JP2015140379A - Adhesive composition for film and adhesive film and heat shielding adhesive film using the same, construction method of adhesive film and construction method of heat shielding adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition for film improving workability of a film to an adherend such as window glass, an adhesive film and a heat shielding adhesive film using the same, a construction method of the adhesive film and the heat shielding adhesive film.SOLUTION: There is provided an adhesive composition for film containing an acryl block copolymer and a plasticizer. There is also provided an adhesive film, a heat shielding adhesive film 10 having an adhesive layer 22 formed by using the adhesive composition for film on a film face and capable of being adhered to a face of an adherend with water containing no additive providing slipperiness.

Description

  The present invention relates to a pressure-sensitive adhesive composition for a film, a pressure-sensitive adhesive film using the same, a heat-shielding pressure-sensitive adhesive film, a method for applying a pressure-sensitive adhesive film, and a method for applying a heat-shielding pressure-sensitive adhesive film.

  A heat insulating film having a heat insulating property may be applied to a window glass of a building such as a building or a house or a window glass of a vehicle such as an automobile for the purpose of shielding solar radiation. As this type of heat-shielding film, an infrared reflective substrate having an infrared reflective layer, a protective layer made of a polycycloolefin layer provided on the surface of the infrared reflective layer, and a transparent substrate that supports the infrared reflective layer from the back side (patent) Document 1), a transparent laminated film (Patent Document 2) having a transparent laminated portion in which metal oxide layers and metal layers are alternately laminated on a surface of a transparent polymer film, and a protective layer made of a cured product (Patent Document 2), An infrared reflective film (Patent Document 3) having a reflective layer and a protective layer composed of an olefin-based resin layer and a hard coat layer on the surface is known.

JP 2011-104887 A JP 2012-030577 A JP 2013-010341 A

  This type of heat-shielding film is attached to a window glass or the like using an adhesive. Conventional pressure-sensitive adhesives are pressure-sensitive and have strong adhesive strength from the beginning. When a heat-shielding film using this pressure-sensitive adhesive is brought into close contact with a window glass or the like with pressure, it is immediately shielded against the window glass or the like with a strong adhesive force. A thermal film can be adhered.

  However, since the pressure-sensitive adhesive has strong adhesive force from the beginning, it is not easy to shift the position of the heat-shielding film after aligning the adhesive surface with a window glass or the like. In addition, it is not easy to remove bubbles generated between the heat insulating film and the window glass, wrinkles generated in the heat insulating film, and the like. Therefore, conventionally, using a construction liquid in which an additive that improves slipperiness, such as a detergent, is diluted with water, it is easy to slip between the heat shield film and the window glass, etc. And wrinkle removal. However, it is still difficult to perform bonding with high quality, and for example, in Japan, glass pane construction technicians who are national qualifications are often required for construction on window glass. In addition, the preparation of such a construction liquid requires the experience and intuition of the installer, and the preparation according to the situation is required.

  Moreover, when a pressure-sensitive adhesive is used, it is necessary to make the heat-shielding film adhere to a window glass or the like with pressure, and in order to construct it evenly, force adjustment is required and construction technology is required.

  The problem to be solved by the present invention is a film pressure-sensitive adhesive composition for improving the workability of a film on an adherend such as a window glass, a pressure-sensitive adhesive film using the same, a heat-shielding pressure-sensitive adhesive film, and a method for applying the pressure-sensitive adhesive film An object of the present invention is to provide a method for constructing a heat-shielding adhesive film.

  In order to solve the above-described problems, the pressure-sensitive adhesive composition for a film according to the present invention includes an acrylic block copolymer and a plasticizer.

  In this case, it is preferable that the shear modulus measured at 20 ° C. according to JIS-K-7244-1 is 0.56 MPa or less.

  Further, in accordance with JIS-K-6854-2, the initial adhesion measured under the condition of a tensile speed of 50 mm / min is 0.5 N / 25 mm or less, and one month has elapsed after being attached to the adherend. It is preferable that the subsequent adhesion is 3.0 N / 25 mm or more.

  And it is preferable that content of the said plasticizer exists in the range of 5-60 mass parts with respect to 100 mass parts of said acrylic block copolymers.

  The solubility parameter of the plasticizer is preferably in the range of 8.0 to 9.9.

  The molecular weight of the plasticizer is preferably in the range of 300 to 500.

  The plasticizer is preferably one or more selected from dioctyl phthalate, dioctyl adipate, diisononyl phthalate, and tributyl acetylcitrate.

  Furthermore, it is preferable to contain a silane coupling agent.

  The silane coupling agent is preferably a silane coupling agent having an epoxy group, a methacryloxy group, an acryloxy group, or an amino group.

  Furthermore, it is preferable to contain at least one of an antioxidant and a light stabilizer.

  And the adhesive film which concerns on this invention makes it a summary to have an adhesive layer formed using said adhesive composition for films on a film surface.

  Moreover, the heat-shielding adhesive film which concerns on this invention makes it a summary to have the thin film layer which consists of a single layer or multiple layers in which the metal thin film is further contained in said adhesive film.

  In this case, the metal of the metal thin film is preferably silver or a silver alloy.

  The gist of the pressure-sensitive adhesive film construction method according to the present invention is to attach the pressure-sensitive adhesive film to the surface of an adherend using water that does not contain an additive that imparts slipperiness.

  Moreover, the construction method of the heat-shielding pressure-sensitive adhesive film according to the present invention is summarized in that the heat-shielding pressure-sensitive adhesive film is attached to the surface of the adherend using water that does not contain an additive that imparts slipperiness. Is.

  Examples of the additive that imparts slipperiness include surfactants.

  The film pressure-sensitive adhesive composition according to the present invention has a high level of self-adhesiveness by containing an acrylic block copolymer and a plasticizer. That is, when adhering to a hard surface such as glass, the air easily escapes from the adhesion interface, the residual amount of air at the interface is extremely small, and it can be peeled off and reattached. According to this composition, since the initial adhesive force is kept low, it is easy to reattach the film to the adherend during construction, and the adjustment of the construction position of the film is facilitated. Further, even if water is used as the construction liquid, the slipperiness between the film and the adherend is ensured, so that no preparation of the construction liquid is required, and a high level of experience and intuition is not required of the construction person. And although the initial adhesion is kept low, the adhesion increases to a predetermined size over time, so unlike the pressure-sensitive adhesive, there is no need to apply force to the film during construction, and advanced construction technology Is not required. Therefore, the construction of the film becomes simpler than before, and the workability of the film on an adherend such as a window glass can be improved.

  In this case, when the shear modulus measured in accordance with JIS-K-7244-1 at 20 ° C. is 0.56 MPa or less, foreign matter is easily embedded, so that a smooth and uniform construction surface is formed. Cheap.

  And in accordance with JIS-K-6854-2, the initial adhesive force measured under the condition of a tensile speed of 50 mm / min is 0.5 N / 25 mm or less, and one month has elapsed since it was attached to the adherend. When the subsequent adhesion is 3.0 N / 25 mm or more, it becomes easy to reattach the film to the adherend during construction, and the adjustment of the construction position of the film becomes easy. Further, even if water is used as the construction liquid, the slipperiness between the film and the adherend is ensured, so that no preparation of the construction liquid is required, and a high level of experience and intuition is not required of the construction person. Unlike pressure-sensitive adhesives, it is not necessary to apply force to the film during construction, and advanced construction techniques are not required. Therefore, the construction of the film becomes simpler than before, and the workability of the film on an adherend such as a window glass can be improved. Note that if the initial adhesion is extremely low, for example, when a heavily curled film is attached, the end may float or peel off. However, if the initial adhesion is 0.01 N / 25 mm or more, this Such a problem does not occur.

  And when content of the said plasticizer exists in the range of 5-60 mass parts with respect to 100 mass parts of said acrylic block copolymers, the balance of the increase of self-adhesiveness, initial adhesiveness, and adhesive force with time is included. Excellent.

  When the solubility parameter of the plasticizer is within the range of 8.0 to 9.9, it is excellent in compatibility between the plasticizer and the acrylic block copolymer and can form a uniform composition without phase separation. it can. Thereby, an adhesive surface with less unevenness in terms of adhesion can be formed.

  And when the molecular weight of the said plasticizer exists in the range of 300-500, it is excellent in compatibility of a plasticizer and an acrylic block copolymer, and can form the uniform composition without phase separation. Thereby, an adhesive surface with less unevenness in terms of adhesion can be formed.

  And, when the plasticizer is one or more selected from dioctyl phthalate, dioctyl adipate, diisononyl phthalate and tributyl acetylcitrate, the initial adhesion is excellent in the effect of imparting self-adhesiveness. Excellent adhesion, large increase in adhesion over time, excellent compatibility between plasticizer and acrylic block copolymer, forming a uniform composition without phase separation, and adhesion with little unevenness in terms of adhesion A surface can be formed.

  And when a silane coupling agent is further contained, self-adhesiveness improves and initial adhesiveness can be improved. In addition, there is an effect of speeding up the increase in adhesion with time. The effect is higher when the silane coupling agent is a silane coupling agent having an epoxy group, a methacryloxy group, an acryloxy group, or an amino group.

  Further, when at least one of an antioxidant and a light stabilizer is further contained, the optical characteristics can be satisfied. In addition, there is an effect of increasing the adhesion force that increases with time.

  And according to the adhesive film which concerns on this invention, since it has an adhesive layer formed using said adhesive composition for films on a film surface, the reattachment of the film to a to-be-adhered body at the time of construction is possible. It becomes easy and adjustment of the construction position of a film becomes easy. Further, even if water is used as the construction liquid, the slipperiness between the film and the adherend is ensured, so that no preparation of the construction liquid is required, and a high level of experience and intuition is not required of the construction person. Further, it is not necessary to apply force to the film during construction, and high construction technology is not required. Therefore, the construction of the film becomes simpler than before, and the workability of the film on an adherend such as a window glass can be improved.

  And according to the heat-shielding pressure-sensitive adhesive film according to the present invention, in the above pressure-sensitive adhesive film, since it has a thin film layer composed of a single layer or a plurality of layers further including a metal thin film, in addition to the effect of the above-mentioned pressure-sensitive adhesive film Excellent heat insulation effect.

  In this case, when the metal of the metal thin film is silver or a silver alloy, a film having particularly excellent light transmittance can be obtained. Therefore, the optical characteristics can be satisfied.

  And according to the construction method of the adhesive film according to the present invention or the construction method of the heat-shielding adhesive film according to the present invention, the adhesive film is covered with water that does not contain an additive that imparts slipperiness. Since it is affixed to the surface of the kimono, it is not necessary to prepare the construction liquid, and a high level of experience and intuition is not required of the installer. Further, it is not necessary to apply force to the film during construction, and high construction technology is not required. Therefore, the construction of the film becomes simpler than before, and the workability of the film on an adherend such as a window glass can be improved.

It is sectional drawing of the heat-shielding adhesive film which concerns on one Embodiment of this invention. It is sectional drawing which shows the state which constructed the heat-shielding adhesive film to adherends, such as a window glass. It is a schematic diagram explaining the sticking method of the adhesive film to a to-be-adhered body.

  Hereinafter, the present invention will be described in detail.

  The film pressure-sensitive adhesive composition according to the present invention contains an acrylic block copolymer and a plasticizer.

  The acrylic block copolymer is a (meth) acrylic acid alkyl ester polymer having a Tg (glass transition temperature) of 60 ° C. or higher, preferably 100 ° C. or higher, and (meth) acrylic acid and Tg of −10 ° C. or lower, preferably − It is a copolymer comprising a (meth) acrylic acid alkyl ester polymer of 30 ° C. or lower. 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. This acrylic block copolymer is an AB type diblock copolymer composed of two polymer blocks A and B, and A′-B′— composed of two polymer blocks A ′ and B ′. A′-type triblock copolymer is exemplified. In this case, A and A '(that is, a polymer having a high Tg) are hard segments, and B and B' (that is, a polymer having a low Tg) are soft segments.

  The film pressure-sensitive adhesive composition according to the present invention may contain only one kind of acrylic block copolymer, or may contain 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. In order to obtain the optimum self-adhesiveness and the property of increasing the adhesive strength over time, it contains at least one selected from diblock copolymers and at least one selected from triblock copolymers. Is preferred. And when it contains 1 type selected from a diblock copolymer and 1 type selected from a triblock copolymer, the polymer block A and A'- of an AB type diblock copolymer The polymer block A ′ of the B′-A ′ type triblock copolymer is a polymer block having the same monomer component, and the polymer block B and the polymer block B ′ are polymer blocks having the same monomer component. Preferably there is.

  The polymer block A is, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid. Examples of the polymer include n-octyl, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, and isobornyl methacrylate. The polymer block B is, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, acrylic acid. Examples include polymers such as n-octyl, lauryl acrylate, tridecyl acrylate, and stearyl acrylate. A larger number of carbon atoms in the alkyl group tends to have a lower Tg and become a soft segment.

  When the pressure-sensitive adhesive composition for a film according to the present invention contains one kind selected from a diblock copolymer and one kind selected from a triblock copolymer, methacryl Examples thereof include methyl acrylate / butyl acrylate, ethyl methacrylate / butyl acrylate, methyl methacrylate / 2-ethylhexyl acrylate, ethyl methacrylate / 2-ethylhexyl acrylate, and the triblock copolymer includes methyl methacrylate / acrylic. Examples thereof include butyl acid / 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.

  The plasticizer can impart self-adhesiveness to the pressure-sensitive adhesive composition containing the acrylic block copolymer. By containing a plasticizer, the pressure-sensitive adhesive composition for a film according to the present invention has self-adhesiveness. Self-adhesive is a characteristic that air can easily escape from the adhesion interface when pasting on a hard surface such as glass, the residual amount of air at the interface is extremely small, and peeling and re-adhesion are possible. is there.

  Since the plasticizer is mixed with the acrylic block copolymer, the solubility parameter (SP value according to the Small method) is preferably 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 having no phase separation can be formed. Thereby, an adhesive surface with less unevenness in terms of adhesion can be formed. Adhesive plasticizers composed of styrene elastomers and plasticizers that are known to have self-adhesive properties are preferred because they have very low compatibility with acrylic copolymers and will separate even if both are dissolved in a solvent. Absent. The SP value of paraffin, which is a typical plasticizer frequently used in combination with a styrenic elastomer, is 7.5. The SP value of the plasticizer 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 and coating properties and appearance after coating. It is.

  Moreover, since a plasticizer is mixed with an acrylic block copolymer, it is preferable that molecular weight exists in the range of 300-500. 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.

  Specific examples of the plasticizer include dioctyl phthalate (DOP), bis (2-butoxyethyl phthalate (DBEP), diisononyl phthalate (DINP), dioctyl adipate (DOA), diisodecyl adipate (DIDA), Examples thereof include bis (2-butoxyethyl) adipate (DBEA), diethylene glycol dibenzoate (DEGDB), tributyl acetylcitrate (ATBC), etc. These may be used alone or in combination of two or more. Among these, the effect of imparting self-adhesion is excellent, the initial adhesion is excellent, the increase in adhesion with time is great, the compatibility with the acrylic block copolymer is excellent, and the phase separation is performed. A uniform composition with no adhesion, and can form an adhesive surface with less unevenness in terms of adhesion, Specifically low cost from the viewpoint of can be obtained by, dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), acetyl tributyl citrate (ATBC) it is particularly preferred.

  The content of the plasticizer is preferably 5 parts by mass or more with respect to 100 parts by mass of the acrylic block copolymer from the viewpoint of excellent self-adhesive effect. More preferably, it is 10 mass parts or more, More preferably, it is 20 mass parts or more. Moreover, it is preferable that it is 60 mass parts or less from a viewpoint of the increase in the adhesive force with time. More preferably, it is 40 mass parts or less, More preferably, it is 30 mass parts or less.

  The pressure-sensitive adhesive composition for a film according to the present invention has self-adhesiveness by containing an acrylic block copolymer and a plasticizer. Moreover, the adhesiveness (initial adhesion) is kept relatively low. The initial adhesion is kept low, but the adhesion increases with time. In this case, based on JIS-K-6854-2, it is preferable that the initial adhesive force measured on conditions with a tensile speed of 50 mm / min is 0.5 N / 25 mm or less. Moreover, it is preferable that the adhesive force after one month passes after sticking to a to-be-adhered body will be 3.0 N / 25mm or more.

  The film pressure-sensitive adhesive composition according to the present invention may further contain a silane coupling agent in addition to the acrylic block copolymer and the plasticizer. Silane coupling agents act on self-adhesion and increase in adhesion over time. By improving self-adhesiveness, initial adhesion can be enhanced. When the initial adhesiveness is high, the corners of the adhesive film are difficult to peel off from the adherend such as glass due to the curl of the film.

  The silane coupling agent may have a functional group other than an alkoxysilyl group, or may have no other functional group. From the viewpoint of increasing the adhesion strength over time, speed, and the like, it is more preferable to further have a functional group other than the alkoxysilyl group. Examples of functional groups other than alkoxysilyl groups include vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, mercapto groups, sulfide groups, and isocyanate groups. Among these functional groups, an epoxy group, a methacryloxy group, an acryloxy group, and an amino group are more preferable from the viewpoint that the effect of increasing the adhesion strength over time is particularly high.

  Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane. As the silane coupling agent having an epoxy group, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Examples thereof include xylpropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent having a methacryloxy group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane. It is done. Examples of the silane coupling agent having an acryloxy group include 3-acryloxypropyltrimethoxysilane. Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- ( Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- Examples include phenyl-3-aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane. Examples of the silane coupling agent having a sulfide group include bis (triethoxysilylpropyl) tetrasulfide.

  It is preferable that content of a silane coupling agent is 0.05 mass part or more with respect to 100 mass parts of said styrene-type elastomer from viewpoints, such as the increase in the adhesive force with time. More preferably, it is 0.1 mass part or more, More preferably, it is 0.3 mass part or more. Moreover, it is preferable that it is 3 mass parts or less from a viewpoint that a silane coupling agent is expensive. More preferably, it is 2 mass parts or less, More preferably, it is 1 mass part or less.

  Further, the pressure-sensitive adhesive composition for a film according to the present invention is further oxidized in addition to the acrylic block copolymer and the plasticizer, or in addition to the acrylic block copolymer, the plasticizer, and the silane coupling agent. You may contain at least 1 sort (s) of an inhibitor and a light stabilizer. Addition of an antioxidant and a light stabilizer improves the weather resistance and suppresses deterioration of characteristics over time due to light irradiation or the like. In addition, depending on the type, there is also an effect of increasing the adhesion force over time.

  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 styrenic elastomer from the viewpoints of desired weather resistance, deterioration of characteristics over time, and thickness of the adhesive layer. Is preferred. 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.

  Examples of the light stabilizer include benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, and HALS (hindered amine light stabilizer).

  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 preferably 1 part by mass or more with respect to 100 parts by mass of the styrene-based elastomer from the viewpoints of desired weather resistance, deterioration of characteristics over time, and thickness of the adhesive layer. . 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.

  The film adhesive composition according to the present invention preferably has a shear modulus of 0.56 MPa or less measured at 20 ° C. according to JIS-K 7244-1. By using a relatively soft material, foreign objects are easily embedded, and a smooth and uniform construction surface can be easily formed. Moreover, it is preferable that it is 0.02 Mpa or more from viewpoints, such as handling property. The shear modulus can be adjusted to be relatively low, for example, by increasing the proportion of the diblock copolymer of the acrylic block copolymer or increasing the plasticizer content.

  The film pressure-sensitive adhesive composition according to the present invention is used as a material for a pressure-sensitive adhesive layer formed on a film surface. Thereby, an adhesive film can be comprised. 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, 15 μm or more is preferable from the viewpoints 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 adhesive film, A polymer film etc. can be mentioned. The pressure-sensitive adhesive 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.

  In said adhesive film, a heat-shielding adhesive film can be comprised by having a heat ray reflective layer (sunlight shielding layer) which reflects a heat ray (sunlight) further. Although it does not specifically limit as a heat ray reflective layer, The thin film layer which consists of a single | mono layer or multiple layers in which a metal thin film is contained can be mentioned. The heat-shielding adhesive film can be suitably used as a film that can be attached to the surface of an adherend of an opening 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.

  The above-mentioned pressure-sensitive adhesive film or the above-described heat-shielding pressure-sensitive adhesive film (hereinafter sometimes referred to as (heat-shielding) pressure-sensitive adhesive film) is attached to the surface of an adherend such as a window glass via a pressure-sensitive adhesive layer. The (heat shielding) adhesive film may be applied to the adherend using a construction liquid, or may be applied to the adherend without using the construction liquid. It is easy to adjust the position of the (thermal barrier) adhesive film with respect to the adherend during construction, and it is easy to remove bubbles, wrinkles, etc. generated between the (thermal barrier) adhesive film and the adherend during construction From the viewpoint of, for example, it is preferable to use a construction liquid.

  In the film construction using the construction liquid, for example, the construction liquid is applied to the surface of the adherend or the adhesive surface, and then the adhesive surface of the (thermal barrier) adhesive film is aligned with the surface of the adherend applied with the construction liquid. At this time, the construction position of the pressure-sensitive adhesive film is adjusted while sliding the (heat-shielding) pressure-sensitive adhesive film against the adherend (heat-shielding) using the construction liquid as a medium. In addition, the application liquid is applied from the outside of the (heat-shielding) adhesive film, and the adhesive film and adherend are adhered with a jig such as a spatula without causing damage to the film through the application liquid. Air bubbles generated between them are pushed out, and wrinkles generated in the (heat shielding) adhesive film are stretched. At the same time, the construction liquid between the (heat-shielding) adhesive film and the adherend and the construction liquid on the outer surface of the (heat-shielding) adhesive 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. In the case of the pressure-sensitive adhesive composition for a film according to the present invention, the construction liquid containing an additive that imparts slipperiness requires the experience and intuition of the installer in its preparation, and depending on the type of additive, heat shielding properties. In the case of an adhesive film, there is a possibility that the properties of the metal thin film layer may be impaired, and water (or water alone) that does not contain an additive that imparts slipperiness has a greater increase in adhesion over time. From the viewpoint of good drainage (drainage), the construction liquid is more preferably water (or water alone) that does not contain an additive that imparts slipperiness such as a surfactant. Since the pressure-sensitive film of the prior art does not have self-adhesiveness, it is essential to use a construction liquid containing an additive that imparts slipperiness in construction. In the case of the film pressure-sensitive adhesive composition according to the present invention, since it has a high level of self-adhesiveness, water (or water alone) that does not contain an additive that imparts slipperiness such as a surfactant is used as a construction liquid. However, it is possible to easily slide between the heat-shielding film and the adherend, and it is possible to adjust the position of the heat-shielding film and remove bubbles and wrinkles.

  The film construction without using the construction liquid can be performed by aligning the adhesive surface of the (heat shielding) adhesive film with the surface of the adherend to which the construction liquid is not applied. Under the present circumstances, the construction position of the (heat-shielding) adhesive film is adjusted by re-sticking. Then, without using the construction liquid as a medium, using a jig or cloth, the air bubbles generated between the (thermal barrier) adhesive film and the adherend are extruded, and the wrinkles generated in the (thermal barrier) adhesive film are stretched. . At that time, it is preferable to use a soft material for the jig or cloth so as not to damage the film.

  Since no construction liquid is used, it is not necessary to drain the construction liquid during construction, but the (thermal insulation) adhesive film is less likely to slide against the adherend because the construction liquid is not used as a medium. There is a little difficulty in adjusting the construction position. In addition, since the construction liquid is not used as a medium, there is a slight difficulty in pushing out bubbles generated between the (heat-shielding) pressure-sensitive adhesive film and the adherend and extending the wrinkles generated in the (heat-shielding) pressure-sensitive adhesive film.

  In the construction method of the (thermal barrier) adhesive film, the adhesive layer of the (thermal barrier) adhesive film is formed by the adhesive composition for a film according to the present invention. The (thermal barrier) adhesive film adheres to the surface of the adherend simply by lightly matching the adhesive surface of the (thermal barrier) adhesive film to the surface. And since the initial adhesive force is kept low, it becomes easy to re-attach the (thermal barrier) adhesive film to the adherend during construction, and the adjustment of the construction position of the (thermal barrier) adhesive film becomes easy. . Therefore, the construction liquid may not be used, and water (or water alone) that does not contain an additive that imparts slipperiness such as a surfactant may be used as the construction liquid. In other words, even if such a construction liquid is not used, the slipperiness between the (heat-shielding) adhesive film and the adherend is ensured. Advanced experience and intuition are not required.

  And although the initial adhesive strength is kept low, the adhesive strength increases over time, so unlike pressure-sensitive adhesives, force is applied to the (thermal barrier) adhesive film during construction ((thermal barrier) adhesive film It is not necessary to apply a pressing force to the outer surface of the metal to make it closely adhere to the outer surface, and advanced construction technology is not required. Therefore, the construction of the film becomes simpler than before, and the workability of the film on an adherend such as a window glass can be improved.

  As influence factors of adhesion force, a) contact area between the adhesive surface and the adherend surface, b) dirt on the adherend surface, c) residual stress of the adhesive, d) chemical bond between the adhesive surface and the adherend surface (intermolecular) Attractive force, hydrogen bond, covalent bond), and the like. a) The contact area is affected by surface irregularities on the adherend surface, interface voids (air layer) between the adhesive surface and the adherend surface, and the like.

  Factors that increase the adhesion strength over time include the progress of wetting between the adhesive surface and the adherent surface, and the formation of chemical bonds between the adhesive surface and the adherent surface. The progress of wetting is considered to be caused by the ease of deformation of the pressure-sensitive adhesive composition. The ease of deformation of the pressure-sensitive adhesive composition is such that the low-blocking Tg polymer of the acrylic block copolymer of the pressure-sensitive adhesive composition, that is, a polymer having a low Tg that increases the proportion of the soft segment is a constituent. It is presumed that it can be adjusted by a method such as increasing the proportion of the polymer or increasing the plasticizer content. The chemical bond can be formed by blending a silane coupling agent.

  a) The contact area between the adhesive surface and the adherend surface can be increased by the progress of wetting between the adhesive surface and the adherend surface, the removal of an air layer or foreign matter from the interface, and the like. The film construction using a construction liquid is preferable in that it is easy to remove the air layer and foreign matter.

  b) Film construction using a construction liquid is preferred in that dirt on the adherend surface can be removed during construction.

  c) The residual stress of the pressure-sensitive adhesive is easily relaxed by the ease of deformation of the pressure-sensitive adhesive composition and the film construction using the construction liquid. In this respect, film construction using a construction liquid is preferable.

  A heat-shielding adhesive film consists of what has at least said thin film layer and said adhesive layer on the surface of a base film. The pressure-sensitive adhesive layer may be formed on the same surface as the surface on which the thin film layer is formed, or may be formed on the surface on the opposite side. May be. When the heat-shielding pressure-sensitive adhesive film is disposed on the indoor side of the window, the pressure-sensitive adhesive layer is formed on the surface of the base film opposite to the surface on which the thin film layer is formed. It is preferable that This is because heat such as heating generated indoors is difficult to be absorbed by the pressure-sensitive adhesive layer and is excellent in heat insulation.

  FIG. 1 is a cross-sectional view of an embodiment of a heat-shielding adhesive film. The heat-shielding adhesive film 10 has a thin film layer 14 including a metal thin film and an adhesive layer 22 on the surface of the base film 12.

  On one surface of the base film 12, a thin film layer 14 containing a metal thin film and a cured resin layer 20 are provided in this order. On the other surface of the base film 12, an adhesive layer 22 and a separator 24 are provided in this order.

  The thin film layer 14 is directly formed on one surface of the base film 12. The cured resin layer 20 is directly formed on the surface of the thin film layer 14. Therefore, on one surface of the base film 12, the thin film layer 14 in contact with the base film 12 and the cured resin layer 20 in contact with the thin film layer 14 are provided in this order.

  The pressure-sensitive adhesive layer 22 is directly formed on the other surface of the base film 12. The separator 24 is directly formed on the surface of the pressure-sensitive adhesive layer 22. Therefore, on the other surface of the base film 12, an adhesive layer 22 in contact with the base film 12 and a separator 24 in contact with the adhesive layer 22 are provided in this order.

  The pressure-sensitive adhesive layer 22 is for attaching the heat-shielding pressure-sensitive adhesive film 10 to an adherend such as a window glass. The separator 24 is peeled off and the heat-shielding pressure-sensitive adhesive film 10 is attached to the window glass or the like via the pressure-sensitive adhesive layer 22. It can be attached to an adherend. The pressure-sensitive adhesive layer 22 is formed by the film pressure-sensitive adhesive composition according to the present invention. As the separator 24, paper, an olefin film, a PET film, or the like is used. What has been subjected to a release agent treatment for controlling the adhesion is preferable.

  The substrate film 12 is a substrate serving as a base for forming the thin film layer 14. The material of the base film 12 is preferably a material having optical transparency, capable of forming a thin film on its surface without hindrance, and having flexibility. For example, a light transmissive polymer film and the like can be mentioned. 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 for the light-transmitting polymer film include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethyl methacrylate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polystyrene, polyamide, polybutylene terephthalate, Polymer materials such as polyetheretherketone, polyvinyl chloride, polyvinylidene chloride, triacetyl cellulose, polyurethane, and cycloolefin polymer can be used. These may be used alone or in combination of two or more. Among these, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyethylene, polypropylene, and cycloolefin polymer are more preferable materials from the viewpoint of excellent transparency, durability, and workability.

  The thickness of the light transmissive polymer 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 viewpoint of being difficult to wrinkle during processing and difficult to break. More preferably, it is 40 μm or more. Moreover, 500 micrometers or less are preferable from viewpoints, such as a softness | flexibility, a handleability, and economical efficiency. More preferably, it is 250 μm or less.

  The thin film layer 14 may be composed of a single layer of a metal thin film, but is preferably formed by laminating a plurality of thin films including a metal thin film and a high refractive index thin film. The number of metal thin films and high refractive index thin films included in the thin film layer 14 and their positions are not particularly limited. More preferable configuration of the thin film layer 14 includes a configuration in which metal thin films and high refractive index thin films are alternately arranged, a configuration in which high refractive index thin films are respectively disposed on both sides of the thin film layer 14, and combinations thereof. .

  The number of layers of the thin film layer 14 may be set as appropriate in accordance with requirements for optical properties such as light transmittance and solar shading. The number of thin film layers 14 is preferably in the range of 2 to 10 layers in consideration of the material, film thickness, manufacturing cost, etc. of each thin film. In consideration of optical characteristics, odd-numbered layers are more preferable, and 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 of the thin film layer 14 is shown in order from the light-transmitting substrate 12 side: high refractive index thin film / metal thin film (2 layers), metal thin film / high refractive index thin film (2 layers), high refractive index. Thin film / metal thin film / high refractive index thin film (3 layers), metal thin film / high refractive index thin film / metal thin film (3 layers), high refractive index thin film / metal thin film / high refractive index thin film / metal thin film / high refractive index thin film ( 5 layers), metal thin film / high refractive index thin film / metal thin film / high refractive index thin film / metal thin film (5 layers), high refractive index thin film / metal thin film / high refractive index thin film / metal thin film / high refractive index thin film / metal thin film / High refractive index thin film (7 layers), metal thin film / high refractive index thin film / metal thin film / high refractive index thin film / metal thin film / high refractive index thin film / metal thin film (7 layers), etc.

  A metal thin film is comprised from the metal which is easy to reflect a far infrared ray, and can function as a solar radiation shielding layer. The high refractive index thin film can exhibit functions such as enhancing light transmittance by being laminated together with the metal thin film. The high refractive index thin film has a higher refractive index than the light transmissive substrate. The refractive index refers to the refractive index for light of 633 nm. An example of the high refractive index thin film is a metal oxide thin film.

  In the case of having two or more high refractive index thin films, all the high refractive index thin films may be made of the same material, or some of the high refractive index thin films are made of a material different from others. Alternatively, all the high refractive index thin films may be made of different materials.

  The thin film layer 14 may further include a barrier thin film. The barrier thin film is formed on one side or both sides of the metal thin film. The barrier thin film is a thin film accompanying the metal thin film, and is counted as one layer together with the metal thin film. The barrier thin film suppresses diffusion of elements constituting the metal thin film into the metal oxide thin film.

  The cured resin layer 20 covers the surface of the thin film layer 14 and can suppress the surface from being scratched. Examples of the material of the cured resin layer 20 include a silicone resin and an acrylic resin. The silicone resin and acrylic resin may be thermosetting, photocurable, or water curable. Examples of the acrylic resin include acrylic / urethane resin, silicon acrylic resin, acrylic / melamine resin, and the like.

  The thickness of the cured resin layer 20 is preferably 2.0 μm or less from the viewpoint of excellent heat insulation properties (suppressing the heat transmissivity low). More preferably, it is 1.6 micrometers or less, More preferably, it is 1.0 micrometers or less. Moreover, it is preferable that it is 0.4 micrometer or more from a viewpoint of being excellent in abrasion resistance. More preferably, it is 0.6 micrometer or more, More preferably, it is 0.8 micrometer or more.

  The heat-shielding pressure-sensitive adhesive film 10 can be produced, for example, as follows. The thin film layer 14 is formed by sequentially stacking the thin films on one surface of the base film 12 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, a curable resin is applied to the surface of the thin film layer 14 to form a coating film, and the cured resin layer 20 can be formed by performing a curing process on the formed coating film. The pressure-sensitive adhesive layer 22 may be formed either before or after the thin film layer 14 is formed, but is formed by coating the pressure-sensitive adhesive composition for a film on the other surface of the base film 12. Thus, the heat-shielding adhesive film 10 can be obtained. In addition, in the state before use, the separator 24 is provided on the surface of the pressure-sensitive adhesive layer 22, and the separator 24 is bonded to the surface of the pressure-sensitive adhesive layer 22.

  The heat-shielding adhesive film 10 is suitably applied to window glass of buildings such as buildings and houses, and window glass of vehicles such as automobiles. FIG. 2 shows a state where the heat-shielding adhesive film 10 is applied to an adherend 30 such as a window glass. As shown in FIG. 2, the heat-shielding adhesive film 10 is disposed on the indoor side, and the surface on which the thin film layer 14 is formed is on the indoor side, and the surface on which the thin film layer 14 is not formed is on the outdoor side. Affixed to the body 30. At this time, the heat-shielding adhesive film 10 can be attached to the adherend 30 by the adhesive layer 22.

  In this way, the light transmissive laminate 10 reflects the solar radiation inserted from the outside by the thin film layer 14, and thus has good solar shielding properties. Moreover, since the air-conditioning effect in a room improves with the thin film layer 14, it has the outstanding heat insulation. The cured resin layer 20 exhibits good scratch resistance.

  In the heat-shielding adhesive film 10, the thin film layer 14 is provided only on one surface of the base film 12. However, the present invention is not limited to this configuration, and the thin film layer is formed on both surfaces of the base film 12. May be provided respectively. In this case, the pressure-sensitive adhesive layer 22 to be attached to an adherend such as a window glass can be provided on the surface of the thin film layer provided on the other surface of the base film 12. A separator 24 can be provided on the surface of the pressure-sensitive adhesive layer 22.

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

  Metal oxide of thin film layer As metal oxide of thin film, oxide of titanium, oxide of zinc, oxide of indium, oxide of tin, oxide of indium and tin, oxide of magnesium, oxidation of aluminum 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 a light-transmitting laminate is applied with water to a window glass of a building, even when water remains between the window glass, good water drainage is obtained, and the water application workability is improved. This is because there is an advantage such as being able to be made.

  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. Moreover, by forming it thinly, the film formation cost is reduced correspondingly, which can contribute to the reduction of the manufacturing cost of the light-transmitting laminate.

  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 in the cross-sectional direction of a thin film layer including the thin film to be analyzed is 100 nm or less using an ultrathin section method (microtome) or the like. Next, the position of the thin film layer and the thin film is confirmed with 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 thin film 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, after forming the above-described thin film layer on a light-transmitting substrate, the thin film 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-transmitting polymer film having the above-described thin film 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 thin film layer, since the moisture and oxygen contained in the metal oxide thin film are consumed during 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 changes such as curing shrinkage, and it becomes easy to suppress interfacial peeling of the thin film layer, and to improve durability against sunlight.

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

  As a heat-shielding pressure-sensitive adhesive film according to Examples and Comparative Examples, a base film, a thin film layer composed of approximately the following three-layer thin film formed on one surface of the base film, and the other surface of the base film were formed. A heat shielding adhesive film having an adhesive layer was prepared.

The heat-shielding pressure-sensitive adhesive films according to the examples and comparative examples are formed on one surface of a base film by a TiO ₂ thin film (first layer) by a sol-gel method and UV irradiation. | Titanium oxide thin film / Ag-Cu alloy thin film / titanium Oxide thin film (second layer) | It has a thin film layer in which a TiO ₂ thin film (third layer) by sol-gel method and UV irradiation is laminated in order.

  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 mixed this for 10 minutes using the stirrer, and prepared the coating liquid. 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. Subsequently, the coating film was dried 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 irradiation machine [high pressure mercury lamp (160 W / cm)]. As a result, a TiO ₂ thin film (first layer) was formed on the PET film.

  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 was heat-treated in the atmosphere in a heating furnace, whereby the metal Ti thin film contained in the thin film layer was thermally oxidized to obtain a titanium oxide thin film.

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, 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 a thin film layer containing a titanium oxide thin film (barrier thin film) to be analyzed has a thickness in the cross-sectional direction of 100 nm or less. 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.

(Preparation of adhesive liquid)
A pressure-sensitive adhesive solution was prepared by dissolving each component in toluene so as to have the composition (parts by mass) described in Tables 2 and 3. The details of each component are as shown below.

(Acrylic block copolymer)
・ Clarity LA2250: (Kuraray)
(Acrylic polymer)
・ Taisin Resin WS023: (manufactured by Nagase ChemteX Corporation)
(Plasticizer)
DIDA: Diisodecyl adipate (reagent)
DOA: Dioctyl adipate (reagent)
DBEA: bis (2-butoxyethyl) adipate (reagent)
・ DOP: Dioctyl phthalate (reagent)
DINP: diisononyl phthalate (reagent)
ATBC: Tributyl acetyl citrate (reagent)
DBEP: bis (2-butoxyethyl) phthalate (reagent)
・ DEGDB: Diethylene glycol dibenzoate (reagent)
(UV absorber)
Tinuvin 326: manufactured by BASF (antioxidant)
・ Irganox 1010: manufactured by BASF (silane coupling agent)
KBM-303: Epoxy group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBE-502: Methacryloxy group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-603: Amino group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Formation of adhesive layer)
The pressure-sensitive adhesive solution was applied onto the easily adhesive layer surface of the PET film by a blade method and dried at 130 ° C. to form a pressure-sensitive adhesive layer (thickness 30 μm).

  Self-adhesiveness was evaluated about each produced heat-shielding adhesive film. Further, the adhesion to glass (initial, time) and shear modulus were measured. Moreover, the uniformity, coating property, and peelability of the liquid were evaluated. Further, optical characteristics (visible light transmittance, shielding coefficient) and durability were evaluated. The measurement method, evaluation method, and evaluation criteria are as shown below. In addition, each heat-shielding adhesive film was affixed on the single side | surface of 3 mm thick float glass.

(Self-adhesive)
As shown in FIG. 3, one end side of the heat-shielding adhesive film 1 is fixed to the support 2 with the tape 3, and the heat-shielding adhesive film 1 is bent 180 ° with the adhesive surface 1 a facing outside. The side of the glass plate 4 having a width of 50 mm and a thickness of 3 mm is aligned with one side of the glass plate 4, and the support 2 is moved from one side of the glass plate 4 toward the opposite side. The heat shielding adhesive film 1 was bonded to the glass plate 4 by combining the surfaces 1a. The bonding speed was 1.0 m / min. After bonding, the area occupied by the air layer remaining at the interface between the glass surface 4a and the adhesive surface 1a was measured within a range of 45 mm × 55 mm. The smaller the area occupied by the air layer, the better the self-adhesiveness. When the glass surface and the adhesive surface touch each other, the bonding proceeds spontaneously, and the area occupied by the air layer remaining at the adhesion interface is 3% or less as “A”, more than 3% to 7% % Is less than “B”, and the glass layer and the adhesive surface do not have the property that the bonding proceeds spontaneously as soon as they come into contact with each other, or the area occupied by the air layer remaining at the adhesion interface exceeds 7% The case of “C” was designated as “C”.

(Adhesion)
The heat-shielding adhesive film was bonded to the glass plate by matching the adhesive surface of the heat-shielding adhesive film to the glass surface in the same manner as the bonding method performed in the self-adhesive evaluation. However, the bonding was performed by a method using the construction liquid A (water only). The application liquid A is sprayed on both the glass surface and the adhesive surface before bonding, and then bonded together. After the bonding, the application liquid A is sprayed again on the film surface and the surface is rubbed with a spatula. The construction liquid was extruded from the mating interface and brought into close contact. Adhesive strength (N / 25 mm) was measured by a 180-degree peeling method defined in JIS-A-5759 after a predetermined time had elapsed after bonding (3 hours, 2 weeks, and 1 month). The width of the sample was 50 mm, and the tensile speed was 50 mm / min.

(Shear modulus)
After the adhesive liquid was applied onto the peeled PET and dried, the peeled PET was peeled off, and the shear modulus measurement method defined in JIS K-7244-1 was applied to a temperature of 2 to 5 ° C from -100 ° C to 100 ° C. The temperature was raised in steps, the equilibrium was reached in each step, and the shear modulus was measured.

(Liquid uniformity)
The prepared pressure-sensitive adhesive liquid was allowed to stand for 3 hours, and then judged based on whether or not the liquid was separated. The case where the liquid was separated was indicated as “separation”, and the case where the liquid was not separated was indicated as “uniform”.

(Coating property)
After the pressure-sensitive adhesive liquid was applied on the easy-adhesion layer surface of the PET film and dried, it was judged by whether or not the pressure-sensitive adhesive surface was uniform. The case where streaks due to coating were seen on the adhesive surface was designated as “B”, and the case where no streaks were seen was designated as “A”.

(Peelability)
After 15 minutes have passed since the heat-shielding adhesive film was attached to the glass plate in the same manner as the bonding method performed in the adhesion evaluation, the heat-shielding adhesive was applied by the 180-degree peeling method defined in JIS K6854-2. The film was peeled off. At this time, when there is no large variation in the peel force within the adhesive surface, the entire surface peels smoothly (uniformly) and no adhesive remains on the glass surface, “A”, and the peel force varies within the adhesive surface. As a result, the sound was intermittently crisp and peeled non-uniformly overall, but “B” when the adhesive did not remain on the glass surface. The case where it peeled unevenly and the adhesive remained on the glass surface was defined as “C”.

(Reworkability)
After bonding the heat-shielding adhesive film to the glass plate by the method using the construction liquid A described in (Adhesion), peeling and re-sticking after 3 hours, that is, whether reworkability was possible was confirmed. If there is a problem that the film is broken or glue remains on the glass surface, rework is impossible.

(Workability)
Adhesive film with a width of 50 cm x length of 100 cm is bonded to the window glass, the amount of air remaining at the interface after bonding, reworkability (rework if there is a problem such as film breaks or glue remains on the glass surface) Impossible). Bonding was performed by two methods: a method using no construction liquid and a method using the construction liquid A. A large shower and spatula were used instead of a spray bottle. The person who performed the bonding is not a construction technician. When the reworkability was impossible, it was judged as x, when the reworkability was good, and the amount of residual air was zero, 、, when a small amount of air remained, ◯, and when a large amount of air remained, Δ.

(Visible light transmittance)
Based on JIS A5759, the transmission spectrum of wavelength 300-1000 nm was measured using the spectrophotometer (Shimadzu Corporation make, "UV3100"), and it calculated | required by calculation.

(Solar radiation shielding coefficient)
The measurement was performed according to JIS A5759. Using a spectrophotometer (Shimadzu Corporation "UV3100"), by measuring the transmission spectrum and reflection spectrum of the wavelength 300-2500nm, calculate the solar transmittance, solar reflectance, solar transmittance, solar reflectance, correction The solar shading coefficient was calculated from the emissivity.

(durability)
UV irradiation was performed to the adhesive layer of the heat-shielding adhesive film adhered to the glass surface from the glass surface side. Under the following conditions, the heat-shielding pressure-sensitive adhesive film peeled off on the pressure-sensitive adhesive surface was judged as defective “B”, and the film where no peeling occurred was judged as good “A”.
Irradiation conditions:
-Optical filter (spectral transmittance: 2% or less at 275 nm, 90% or more at 400 nm)
・ Average discharge voltage current (50V ± 1V, 60A ± 1.2A)
・ Temperature indicated by black panel thermometer (63 ℃ ± 3 ℃)
・ Irradiance on the surface of the specimen (at 255 (± 10%) W / m ² , 300 to 700 nm)
・ Water injection (water injection for 18 minutes during irradiation for 120 minutes)
・ Light source: 1 carbon sunshine arc

  According to the pressure-sensitive adhesive composition of the examples, it has self-adhesiveness and low initial adhesion, so even without using a construction liquid, the position of the heat-shielding pressure-sensitive adhesive film can be adjusted by re-attaching without misalignment. Attached and removed bubbles and wrinkles with a spatula. Moreover, even when using a construction liquid consisting of only water, the heat-shielding adhesive film is slippery on the glass surface, and by adjusting the position of the heat-shielding adhesive film by sliding the heat-shielding adhesive film, there is no displacement. Attached and removed bubbles and wrinkles with a spatula. In addition, it was possible to perform high-quality pasting more easily when using the construction liquid than when using no construction liquid. And even if it did not make heat-shielding adhesive film adhere to glass with pressure, it has confirmed that it had the adhesiveness which was excellent by the increase in adhesiveness. Therefore, it was confirmed that the workability was excellent.

  On the other hand, from Comparative Example 2, the pressure-sensitive adhesive has strong adhesiveness and cannot be re-applied. Moreover, even if it used construction liquid (water), the slip of the heat insulating adhesive film on a glass surface was bad, and it was difficult to adjust the position of a heat insulating adhesive film.

  In addition, according to the pressure-sensitive adhesive composition of the examples, although the initial adhesiveness is low, since it has a predetermined adhesive force from the initial stage, there is also a problem that the corners of the film are peeled off from the glass surface due to film curl etc. Did not occur.

  From the examples, it can be seen that when the SP value of the plasticizer is 8.0 to 9.9, the uniformity of the pressure-sensitive adhesive liquid is excellent, and the coating property and the peelability are excellent. And since it is excellent in coating property and peelability, it turns out that the adhesive surface with few nonuniformity is formed in the surface of adhesiveness. Moreover, it turns out that it is excellent in the uniformity of an adhesive liquid as the molecular weight of a plasticizer is 300-500 from an Example, and it is excellent in coating property and peelability. And since it is excellent in coating property and peelability, it turns out that the adhesive surface with few nonuniformity is formed in the surface of adhesiveness.

  From the examples, those containing dioctyl phthalate (DOP), dioctyl adipate (DOA), diisononyl phthalate (DINP), or tributyl acetylcitrate (ATBC) as plasticizers increased adhesion over time. Is particularly large, so the adhesion strength over 3N / 25mm over time (1 month) is particularly high when adhered to glass, and the glass scattering prevention function prevents the glass from scattering when the glass breaks It can also be seen that

  Also, from the examples, the one containing a silane coupling agent in addition to the plasticizer has an increased initial adhesion, so the film corners are peeled off from the glass surface due to film curl etc. Also did not occur. Moreover, it has the effect of accelerating the speed at which the adhesion force increases with time, and it can be seen that the adhesion force exceeds 3 N / 25 mm over time (2 weeks).

  In Comparative Example 1, since the plasticizer was not blended, the level of self-adhesiveness was extremely low, that is, the residual area at the time of bonding was large, and the adhesive force was not uniform at the time of peeling and intermittently crisp and audible. The film is easy to break because it is peeled up.

  And according to the heat-shielding adhesive film of an Example, it was confirmed that it was excellent in light transmittance, heat-shielding property, durability, and satisfied optical characteristics.

  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. .

DESCRIPTION OF SYMBOLS 10 Heat-shielding adhesive film 12 Base film 14 Thin film layer 20 Cured resin layer 22 Adhesive layer 24 Separator

Claims (17)

  A pressure-sensitive adhesive composition for a film, comprising an acrylic block copolymer and a plasticizer.   The pressure-sensitive adhesive composition for a film according to claim 1, wherein the shear elastic modulus measured at 20 ° C according to JIS-K-7244-1 is 0.56 MPa or less.   Based on JIS-K-6854-2, the initial adhesive force measured under the condition of a tensile speed of 50 mm / min is 0.5 N / 25 mm or less, and after one month has elapsed since it was attached to the adherend. The pressure-sensitive adhesive composition for a film according to claim 1 or 2, wherein the adhesive strength is 3.0 N / 25 mm or more.   The content of the plasticizer is in the range of 5 to 60 parts by mass with respect to 100 parts by mass of the acrylic block copolymer. Adhesive composition.   The pressure-sensitive adhesive composition for a film according to any one of claims 1 to 4, wherein a solubility parameter of the plasticizer is within a range of 8.0 to 9.9.   The pressure-sensitive adhesive composition for a film according to any one of claims 1 to 5, wherein the plasticizer has a molecular weight in the range of 300 to 500.   7. The plasticizer according to claim 1, wherein the plasticizer is one or more selected from dioctyl phthalate, dioctyl adipate, diisononyl phthalate, and tributyl acetylcitrate. An adhesive composition for film.   Furthermore, a silane coupling agent is contained, The adhesive composition for films of any one of Claim 1 to 7 characterized by the above-mentioned.   The pressure-sensitive adhesive composition for a film according to claim 8, wherein the silane coupling agent is a silane coupling agent having an epoxy group, a methacryloxy group, an acryloxy group, or an amino group.   Furthermore, at least 1 sort (s) of antioxidant and a light stabilizer is contained, The adhesive composition for films of any one of Claim 1 to 9 characterized by the above-mentioned.   A pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition for a film according to claim 1 on the film surface.   The pressure-sensitive adhesive film according to claim 11, further comprising a thin film layer comprising a single layer or a plurality of layers including a metal thin film.   The heat-shielding pressure-sensitive adhesive film according to claim 12, wherein the metal of the metal thin film is silver or a silver alloy.   The construction method of the adhesive film characterized by sticking the adhesive film of Claim 11 on the surface of a to-be-adhered body using the water which does not contain the additive which provides slipperiness.   The adhesive film construction method according to claim 14, wherein the additive imparting slipperiness is a surfactant.   The construction method of the heat-shielding adhesive film characterized by sticking the heat-shielding adhesive film of Claim 12 or 13 on the surface of a to-be-adhered body using the water which does not contain the additive which provides slipperiness.   The method for applying a heat-shielding pressure-sensitive adhesive film according to claim 16, wherein the additive imparting slipperiness is a surfactant.

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