere, or a high humidity atmosphere. Particularly preferably, it is in the air from the viewpoint of manufacturability and cost reduction.

  When the above-mentioned post-oxidation thin film is included in the functional layer, since the moisture and oxygen contained in the metal oxide thin film are consumed during the post-oxidation, the metal oxide is exposed to sunlight. The thin film becomes difficult to chemically react. Specifically, for example, when the metal oxide thin film is formed by a sol-gel method, the water and oxygen contained in the metal oxide thin film are consumed during post-oxidation. The starting material (metal alkoxide, etc.) by the sol-gel method remaining in the thin film and moisture (adsorbed water, etc.), oxygen, etc. are difficult to undergo a sol-gel curing reaction by sunlight. Therefore, it becomes possible to relieve internal stress caused by volume change such as curing shrinkage, and it becomes easy to suppress interfacial peeling of the functional layer, and to improve durability against sunlight.

  When the base film is a polyethylene terephthalate film, the organic thin film has a refractive index of 1.58 for the light of 633 nm of the polyethylene terephthalate film, so the refractive index of the organic thin film for the light of 633 nm is at least 1.59 or more. , Preferably 1.60 or more. More preferably, it is 1.65 or more.

  An organic thin film consists of a polymer which has a higher refractive index than a metal thin film and a base film, and has a functional group containing at least one element selected from N, S, and O. Further, among N, S, and O, a polymer containing N and S is preferable in that the refractive index tends to be relatively high.

  Examples of the functional group containing N include a carbazole group, an imide group, and a nitrile group. Examples of the polymer having a functional group containing N include polyvinyl carbazole (PVK) and polyimide.

Examples of the functional group containing S include a sulfonyl group (—SO ₂ —), a thiol group, and a thioester group. Examples of the polymer having a functional group containing S include polyethersulfone (PES), polysulfone, and polyphenylsulfone.

  Examples of the functional group containing O include a carboxyl group, an ester group, a ketone group, and a hydroxyl group. And as a polymer which has a functional group containing O, an epoxy resin etc. are mentioned.

  However, even if the polymer has a functional group including N, S, and O, those having a refractive index of less than 1.60 with respect to light of 633 nm cannot obtain good optical characteristics as a heat ray cut film, so that an organic thin film It cannot be used as a material. Examples of such materials include polymethacrylonitrile (n = 1.40), acrylates such as 2-hydroxyethyl methacrylate (n = about 1.4), polyvinyl alcohol (n = 1.53), polyester resin (n = 1.58), polyvinyl butyral (n = 1.485), and the like. Further, although it is a polymer that does not contain N, S, or O, a vinyl fluoride-hexafluoropropylene copolymer (n = 1.4188) is also a material having a relatively low refractive index. Tetrabutyl titanate (n = 1.491) is also a relatively low refractive index material.

  Isocyanate compounds are difficult to use as organic thin film materials from the standpoint of toxicity. Polyurethane resins are vulnerable to heat and are difficult to use as materials for heat ray cut films that are exposed to solar radiation. In addition, since it is highly hydrolyzable and deteriorates over time due to moisture, it is not practical in terms of durability as a material for a heat ray cut film that is stuck to an adherend such as a window glass for a long time. Polystyrene resin does not have a functional group of N, S, and O, so it does not adhere to the metal thin film, and has a hard and brittle property, so it is difficult to use as a material for a heat ray cut film.

  Moreover, it is preferable that the polymer of an organic thin film is excellent in heat resistance. From this viewpoint, the glass transition point (Tg) of the polymer of the organic thin film is preferably 60 ° C. or higher. More preferably, it is 80 ° C. or higher.

  The thickness of the organic thin film can be adjusted in consideration of solar shading, visibility, reflection color, and the like. The film thickness of the organic thin film may be the same or different. The lower limit of the film thickness of the organic thin film is preferably 10 nm or more, more preferably 15 nm or more, from the viewpoints of easily suppressing the red and yellow colors of the reflected color and easily obtaining high light transmittance. More preferably, it is 20 nm or more. On the other hand, the upper limit value of the film thickness of the organic thin film is preferably 90 nm or less, more preferably 85 nm or less, from the viewpoints of easily suppressing the green color of the reflected color and easily obtaining high light transmittance. More preferably, it is 80 nm or less.

  The organic thin film can be formed by preparing a coating solution containing a polymer, coating the surface of the substrate film and the like, and then drying to form a coating film. In preparing the coating solution, a solvent for dissolving the polymer can be used as necessary. Examples of such solvents include alcohols such as methanol, ethanol, propanol, butanol, heptanol and isopropyl alcohol, organic acid esters such as ethyl acetate, ketones such as acetonitrile, acetone and methyl ethyl ketone, and cycloethers such as tetrahydrofuran and dioxane. Acid amides such as formamide and N, N-dimethylformamide, hydrocarbons such as hexane, and aromatics such as toluene and xylene. These may be used alone or in combination.

  Hereinafter, the present invention will be described in detail using Examples and Comparative Examples.

Example 1
As an optical film according to Example 1, on one surface of a base film, a thin film layer composed of the following three-layer thin films, an adhesive layer laminated in contact with the thin film layer, and laminated in contact with the adhesive layer An optical film having an adhesive layer and a hard coat layer laminated in contact with the polyolefin layer and having an adhesive layer on the other surface of the base film was produced.

In the optical film according to Example 1, the TiO ₂ thin film (first layer) by the sol-gel method and the UV irradiation (first layer) | titanium oxide thin film / Ag—Cu alloy thin film / titanium oxide thin film (on the one surface of the base film) (Second layer) | It has a thin film layer in which TiO ₂ thin films (third layer) by sol-gel method and UV irradiation are sequentially laminated.

  The titanium oxide thin film is formed by thermally oxidizing a metal Ti thin film, and this corresponds to a barrier thin film. This titanium oxide thin film is included in the Ag—Cu alloy thin film as a thin film accompanying the Ag—Cu alloy thin film, and the number of laminated layers is counted.

  A specific manufacturing procedure will be described below.

(Preparation of coating solution)
First, a coating solution used for forming a TiO ₂ thin film by a sol-gel method was prepared. That is, tetra-n-butoxytitanium tetramer (manufactured by Nippon Soda Co., Ltd., “B4”) as titanium alkoxide, and acetylacetone as an additive that forms an ultraviolet-absorbing chelate, n-butanol and isopropyl It mix | blended with the mixed solvent with alcohol, and this was mixed for 10 minutes using the stirrer, and the coating liquid was prepared. At this time, the composition of tetra-n-butoxy titanium tetramer / acetylacetone / n-butanol / isopropyl alcohol was 6.75% by mass / 3.38% by mass / 59.87% by mass / 30.00% by mass, respectively. did.

(Formation of thin film layer)
As a base film, a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., “Cosmo Shine (registered trademark) A4100”) (hereinafter referred to as “PET film”) having an easy-adhesion layer on one side is used. A TiO ₂ thin film was formed as a first layer on the surface (PET surface) side opposite to the easily adhesive layer surface side of this PET film by the following procedure.

That is, the coating liquid was continuously applied to the PET surface side of the PET film with a gravure roll having a predetermined groove volume using a micro gravure coater. Next, the coating film was dried at 100 ° C. for 80 seconds using an in-line drying furnace to form a precursor film of a TiO ₂ thin film. Subsequently, the precursor film was continuously irradiated with ultraviolet rays at the same linear velocity as that during the coating using an in-line ultraviolet irradiator. Thereby, a TiO ₂ thin film (first layer) was formed on the PET film by a sol-gel method using ultraviolet energy at the time of sol-gel curing (hereinafter sometimes abbreviated as “(sol gel + UV)”).

Next, each thin film constituting the second layer was formed on the first layer. That is, a lower metal Ti thin film was formed by sputtering on the first TiO ₂ thin film using a DC magnetron sputtering apparatus. Next, an Ag—Cu alloy thin film was formed on the lower metal Ti thin film by sputtering. Next, an upper metal Ti thin film was formed on the Ag—Cu alloy thin film by sputtering.

Next, as the third layer, a TiO ₂ thin film by (sol gel + UV) was formed on the second layer.

  Next, the obtained film with a thin film layer is heat-treated in the heating furnace at 40 ° C. for 300 hours in the atmosphere to thermally oxidize the metal Ti thin film contained in the thin film layer, thereby obtaining a titanium oxide thin film. It was.

In addition, the refractive index (measurement wavelength is 633 nm) of the TiO ₂ thin film was measured by FilmTek 3000 (manufactured by Scientific Computing International).

Moreover, content of the organic component contained in the TiO ₂ thin film was measured by X-ray photoelectron spectroscopy (XPS).

  Moreover, the EDX analysis was performed about the titanium oxide thin film formed by thermally oxidizing the metal Ti thin film, and Ti / O ratio was calculated | required as follows.

  That is, a thin film layer-attached film is cut out by a microtome (LKB Co., Ltd., “Ultrome V2088”), and the thickness of the thin film layer including the titanium oxide thin film (barrier thin film) to be analyzed is 100 nm or less in thickness Was made. The cross section of the produced test piece was confirmed with a field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”). Then, using an EDX apparatus (resolution of 133 eV or less) (“JED-2300T” manufactured by JEOL Ltd.), an electron beam is emitted from the electron gun of this apparatus, and a titanium oxide thin film (barrier thin film) to be analyzed The elemental element of the titanium oxide thin film (barrier thin film) was analyzed by detecting the incident characteristic X-ray and analyzing it.

Further, the content of the subelement (Cu) in the alloy thin film was determined as follows. That is, under each film forming condition, a test piece in which an Ag—Cu alloy thin film was formed on a glass substrate was separately prepared, and this test piece was immersed in a 6% HNO ₃ solution and eluted with ultrasonic waves for 20 minutes. Then, it measured by the concentration method of ICP analysis method using the obtained sample solution.

  Moreover, the film thickness of each thin film was measured from the cross-sectional observation of the test piece by the said field emission electron microscope (HRTEM) (the JEOL Co., Ltd. make, "JEM2001F").

  Table 1 shows the detailed layer structure of the thin film layer.

(Formation of adhesive layer)
On the surface of the thin film layer, an acrylic resin adhesive (“Main Agent: BPS5260, Curing Agent: BHS8515” manufactured by Toyo Ink Co., Ltd.) was applied to form an adhesive layer (thickness: 1.5 μm). The mixing ratio of the main agent: curing agent was 100: 3.0 by mass ratio.

(Formation of polyolefin layer)
Corona treatment is applied to the surface of the OPP film ("P2111" manufactured by Toyobo Co., Ltd., thickness: 20μm, single side: corona treatment), and the OPP film is placed on the adhesive layer and is in close contact with pressure. To form a polyolefin layer (thickness: 20 μm).

(Formation of hard coat layer)
A hard coat layer was formed on the polyolefin layer. The material of the hard coat layer is the following UV curable organic-inorganic hybrid material, which was UV cured after coating.
・ Organic / inorganic hybrid material: TG series manufactured by Dainichi Seika Kogyo, UV curing type

(Preparation of adhesive liquid)
A pressure-sensitive adhesive solution according to Example 1 was prepared by dissolving each component in toluene so as to have the composition (parts by mass) shown in Table 2. The details of each component are as shown below.
・ Acrylic block copolymer: Kuraray "Clarity LA2330" (surface treatment with fatty acid amide)
-Tackifying resin (1): Aromatically modified hydrogenated terpene resin, "Clearon K4100" manufactured by Yasuhara Chemical
Plasticizer 1: tricresyl phosphate, “TCP” manufactured by Daihachi Chemical Industry
・ UV absorber: “TINUVIN326” manufactured by BASF
・ Light stabilizer: “TINUVIN622SF” manufactured by BASF

(Formation of adhesive layer)
The pressure-sensitive adhesive liquid was coated on the easy-adhesion layer of the PET film by a blade method and dried at 110 ° C. to form a pressure-sensitive adhesive layer (thickness 40 μm). The optical film which concerns on Example 1 was produced by the above.

(Example 2-3)
In the preparation of the pressure-sensitive adhesive solution, a pressure-sensitive adhesive solution and an optical film according to Example 2-3 were produced in the same manner as in Example 1 except that the amount of the tackifier resin (1) was changed.

(Example 4-5)
In the preparation of the pressure-sensitive adhesive solution, a pressure-sensitive adhesive solution and an optical film according to Example 4-5 were produced in the same manner as in Example 2 except that the blending amount of the UV absorber was changed.

(Example 6)
In the preparation of the pressure-sensitive adhesive liquid, the pressure-sensitive adhesive liquid and optical film according to Example 6 were produced in the same manner as in Example 2 except that the blending amount of the UV absorber was changed and the thickness of the pressure-sensitive adhesive layer was changed.

(Example 7)
In the preparation of the pressure-sensitive adhesive solution, a pressure-sensitive adhesive solution and an optical film according to Example 7 were produced in the same manner as in Example 2 except that an epoxy resin was further added.
Epoxy resin: “Epicoat” manufactured by Momentive Specialty Chemicals

(Example 8-9)
In the preparation of the pressure-sensitive adhesive liquid, the pressure-sensitive adhesive liquid according to Example 8-9 and the pressure-sensitive adhesive liquid according to Example 8-9 were obtained in the same manner as in Example 2 except that tackifying resins (2) to (3) were used instead of the tackifying resin (1). An optical film was produced.
・ Tackifying resin (2): aromatic modified petroleum resin (α-methylstyrene aromatic monomer copolymer), “FTR2120” manufactured by Mitsui Chemicals
・ Tackifying resin (3): aromatic modified petroleum resin (aromatic / aliphatic hydrocarbon copolymer resin), “FTR6100” manufactured by Mitsui Chemicals

(Example 10)
An optical film having a base film, a functional layer and an adhesive layer formed on one side of the base film, and a hard coat layer formed on the other side of the base film was produced. That is, an optical film was prepared by laminating an adhesive layer / organic thin film / metal layer / organic thin film / hard coat layer in this order. As the pressure-sensitive adhesive liquid for forming the pressure-sensitive adhesive layer, the same composition as in Example 4 was used.

<Preparation of coating solution for organic thin film>
By diluting a triazine ring-containing polymer (“UR-108NT3” manufactured by Nissan Chemical Industries, Ltd.) to a viscosity (0.1 to 3.0 mPa · s) that can be applied with a gravure coater (solvent: PGMEA), an organic thin film A coating solution was prepared.

(Formation of thin film layer)
By applying the coating solution for organic thin film on one side of an OPP film ("Torphan BO 40-2500" manufactured by Toray Industries, Inc.) previously subjected to corona treatment using a micro gravure coater, and drying it An organic thin film (first layer) was formed. Next, an Ag—Cu alloy thin film was formed on the first organic thin film by sputtering. Next, a second organic thin film was formed on the Ag-Cu alloy thin film in the same manner as the formation of the first organic thin film. Furthermore, a hard coat layer was formed on the other side of the OPP film that had been previously subjected to corona treatment. The material of the hard coat layer was the same as that of Example 1-9.

(Comparative Example 1)
In the preparation of the pressure-sensitive adhesive liquid, the pressure-sensitive adhesive liquid and the optical film according to Comparative Example 1 were produced in the same manner as in Example 2 except that the plasticizer 2 was used instead of the plasticizer 1 and the tackifier resin was not blended. did.
Plasticizer 2: Di-2-ethylhexyl adipate (DOA), “DOA” manufactured by Daihachi Chemical Industry

(Comparative Example 2)
In the preparation of the pressure-sensitive adhesive solution, a pressure-sensitive adhesive solution and an optical film according to Comparative Example 2 were produced in the same manner as in Example 2 except that the tackifying resin (4) was used instead of the tackifying resin (1).
・ Tackifying resin (4): Hydrogenated terpene phenol resin, “YS Polystar TH130” manufactured by Yasuhara Chemical

(Water sticking construction)
Each optical film was affixed on one side of a 3 mm thick float glass. Specifically, as shown in FIG. 4, one end side of the optical film 1 is fixed to the support 2 with the tape 3, and the optical film 1 is bent 180 ° with the adhesive surface 1a facing outside. The side of the glass film 4 having a width of 50 mm and a thickness of 3 mm is aligned, and the support 2 is moved from one side of the glass plate 4 to the other side facing the glass plate 4. The optical film 1 was bonded to the glass plate 4 by combining the surfaces 1a. The bonding speed was 1.0 m / min. However, the bonding was performed by a method using the construction liquid A (water containing 0.1% by mass of neutral detergent “Charmy V Quick”). The application liquid A was sprayed onto both the glass surface 4a and the adhesive surface 1a before bonding, and bonded together. After bonding, the coating liquid A was sprayed again onto the film surface, and the surface was rubbed with a squeegee. Then, the construction liquid was extruded from the bonding interface and brought into close contact.

(Adhesion evaluation 1)
Each of the produced optical films is not heat-treated, and is bonded by the above water-pasting method, and after a predetermined time has elapsed (3 hours and 1 month later), the 180 degree peeling method defined in JIS-A-5759 is used. The adhesion (N / 25 mm) was measured. The width of the sample was 50 mm, and the tensile speed was 50 mm / min.

(Adhesion evaluation 2)
Each manufactured optical film is heat treated at 80 ° C. for 72 hours, and then pasted by the above-mentioned water pasting method, after a predetermined time has elapsed (3 hours and 1 month later), it is defined in JIS-A-5759. The adhesion (N / 25 mm) was measured by a 180 degree peeling method. The width of the sample was 50 mm, and the tensile speed was 50 mm / min.

(Visible light transmittance)
In accordance with JIS A5759, a transmission spectrum with a wavelength of 300 to 1000 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, “UV3100”), and the visible light transmittance was calculated. The greater the visible light transmittance, the better the transparency.

(UV transmittance)
In accordance with JIS A5759, a transmission spectrum with a wavelength of 300 to 1000 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, “UV3100”), and the UV transmittance was calculated.

(Haze)
The haze value was calculated | required using each produced optical film using the haze meter (HGM-2DP by Suga Test Instruments) based on JISK7105.

(Water remaining rate)
At the time of the water application, the size of the float glass 4 was 200 mm × 300 mm × 3 mmt. The construction solution used was a Charmy V Quick 0.1 wt% dilution. The adhesive film 1 is a bonding jig, and the squeegee is a urethane squeegee (size: 200 × 120 mm, thickness: 6 mm, “33-6082” manufactured by Kyokuto Sangyo Co., Ltd.). The number of times was one. The remaining water rate was evaluated when 24 hours (one day) had passed after the water application. From this water remaining rate, water drainage was evaluated. The remaining water ratio was the ratio (%) of the remaining water area to the glass area. The remaining water area was determined from the area of water bubbles remaining between the float glass 4 and the adhesive film 1.

  In Comparative Example 1, no tackifying resin was blended in the preparation of the pressure-sensitive adhesive liquid. For this reason, after holding the produced optical film in a high temperature environment (72 hours at 80 ° C.), the surface of the pressure-sensitive adhesive layer is analyzed (TOF-SIMS). Was observed. And in the adhesiveness 2 after holding | maintenance in a high temperature environment, the adhesive force of the passage of time (after one month) was low, and it was inferior to durability.

  In Comparative Example 2, hydrogenated terpene phenol was blended as a tackifying resin in the preparation of the pressure-sensitive adhesive solution. In the adhesion 2 after being held in a high temperature environment, the adhesion over time (after one month) was low and the durability was poor.

  In contrast, in Examples 1 to 7, an aromatic modified hydrogenated terpene resin was blended as a tackifier resin, and in 8 to 10, an aromatic modified petroleum resin was blended. After maintaining the prepared optical film in a high-temperature environment (72 hours at 80 ° C.), when the surface of the pressure-sensitive adhesive layer is analyzed (TOF-SIMS), the surface of the pressure-sensitive adhesive layer is adhered together with fatty acid amide as an anti-adhesive agent. An imparted resin was also observed. In the adhesion 2 after being held in a high-temperature environment, the initial (after 3 hours) adhesion was sufficient to ensure reworkability, and the adhesion over time (after one month) was very high. (4.0 N / 25 mm or more). Moreover, it turns out that an Example is excellent in transparency and there is also little water residue.

  And from an Example, the compounding quantity of tackifying resin is 4.5 mass parts or more with respect to 100 mass parts of acrylic block copolymers, and it is adhesiveness 2 after holding | maintenance in a high temperature environment, and time (after one month). It can be seen that the adhesion is higher. Moreover, it turns out that the compounding quantity of tackifying resin is 5.5 mass parts or less with respect to 100 mass parts of acrylic block copolymers, and a haze is more excellent.

  Next, the compatibility of the adhesion-preventing agent and the tackifying resin was evaluated. Specifically, DSC measurement was performed on the mixture of the adhesion-preventing agent and the tackifier resin, and the crystal melting peak was measured. In FIG. 5, the graph which shows the DSC chart measured about the mixture of an adhesion promoter and tackifying resin is shown. Table 3 shows the evaluation results. The DSC measurement conditions are shown below.

(DSC measurement method)
A sample was prepared by weighing 10 mg of ethylenebisstearic acid amide (EBS) used as an anti-adhesive agent and mixing the same amount of tackifying resin in a mortar. Using a differential scanning calorimeter (“DSC-60A” manufactured by Shimadzu Corporation), the temperature was melted to 200 ° C. at 10 ° C./min and immediately cooled to room temperature at −10 ° C./min. Thereafter, the temperature was raised at 10 ° C./min, and the crystal melting peak at that time was measured. The melting point peak of EBS alone is about 145 ° C. On the other hand, the melting point peak derived from the EBS in the mixed system caused a melting point drop, and the case where it was a single peak was marked as “good”, and the melting point peak derived from the EBS in the mixed system did not cause the melting point drop. In the case where there is, “×” indicates that the compatibility is low.
-EBS: NOF "Alflow H-50ES"

  In the mixed system with the tackifier resins (1) to (3), the melting point peak is single and the melting point drop is caused from the melting point peak derived from EBS. For this reason, it can be said that tackifying resin (1)-(3) and an adhesion preventive agent have compatibility. On the other hand, the mixed system with the tackifying resin (4) has a melting point peak (about 145 ° C.) derived from EBS, and the melting point peak is not single. For this reason, it cannot be said that the tackifier resin (4) and the anti-adhesive agent have high compatibility. This result is considered to be a factor that causes a difference particularly in the adhesion evaluation 2 after the heat treatment. That is, although the adhesion-preventing agent and the tackifier resin are transferred to the surface layer by heat treatment, it is presumed that those having compatibility have the tackifier resin wrapping the adhesion-preventing agent, thereby suppressing a decrease in adhesion.

  Although the embodiments and examples of the present invention have been described above, the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention. .

Claims (16)

  (A) Acrylic block copolymer, (B) Anti-adhesive, (C) Tackifying resin, and after standing at 80 ° C. for 72 hours, in accordance with JIS-K-6854-2, tensile speed 50 mm A pressure-sensitive adhesive composition for an optical film, characterized by having an adhesive force of 4.0 N / 25 mm or more after one month has elapsed after being attached to an adherend, measured under the conditions of / min.   In accordance with JIS-K-6854-2 after being left at 80 ° C. for 72 hours, the initial adhesive force measured under conditions of a tensile speed of 50 mm / min is 0.5 N / 25 mm or less. The pressure-sensitive adhesive composition for an optical film according to claim 1.   The pressure-sensitive adhesive composition for an optical film according to claim 1 or 2, wherein the (B) adhesion-preventing agent and the (C) tackifying resin are compatible combinations.   The pressure-sensitive adhesive composition for an optical film according to any one of claims 1 to 3, wherein the (C) is a styrene copolymer.   5. The styrene copolymer is one or more of a copolymer of a styrene monomer and a terpene resin and a copolymer of a styrene monomer and a petroleum resin, according to claim 4. An optical film pressure-sensitive adhesive composition.   The content of (C) is in a range of 3.0 to 7.0 parts by mass with respect to 100 parts by mass of (A), 6. An optical film pressure-sensitive adhesive composition.   An optical film having a pressure-sensitive adhesive layer formed on the film surface using the pressure-sensitive adhesive composition for an optical film according to claim 1.   Furthermore, it has a metal layer, The optical film of Claim 7 characterized by the above-mentioned.   The optical film according to claim 8, wherein the metal of the metal layer is one or more of silver, silver alloy, aluminum, alloy steel, and gold.   Furthermore, it has a high refractive index layer whose refractive index is higher than the said metal layer, The optical film of Claim 8 or 9 characterized by the above-mentioned.   The optical film according to claim 10, wherein the high refractive index layer is one or more of a metal oxide thin film and an organic thin film.   The optical film according to claim 11, wherein the metal oxide thin film is formed by a sol-gel method.   The thickness of a base film is in the range of 25-125 micrometers, The optical film of any one of Claims 7-12 characterized by the above-mentioned.   14. The base polymer of the base film is any one of a polyester resin, a polyolefin resin, an acrylic resin, a polycarbonate resin, and a vinyl chloride resin. The optical film described in 1.   The optical film according to claim 7, wherein the base film is a biaxially stretched polypropylene film.   The pressure-sensitive adhesive layer, the metal layer, the organic thin film as a high refractive index layer having a refractive index higher than that of the metal layer, and a base film, and include a pressure-sensitive adhesive layer / organic thin film / metal layer / organic thin film / base film. The optical film according to any one of claims 13 to 15, wherein the optical film is laminated in the order of.