CN100442087C - Near-infrared absorbing film, process for producing the same, near-infrared absorbing film roll, process for producing the same and near-infrared absorbing filter - Google Patents

Abstract

The near-infrared ray absorption film of the present invention is a near-infrared ray absorption film in which a near-infrared ray absorption layer comprising a composition containing a near-infrared ray absorbing dye having maximum absorption at a wavelength of 800 to 1200 nm, and a resin is provided on a transparent substrate film, and is characterized that a surfactant having HLB of 2 to 12 is contained in the composition at 0.01 to 2.0% by mass. There can be provided a near-infrared ray absorption film excellent in coated film appearance which has the wide absorbing ability in the near-infrared ray absorbing region, has a high light transmittance in the visible light region, has little change in optical properties with time, and can respond to a higher luminance of a display, and higher-definition and higher image quality by Hi-Vision broadcasting in recent years.

Description

Near-infrared absorbing film and manufacture method thereof, near-infrared absorbing film volume and manufacture method thereof and near-infrared absorbing light filter

Technical field

The present invention relates to the visible region the transmitance height, aging less and also appearance of film evenly, be suitable for the near-infrared absorbing film and the manufacture method thereof of filter of display, in addition, near-infrared absorbing film volume and the manufacture method thereof with low uncertainty that also relate in long film tone etc., and the near-infrared absorbing light filter that has used this film.

Background technology

Film with ability of absorption near infrared ray has the block near infrared line and character that visible light is passed through, and it can be used as near-infrared absorbing film and is used to various uses.

For example, in recent years, as slim big view display, plasma display has received concern, but can use the electronic device of near infrared ray telepilot maloperation to occur from the near infrared ray of plasma display emission, so need be at the above-mentioned near-infrared absorbing light filter of the former configuration of plasma display, to prevent these maloperations.

All the time, be that (1) contains metallic ions such as copper or iron in phosphate glass light filter, (2) is at the layer of stacked different refractivity on the substrate and by interfering the interference light filter that sees through light certain wavelengths is seen through, (3) contain copper ion in multipolymer acrylic resin light filter, (4) at the light filter of the stacked layer that has dispersed or dissolved pigment in resin on the matrix material etc. as what the near-infrared absorbing light filter used.

Wherein, with regard to the light filter of (4), its processability, throughput rate are good, and the degree of freedom of optical design is also bigger, is directed to this and has proposed the whole bag of tricks.For example, the spy opens 2002-82219 communique, spy and opens 2002-214427 communique, spy and open 2002-264278 communique, spy and open 2002-303720 communique, spy and open 2002-333517 communique, spy and open that 2003-82302 communique, spy are opened the 2003-96040 communique, the spy opens 2003-114323 communique etc.

But, wherein, even have near infrared ability and the long-time light filter that also can not wear out that uses that can block fully from the plasma display emission although exist, the appearance of film of near infrared ray absorption layer still can't fully satisfy the high brightnessization of plasma display in recent years, height that Hi-vision is broadcasted becomes more meticulous or the requirement of high image qualityization.For the appearance of film of near infrared ray absorption layer, must assurance not having diameter is above, the defectives of the size of 100 μ m more preferably of 300 μ m.If be arranged on the front of plasma display, then size is that the above defective of 300 μ m can become the point that is similar to bright spot, and defective can obviously be changed.100 μ m are above and also can emphasize because of applying such as bonding processing are carried out under the effect of lens sometimes less than the defective of 300 μ m, so in must avoiding defective to be present in as much as possible filming.In addition, the more shallow lines in filming, spot etc. also can become problem because of obviously being changed in the display front.

In addition, light filter also needs to have and gives tone adjusting, the antireflection of specific absorption, other functions such as traumatic resistance on surface to the visible region except having the near-infrared absorbing ability.And then the somebody has proposed to give to light filter the scheme of ultraviolet absorption ability.This be because, in most of the cases from the outside is incident in the light of near-infrared absorbing light filter, contain ultraviolet ray, this ultraviolet ray can cause the deterioration of near infrared absorbing coloring matter, becomes the reason of the characteristic of near-infrared absorbing light filter along with the time deterioration.

In order to give these functions to light filter, the near-infrared absorbing film (WO97/38855 communique) of the multi-layered type of the functional layer multiple stratification that will have multiple function is for example disclosed.In this communique, as layer with the function outside the near-infrared absorbing ability, electromagnetic wave absorbing layer, anti-reflection layer and UV-absorbing layer are disclosed, be electromagnetic wave absorbing layer and anti-reflection layer wherein by write up, about UV-absorbing layer, in detailed description of the invention or embodiment, all do not touch fully.About the electromagnetic wave absorbing layer recorded and narrated in detail and the multiple stratification of anti-reflection layer, the method that functive by will having various functions in this communique and near-infrared absorbing film are fitted is implemented.

In addition, open the near infrared ray cut-out film that discloses the film with anti-reflective function that will comprise antistatic backing in the 2002-189423 communique and be compounded with UV-absorbing layer the spy and directly be attached to directly applying light filter of the lip-deep plasma display device of plasma display device.In this communique in the disclosed light filter, transparent gluing (bonding) agent laminating that contains ultraviolet light absorber by intervention has closed the film with anti-reflective function and the near infrared ray that comprise antistatic backing and has cut off film, so near infrared ray cut off the surface of film on compound again transparent pressure sensitive gluing (bonding) agent layer.

In addition, open the spy and disclose the light filter that near infrared ray absorption is defined to nickel coordination compound and has been laminated with UV-absorbing layer and hard conating in the 2003-4904 communique.In this technology, the film that also will contain ultraviolet light absorber fits together with the thin slice that contains near infrared absorbing coloring matter.

In the conventional art relevant with these compound light filters that form by fitting, owing to fit, so the interface increases the problem that its result exists optical characteristics to descend to some extent by bonding coat, also need to implement bonding process in addition, therefore have disadvantageous economically problem.In addition, because the gross thickness thickening of light filter, so existence is to the problem of the sticking operation deterioration of adherends such as display.

As the UV degradation that prevents the near infrared absorbing coloring matter in the near-infrared absorbing light filter and then move towards the technology of multifunction, open the spy and to disclose the near-infrared shielding duplexer that the sequential cascade according to antireflection film, transparent matrix, near-infrared shielding, transparent bonding coat forms in the 2002-138203 communique.Wherein use this transparency bonding coat, on transparent hard substrates such as display, fixed duplexer, in this communique, mention,, preferably make in the transparent binding compositions that constitutes this transparency bonding coat to contain ultraviolet light absorber if will suppress the deterioration of near infrared absorbing coloring matter.But, in the type of service of its actual light filter, the position of transparent bonding coat is set as than the more close display side of near-infrared shielding, ultraviolet ray and luminous ray etc. absorbed the incident action of ultraviolet ray together from the incident of anti-reflection layer side so this formation can't be brought into play before arriving near infrared absorbing coloring matter.Thus, can't adapt to the so-called requirement that suppresses by the deterioration of the UV-induced near infrared absorbing coloring matter of incident at present.

In addition, at the high brightnessization of in recent years plasma display, become more meticulous or high image qualityization based on the height of Hi-vision broadcasting, not only above-mentioned fundamental characteristics is important, and the less feature of the tonal variation of whole image is also important certainly, also has the outstanding feature of tonal variation appearance of film also minimum, near infrared ray absorption layer between product also very important.But, particularly for long near-infrared absorbing film, in above-mentioned each communique about the variation that improves tone or both not also not promptings of record of method of appearance of film.

In addition, open in the 2002-341132 communique the spy and to mention, because plasma display also has the trend of big pictureization, when being applied to so big view display, as light penetration or the less film of color spot, can use the wavelength control film with low uncertainty of the light penetration of specific wavelength on the length direction of film.With regard to this technology, after coating the light absorption layer on the film, the laser of irradiation specific wavelength before dry or cooling, make coating weight even by the rotating speed of controlling little photogravure (microgravure), thereby the variation that makes it see through intensity is less, in the time of on attaching to the big picture of plasma display etc., can reduce light penetration or color spot in the picture.But, in the method,, can't fully control the variation of the tone on the thin-film width direction (TD direction) though can control the variation of the tone on the length direction (MD direction) of film to a certain extent.In addition, only control coating amount, just can't significantly reduce the variation of tone with respect to long near-infrared absorbing film, and then the outward appearance aspect is difficult to also meet the demands by the rotating speed that utilizes little photogravure.

Summary of the invention

The objective of the invention is to, provide a kind of near infrared region have receptivity widely, the light penetration height of visible region, optical characteristics aging less and can be with the high brightnessization of in recent years display, based on the near-infrared absorbing film that height becomes more meticulous or the corresponding appearance of film of high image qualityization is outstanding and the near-infrared absorbing light filter of Hi-vision broadcasting.In addition, in the present invention, also provide to prevent in large-scale picture or the manufacture method of the near-infrared absorbing film of the deviation of outward appearance or optical property and the manufacture method of near-infrared absorbing film volume between the product.

Near-infrared absorbing film of the present invention, it is the near-infrared absorbing film that transparent base film is provided with the near infrared ray absorption layer that is made of composition, wherein said composition contains near infrared absorbing coloring matter and the resin that has very big absorption in the scope of wavelength 800nm～wavelength 1200nm, contains HLB more than the 0.01 quality %, below the 2.0 quality % and be the surfactant of 2～12 scope in above-mentioned composition.Wherein, said in the present invention " film " is the notion that also comprises what is called " thin slice ".In addition, used the plasma display of the near-infrared absorbing film of the invention described above also to be included within the present invention with the front light filter.

In addition, in the manufacture method of near-infrared absorbing film of the present invention, coating contains the coating fluid of near infrared absorbing coloring matter, resin, surfactant and organic solvent and makes its drying on transparent base film, thereby formation near infrared ray absorption layer, wherein, as above-mentioned surfactant, use HLB is 2～12 surfactant, and the solid state component with respect to above-mentioned coating fluid contains more than this surfactant 0.01 quality %, below the 2.0 quality % simultaneously.

Description of drawings

Fig. 1 is the mode chart that is illustrated in the apparatus for coating of the reverse photogravure coating method that uses in the experiment 5～8 of the present invention.

Fig. 2 is the mode chart of the configuration example of expression near-infrared absorbing film of the present invention.

Fig. 3 is the mode chart of the configuration example of expression near-infrared absorbing film of the present invention.

Fig. 4 is the mode chart of the configuration example of expression near-infrared absorbing film of the present invention.

Fig. 5 is the curve map that is illustrated in the spectral characteristic of the near-infrared absorbing film No.1 that makes among the embodiment 9-1-1.

Among the figure: the transparent base before the 1-coating coating fluid, 2-gravure roll, 3-feed flow dish, 4-scraper, the transparent base after the 5-coating coating fluid, 10-base film, 20-the 1st adhesiveness modified layer, 30-near infrared ray absorption layer.

Embodiment

With regard to near-infrared absorbing film of the present invention,, must possess transparent base film and near infrared ray absorption layer as inscape.Below, describe the present invention in detail.

[transparent base film]

As the transparent base of near-infrared absorbing film of the present invention, can be glass, but from the control of the viewpoint that can guarantee high transparent or cost and, the viewpoint of the easy degree of the property handled, preferably plastic film.Specifically can enumerate various resin films such as polyester system, acrylic acid series, cellulose-based, polyolefin (materials of tygon, polypropylene or other copolymerization types), polyvinyl chloride, polycarbonate, phenol system, carbamate system etc.Wherein, from the good viewpoint of the balance of thermotolerance, flexibility, preferred polyester is a film, more preferably polybutylene terephthalate, poly-2,6-(ethylene naphthalate), polyethylene terephthalate (PET) film, most preferably two-way stretch PET film.

" transparent " of transparent base film is meant that total light transmittance has reached more than 80%, is preferably more than 90%.In addition, the turbidity of base film is preferably below 5%, more preferably below 2%.When the transparent deterioration of base film, except the brightness that reduces display, the readability of image (sharpness) also can be influenced.Wherein, above-mentioned total light transmittance and turbidity are the numerical value of measuring according to the method for JIS-K7136 defined.

As the polyester that is used for ployester series film, can enumerate aromatic dicarboxylic acids such as making terephthalic acid (TPA), m-phthalic acid, naphthalenedicarboxylic acid or its ester and ethylene glycol, diethylene glycol, 1, glycol such as 4-butylene glycol, neopentyl glycol carry out then making it that polycondensation reaction takes place after esterification or the ester exchange reaction and the material that obtains, and the form with polymer chips provides usually.Above-mentioned ployester series film is usually by following method manufacturing, promptly, melt after its polymer chips, extrude with chip shape from the T die head and make non-stretched film, (preferred two-way stretch) stretches at least one direction of this non-stretched film, then carry out heat fixation processing, relaxation processing, produce described film thus.

As ployester series film, from viewpoints such as intensity, preferred especially biaxially oriented film.As drawing process, tubular type pulling method, two-way simultaneous pulling method, two-way pulling method one by one etc. are arranged usually, but, recommend two-way pulling method one by one from viewpoints such as the planarity of the film that obtains, dimensional stability, thickness evenness.Two-way oriented film one by one can be made by the following method, be on the length direction of non-stretched film for example at polyester, under glass temperature (Tg)～Tg+50 ℃ of polyester, be stretched to 2.0～5.0 times with roller, then, on Width, use stenter under 120～150 ℃, to be stretched to 1.2～5.0 times, and then after two-way stretch, under the temperature more than 220 ℃, carry out heat fixation and handle, then, relaxation 3～8% on Width.In addition, for the dimensional stability of the length direction that further improves film, can and with vertical relaxation processing.

As the inscape of base film, best two-way stretch PET film for example can obtain by following manufacture method.Wherein, following manufacture method only is a representation example, and the base film that is used for film of the present invention is not limited to the film made by following method.

After PET resin particle (pellet) is carried out abundant drying under reduced pressure, offer extruder, extrude the fusion PET resin of about 28 ℃ chip shape, use the rotation chill roll from the T die head, apply method by static and make this laminar fusion PET resin cooling curing, make the PET film that do not stretch.This PET film that do not stretch can be an individual layer, can also form multilayer by coetrusion.

Utilization is heated to 80～120 ℃ roller, with above-mentioned not stretching PET film stretching to 2.5～5.0 times, makes unilateral stretching PET film in the longitudinal direction.And then grip the end of monodirectional tension film with clip, and guide the hot blast district that is heated to 70～140 ℃ into, on Width, be stretched to 2.5～5.0 times.Then, guide 160～240 ℃ heat-treatment zone into, carry out 1～60 second thermal treatment, make it crystallization,, just can obtain two-way stretch PET film if finish crystallization.

On base film,, preferably contain particle and make it form projection on the surface in order to improve the property handled (handling) (for example, the coiling behind near infrared ray absorption layer stacked).As particle, can enumerate inorganic particulates such as silicon dioxide, smalite, talcum, lime carbonate, zeolite, aluminium oxide, barium sulphate, carbon black, zinc paste, titanium dioxide, acrylic resin, polyamide-based resin, polystyrene resin, polyester based resin, benzoguanamine (benzoguanamine)-organic fillers such as formalin condensation product.In order to keep the transparency of film, preferably reduce the content of the particle in the base film, for example be preferably below the above 1000ppm of 1ppm.And then, in order to keep the transparency, the preferred selective refraction rate particle close with substrate resin.In addition, in order on base film, to give various functions as required, can contain various adjuvants such as coloured material, photostabilizer (ultraviolet screener), pigment, antistatic agent.

Base film can be a monolayer constructions will, for example can be the lit-par-lit structure of (2 layers, 3 layers, 4 layers etc.) more than 2 layers.Forming under the situation of lit-par-lit structure, have can each layer function of independent design advantage.For example, under the situation that forms 2 layers of structure, with the layer on the top layer of the opposing face of the near infrared ray absorption layer of near-infrared absorbing film as thin layer, and only in this layer, contain above-mentioned particle and form uneven from the teeth outwards, layer (middle layer) between this top layer and the near infrared ray absorption layer as thick-layer, is not contained above-mentioned particle in fact in this layer, can reduce the content of particle thus, improve the transparency, can guarantee the eminence rational faculty simultaneously.

The state of above-mentioned " not containing particle in fact ", be meant the state that except the particle of sneaking into inevitably, does not make it to contain energetically particle from the outside, for example under the situation of inorganic particulate, be meant the state (in this manual, below same) of particle content below the detection boundary when adopting the fluorescent X-ray method to carry out quantitative test.

Manufacture method to the base film of lit-par-lit structure is not particularly limited, but consider throughput rate, so-called co-extrusion platen press below preferred the employing, promptly squeeze out the raw material of each layer from different extruders, guide to the non-stretched film that makes lit-par-lit structure in 1 mould (dice), afterwards it is implemented above-mentioned stretching.

The thickness of base film is different because of raw material, when using mylar, is preferably more than the 35 μ m, more preferably more than the 50 μ m, is preferably especially more than the 100 μ m.On the other hand, the upper limit of thickness is preferably below the 260 μ m, more preferably below the 200 μ m.When thinner thickness, not only the property handled is not good, and heats when drying when reducing the residual solvent of near infrared ray absorption layer, can hot wrinkle occur on the film and cause planarity not good easily.On the other hand, under the thicker situation of thickness, existing problems aspect cost not only when coiling into bobbin shape when preserving, are easy to generate the bad problem of planarity that is caused by the gauffer that curls.

In near infrared absorbing coloring matter described later, its decomposition can obtain promoting under the action of ultraviolet ray that the pigment that has contains in sunray, therefore as the base film of near-infrared absorbing film, the preferred use has the base film that cuts off ultraviolet function (photostability), thereby constitutes the light filter that the near infrared ray absorption layer of near-infrared absorbing film is configured in the display side.

In order to give photostability, preferably in base film, contain ultraviolet light absorber to base film.As ultraviolet light absorber, can enumerate the organic system ultraviolet light absorber and inorganic be ultraviolet light absorber, but from the viewpoint of the transparency, preferred organic system ultraviolet light absorber.As the organic system ultraviolet light absorber, known material can use, but wherein is fit to use benzotriazole, benzophenone, cyclic imide acid esters, particularly from stable on heating viewpoint, and preferred cyclic imide acid esters.In addition, can and with above-mentioned ultraviolet light absorber more than 2 kinds.

As benzotriazole is ultraviolet light absorber, can enumerate 2-[2 '-hydroxyl-5 '-(methacryloxypropyl methyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methylacryoyloxyethyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxypropyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methacryloxypropyl hexyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-the 3 '-tert-butyl group-5 '-(methylacryoyloxyethyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-the 5 '-tert-butyl group-3 '-(methylacryoyloxyethyl) phenyl]-the 2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methylacryoyloxyethyl) phenyl]-5-chloro-2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methylacryoyloxyethyl) phenyl]-5-methoxyl-2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methylacryoyloxyethyl) phenyl]-5-cyano group-2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methylacryoyloxyethyl) phenyl]-the 5-tert-butyl group-2H-benzotriazole, 2-[2 '-hydroxyl-5 '-(methylacryoyloxyethyl) phenyl]-5-nitro-2H-benzotriazole etc.

As the benzophenone series ultraviolet light absorber, can enumerate 2,2 ', 4,4 '-tetrahydroxybenzophenone, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,4 dihydroxyl benzophenone, 2-hydroxyl-4-acetoxyethoxy benzophenone, 2-hydroxyl-4-methoxy benzophenone, 2,2 '-dihydroxy-4-methoxy benzophenone, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, Octabenzone, 2,2 '-dihydroxy-4,4 '-dimethoxy-5,5 '-disulfo benzophenone, 2 sodium salts etc.

As the cyclic imide acid esters is ultraviolet light absorber, can enumerate 2,2 '-(1, the 4-phenylene) two (4H-3,1-benzoxazine-4-ketone), 2-methyl-3,1-benzoxazine-4-ketone, 2-butyl-3,1-benzoxazine-4-ketone, 2-phenyl-3,1-benzoxazine-4-ketone, 2-(1 or 2-naphthyl)-3,1-benzoxazine-4-ketone, 2-(4-xenyl)-3,1-benzoxazine-4-ketone, 2-p-nitrophenyl-3,1-benzoxazine-4-ketone, 2-m-nitro base-3,1-benzoxazine-4-ketone, 2-is to benzoyloxy phenyl-3,1-benzoxazine-4-ketone, 2-p-methoxyphenyl-3,1-benzoxazine-4-ketone, 2-o-methoxyphenyl-3,1-benzoxazine-4-ketone, 2-cyclohexyl-3,1-benzoxazine-4-ketone, 2-is right-(perhaps-) BIDA phenyl-3,1-benzoxazine-4-ketone, 2,2 '-(1, the 4-phenylene) two (4H-3,1-benzoxazinone-4-ketone), 2,2 '-two (3,1-benzoxazine-4-ketone), 2,2 '-ethylenebis (3,1-benzoxazine-4-ketone), 2,2 '-tetramethylene two (3,1-benzoxazine-4-ketone), 2,2 '-decamethylene two (3,1-benzoxazine-4-ketone), 2,2 '-TOPOT 2,2 (3,1-benzoxazine-4-ketone), 2,2 '-metaphenylene two (3,1-benzoxazine-4-ketone), 2,2 '-(4,4 '-diphenylene) two (3,1-benzoxazine-4-ketone), 2,2 '-(2,6-or 1, the 5-naphthalene) two (3,1-benzoxazine-4-ketone), 2,2 '-(the 2-methyl-to phenylene) two (3,1-benzoxazine-4-ketone), 2,2 '-(the 2-nitro-to phenylene) two (3,1-benzoxazine-4-ketone), 2,2 '-(the 2-chloro-is to phenylene) two (3,1-benzoxazine-4-ketone), 2,2 '-(1, the 4-cyclohexylidene) two (3,1-benzoxazine-4-ketone), 1,3,5-three (3,1-benzoxazine-4-ketone-2-yl) benzene etc.

In addition, it is that ultraviolet light absorber uses that following compound etc. also can be used as the cyclic imide acid esters, for example, and 1,3,5-three (3,1-benzoxazine-4-ketone-2-yl) naphthalene and 2,4,6-three (3,1-benzoxazine-4-ketone-2-yl) naphthalene, 2,8-dimethyl-4H, the 6H-benzo (1,2-d; 5,4-d ') two-(1,3)-oxazines-4,6-diketone, 2,7-dimethyl-4H, the 9H-benzo (1,2-d; 5,4-d ') two-(1,3)-oxazines-4,9-diketone, 2,8-diphenyl-4H, the 8H-benzo (1,2-d; 5,4-d ') two-(1,3)-oxazines-4,6-diketone, 2,7-diphenyl-4H, the 9H-benzo (1,2-d; 5; 4-d ') two-(1; 3)-oxazines-4; the 6-diketone; 6; 6 '-two (2-methyl-4H; 3,1-benzoxazine-4-ketone); 6,6 '-two (2-ethyl-4H; 3; 1-benzoxazine-4-ketone); 6,6 '-two (2-phenyl-4H, 3; 1-benzoxazine-4-ketone); 6; 6 '-di-2-ethylhexylphosphine oxide (2-methyl-4H, 3,1-benzoxazine-4-ketone); 6; 6 '-di-2-ethylhexylphosphine oxide (2-phenyl-4H; 3,1-benzoxazine-4-ketone); 6,6 '-ethylenebis (2-methyl-4H; 3; 1-benzoxazine-4-ketone); 6,6 '-ethylenebis (2-phenyl-4H, 3; 1-benzoxazine-4-ketone); 6; 6 '-butylidene two (2-methyl-4H, 3,1-benzoxazine-4-ketone); 6; two (2-phenyl-the 4H of 6 '-butylidene; 3,1-benzoxazine-4-ketone); 6, the two (2-methyl-4H of 6 '-oxygen base; 3; 1-benzoxazine-4-ketone); 6,6 '-oxygen base two (2-phenyl-4H, 3; 1-benzoxazine-4-ketone); 6; 6 '-sulfonyl two (2-methyl-4H, 3,1-benzoxazine-4-ketone); 6; two (2-phenyl-the 4H of 6 '-sulfonyl; 3,1-benzoxazine-4-ketone); 6, the two (2-methyl-4H of 6 '-carbonyl; 3; 1-benzoxazine-4-ketone); 6,6 '-carbonyl two (2-phenyl-4H, 3; 1-benzoxazine-4-ketone); 7; 7 '-di-2-ethylhexylphosphine oxide (2-methyl-4H, 3,1-benzoxazine-4-ketone); 7; 7 '-di-2-ethylhexylphosphine oxide (2-phenyl-4H; 3,1-benzoxazine-4-ketone); 7,7 '-two (2-methyl-4H; 3; 1-benzoxazine-4-ketone); 7,7 '-ethylenebis (2-methyl-4H, 3; 1-benzoxazine-4-ketone); 7; 7 '-oxygen base two (2-methyl-4H, 3,1-benzoxazine-4-ketone); 7; two (2-methyl-the 4H of 7 '-sulfonyl; 3,1-benzoxazine-4-ketone); 7, the two (2-methyl-4H of 7 '-carbonyl; 3; 1-benzoxazine-4-ketone); 6,7 '-two (2-methyl-4H, 3; 1-benzoxazine-4-ketone); 6; 7 '-two (2-phenyl-4H, 3,1-benzoxazines-4-ketone); 6; 7 '-di-2-ethylhexylphosphine oxide (2-methyl-4H; 3,1-benzoxazine-4-ketone); 6,7 '-di-2-ethylhexylphosphine oxide (2-phenyl-4H; 3,1-benzoxazine-4-ketone) etc.

With regard to above-mentioned ultraviolet light absorber, it is more than 290 ℃ that its thermal decomposition begins temperature, is preferred aspect this operation pollution when reduce making base film.When containing thermal decomposition, fusing begins the polyester of temperature less than 290 ℃ ultraviolet light absorber, and when rotation is squeezed into chip shape in the chill roll, the decomposition product of ultraviolet light absorber can be attached on the above-mentioned roller, then once more attached on the film, cause damage to film, form optical defect easily, so not preferred.

The purpose of mixing ultraviolet light absorber in base film is, improve the photostability of near infrared ray absorption layer with respect to outer light, described near infrared ray absorption layer can show the near-infrared absorbing ability as the major function of near-infrared absorbing film of the present invention.Be that its purpose is to embody the effect that deterioration takes place because of ultraviolet ray contained in the outer light near infrared absorbing coloring matter that suppresses to contain in the near infrared ray absorption layer.

Specifically, containing the layer preference of ultraviolet light absorber such as the transmitance at wavelength 380nm place is below 10%.More preferably the transmitance at wavelength 390nm place is below 10%.The transmitance at special optimal wavelength 400nm place is below 10%.Satisfy the content of ultraviolet light absorber of the low molecule type of such characteristic, the resin with respect to constituting UV-absorbing layer is preferably 0.1～4 quality %, more preferably 0.2～3 quality %.When UVA dosage was very few, ultraviolet absorption ability reduced, and had served as for a long time, the situation of film generation xanthochromia occurred, and so the perhaps situation of the system film reduction of film is not preferred.

In addition, from avoiding considering that because of the angle of oozing out the problem that causes to film surface the material of also recommending use macromolecule type is as ultraviolet light absorber.In addition, by reducing, also can improve adhesiveness with other stacked layers to the oozing out of film.The ultraviolet light absorber of macromolecule type is meant the polymkeric substance that has as the useful skeleton of ultraviolet light absorber on side chain.When the mutual capacitive considered with polyester, preferred polyester is ultraviolet light absorber or acrylic acid series polymeric compounds ultraviolet light absorber.For example, with terephthalic acid (TPA) as the dicarboxylic acid composition, ethylene glycol and/or 1, the 4-butylene glycol is as main glycol component, and then the naphthalenedicarboxylic acid that will represent with the naphthalenetetracarbimidec imidec of general formula (I) expression with general formula (II) is as copolymer composition and synthetic polyester is ultraviolet light absorber (Mitsubishi Chemical's system, ノ バ ペ Star Network ス U-110), or has an acrylic acid series polymeric compounds (BASF system of 2-(2-hydroxy phenyl) benzotriazole skeleton at side chain, UVA-1635) etc., except can keeping UVA characteristic as target, from keeping the angle of characteristics such as the transparency, also be preferred.

In above-mentioned general formula (I), R represents organic residue (alkylidene etc.), and X represents hydroxyl etc.

With regard to the content of the ultraviolet light absorber of macromolecule type, the resin with respect to constituting UV-absorbing layer is preferably 0.1～20 quality %, more preferably 0.5～15 quality %.When UVA dosage was very few, ultraviolet absorption ability reduced, and had served as for a long time, the situation of film generation xanthochromia occurred, or the situation of the system film reduction of film, so not preferred.

In base film, the preferred lit-par-lit structure that adopts at least 3 layers (3 layers, 4 layers, 5 layers etc.) makes two top layer not contain ultraviolet light absorber in fact, and the layer (a base material middle layer) of centre is made UV-absorbing layer.

When containing ultraviolet light absorber in the base film at single layer structure, in the extrusion process when the system film, ultraviolet light absorber can distil, attached to the ejiction opening of mould or be used for to being melted the chill roll that the polyester that is squeezed into chip shape cools off, the stenter that is used to stretch etc., these can cause optical defect sometimes attached on the molten polyester that extruding is come out afterwards.But, when making film, be exuded to the phenomenon of film surface by adopting above-mentioned base film, can suppress in the middle layer effectively the ultraviolet light absorber that is closed with lit-par-lit structure.Therefore, can alleviate the pollution of ejiction opening or chill roll, the stenter etc. of mould, suppress the appearance of the film defects that causes by this pollution.In addition, can also suppress the adhering decline of each interlayer of causing by oozing out of ultraviolet light absorber.

When the mylar that constitutes base film is 3-tier architecture, have only the base material middle layer to contain ultraviolet light absorber.Under situation about forming more than 4 layers, any layer more than 1 except two top layers can contain ultraviolet light absorber, can also be all to contain ultraviolet light absorber except all layers more than two top layers.Wherein, " in fact " in " not containing ultraviolet light absorber in fact " in two top layers, its purport is to sneak into inevitably except the situation of ultraviolet light absorber from the situation etc. that the material that oozes out of layer that contains ultraviolet light absorber is diffused into two top layers.Most preferred base film is that 3-tier architecture and base material middle layer are the formations of UV-absorbing layer.

The stacked thickness ratio of the base film of lit-par-lit structure can be set arbitrarily ad lib, but preferred embodiment, the thickness on two top layers is respectively more than 3% of gross thickness, more preferably more than 5%, and is below 15%, more preferably below 10%.In two top layers,, then can't fully prevent the distillation of ultraviolet light absorber sometimes and ooze out as long as there is a side thickness too small.In addition, in two top layers, as long as there is a side thickness blocked up, the effect that then not only prevents the distillation of ultraviolet light absorber/ooze out can reach capacity, and with the content of ultraviolet light absorber between different equilibrium states under, sometimes the UVA agent concentration (amount of per unit area) under the overlooking of film can reduce, and can not give full play to absorb ultraviolet effect, so not preferred.

Each layer of laminated substrate film preferably is made of polyester, these polyester can identical kind, also can be different fully, also can be only some layer be of the same race, but from the easy degree of production management or the viewpoints such as recovery of chip resin, adopting identical type and all layers all to use PET is preferred embodiment.

Wherein, on the film thickness direction of the ultraviolet light absorber that embodies by the multiple stratification of laminated substrate partially in degree, can use surperficial IR analytic approach to estimate.The detailed content of evaluation method has record in the evaluation method of embodiment, the effect that is caused by multiple stratification preferably manages according to the numerical value that obtains from this evaluation assessment.Ultraviolet light absorber on the thickness direction of film partially in degree, can be subjected to the influence of the thickness ratio of two top layers of laminated substrate film and other layers (base material middle layer), even but thickness is identical, for example, also can change because of the molten resin delivery pipe of the light filter behind the system film or the resin temperature of flat-die etc.As the ultraviolet light absorber that obtains by above-mentioned evaluation assessment partially the degree, be preferably below 0.20, more preferably below 0.10, be preferably below 0.05 especially.

To ultraviolet light absorber without limits, but preferably mix when polymeric polyester or during melt extruded to the mixed method of mylar.At this moment, make in advance that to contain the masterbatch pellet of ultraviolet light absorber and add thus be preferred embodiment.For example, as preferred embodiment, but the following method of illustration.At first, mixed polyester and ultraviolet light absorber are modulated masterbatch pellet.This masterbatch pellet is the particle that not contain to give easy sliding property in fact be the particle of purpose.The feed particles of having mixed this masterbatch pellet and original polyester granulate is carried out sufficient vacuum drying, offer extruder then, melt extruded becomes film shape, carries out cooling curing on glue spreader (casting roll), makes not oriented polyester film.In each layer stacked, the preferred employing from different extruders squeezes out the polyester granulate that constitutes each layer and guides to 1 mould and make the co-extrusion platen press of the non-stretched film of lit-par-lit structure.

When carrying out above-mentioned extruding, make the resin temperature that arrives extruder fusing department, kneading part, polymer pipe, gear-type pump, light filter reach 280～290 ℃, making subsequently polymer pipe of arrival, the resin temperature of flat-die is 270～280 ℃, this is from preventing that ultraviolet light absorber from the distillation of mould ejiction opening, the viewpoint of pollution on the chill roll, being preferred.

In addition, in the arbitrary site that molten polyester is maintained at about 280 ℃, preferably carry out high precision and filter to remove foreign matter contained in the polyester.If such foreign matter remains in the base film, when as the near-infrared absorbing filter applications during in plasma display, can become the reason that optical defect occurs, in addition, when making the near-infrared absorbing light filter, also can become the main cause that damage occurs, damage wherein can cause optical defect.

The filter materials that the high precision that is used for molten polyester is filtered is not particularly limited, if the filter materials of stainless steel sintered body, it is that the condensation product and the organic performance of high-melting-point of major component is outstanding that then this material is removed with Si, Ti, Sb, Ge, Cu, so be fit to use.And then the filtered particles size of filter materials (exhibits initial filtration efficiency 95%) is preferably below the 20 μ m, more preferably below the 15 μ m.When the filtered particles size (exhibits initial filtration efficiency 95%) of filter materials surpassed 20 μ m, the size that can't fully remove the appearance reason of the reason that becomes above-mentioned optical defect or damage surpassed the foreign matter of 20 μ m.The filtered particles size (exhibits initial filtration efficiency 95%) of using filter materials is that high precision that the following filter materials of 20 μ m carries out molten resin is when filtering, though throughput rate reduces sometimes, but can obtain the projection that causes by big particle less, when making the near-infrared absorbing light filter, can suppress to lose the film of appearance, be preferred therefore from this angle.

If the foreign matter that is present in the raw material polyester has residual, ooze out the ultraviolet light absorber that comes and pollute mould ejiction opening etc. attached on the film from molten polyester when perhaps making film, then in the stretching process when the system film, this foreign matter or ultraviolet light absorber (below, be generically and collectively referred to as " foreign matter etc. ") around, optical skew appears in the orientation disorder of polyester molecule.Because this optical skew, described defective can be become the also big defective of size than actual foreign matter etc. by identification, so can the apparent damage quality.For example, even the foreign matter of 20 μ m sizes also can be optically become size more than the 50 μ m by identification, and then can be become the optical defect of the size more than the 100 μ m by identification.In addition, the transparency of film is high more, and the optical defect that is caused by fine foreign matters will become distincter.Film is thick more, and the film that the content of the foreign matter of the film per unit area under overlooking etc. can relatively approach is many, and it is more serious that this problem can become.Thus, the foreign matter in the polyester etc. is preferably removed as far as possible, recommends to adopt above-mentioned the whole bag of tricks.

(vertical: as the direction of travel when making laminate film) non-stretched film that obtains to be stretched to 2.5～5.0 times, to make monodirectional tension film with the roller that is heated to 80～120 ℃ at length direction.Then, the end with clip gripping film guides to the hot blast district that is heated to 120～150 ℃, is stretched to 2.5～5.0 times on Width.Then, under 200～250 ℃, heat-treat, in this heat treatment step, carry out about 3% tension and relaxation processing as required at Width, can obtain the laminated substrate film thus.

In the laminated polyester film that is obtained by said method, the degree of depth that is present in the surface is that 1 μ m is above, length is that the above damage of 3mm is preferably 100/m ²Below.The number of above-mentioned damage is 30/m more preferably ²Below, be preferably 10/m especially ²Below.As long as the number that makes above-mentioned damage in such scope, just can not produce the problem that is caused by optical defect.

As preventing that the method for damage from appearring in film, can enumerate (a) and avoid surperficial, particularly can cause damage " defective ", (b) avoid making film on the roller surface of contact, on vertical and horizontal, to occur sliding in the roller surface appearance that contacts with film at film surface itself or roller.Above-mentioned " defective " is meant at the damage of roller surface formation, deposit, attachment, foreign matter etc. by contact all factors that make film fine damage occur with film.Thus, disappear, can reduce the appearance of damage at film surface by making these defectives.In order to prevent above-mentioned defective, for example can adopt the method for enumerating below.

The surface roughness Ra that can enumerate the roller that uses when making above-mentioned film is made as the method below the 0.1 μ m, perhaps on the roller of the preheating inlet of longitudinal stretching operation and chill roll, be provided with the roller clearer with prevent deposit, attachment, foreign matter etc. can cause the factor of damage be deposited in the roller surface method.

In addition, in addition the degree of purification in the above-mentioned thin film fabrication operation is made as the method that (particle more than the 0.5 μ m below 1000 is arranged) below 1000 grades in per 1 cubic feet volume, around the preferred especially roller is below 100 grades, and the ventilation cooling device that is used to cool off anti-roll surface in the cast operation also uses purifying air below 100 grades.

And then, can also enumerate before making above-mentioned film, cut the method that the defective on the roller comes pair roller to clean by using abrasive substance.In addition, for fear of causing thin film adsorbs dust etc. to become defective because of static, can enumerate neutralizer is set so that the carried charge of film is ± method below the 1500V in whole operation.From the operation that being poured into of double orientation laminated polyester film stenter described later is handled, be the operation of main easy appearance damage, should the interval be provided with compactly and make by the time be below 5 minutes, also help to suppress the appearance of defective.

About roller, by forming moisture film, perhaps use the roller of gas holder (air floating) type on the roller surface, the defective that can constitute the roller surface directly is not contacted with the structure of film.In addition,, defective can be reduced, the defective on roller surface can be reduced to the adhering to of roller surface by being controlled to be below the 1000ppm from the oligomer amount that film is separated out.

And then, in the coiling process after stretching, push the surface of the end side of thin-film width direction with the roller that has projection, form jog on this part, the film that will form this jog with spooler batches the rolling tubular simultaneously, and then make the protrusion-shaped in the roller of this band projection become narrow head shapes, and make the top of this projection rounded, the radius-of-curvature of its end face is made as below the 0.4mm, thus, in the take-up mechanism of film, can avoid film to contact with defective.

In addition, making film avoid sliding on the roller surface, also is the effective ways that prevent to damage appearance.For example, can adopt the method for enumerating below.For example, dwindle the diameter of roller, use suction roll, use the adhering apparatus of static adhesion, local clamp (part nip) etc., can increase the adhesion of film, can suppress to occur long damage thus to roller.Particularly dwindle the diameter of roller, also be equivalent to make the slippage sectionalization of film, help to prevent the generation of long damage.In addition, near the end of roller Width, length and frequency just increase in the great majority damage, end at the roller Width, be difficult to obtain damaging few part, so, can obtain damaging few film by to repairing near the central authorities of damaging few roller Width.

In addition, as vertical damage or the horizontal main cause that occurs of damage, can also enumerate distortion such as expansion on each film vertical or horizontal, contraction.The distortion of these films mainly is that the temperature variation by film causes.Thus, the temperature variation of the film by being suppressed at the roller surface can reduce this deformation of thin membrane amount that is caused by temperature, can prevent to produce vertical damage or laterally damage.Specifically, preferably the temperature variation with the film on the every roller is controlled to be below 40 ℃, is preferably below 30 ℃, and is further preferred below 20 ℃, further more preferably below 10 ℃, is preferably especially below 5 ℃.As the method that the temperature variation at the film on this roller surface is suppressed, for example can enumerate aerial cooling between roller, make and cool off in its water that passes through tank etc.And then, by increasing the radical of roller, can reduce film in per 1 roller surface temperature change.Preferably the roller radical in the longitudinal stretching operation is made as more than 10.

In addition, have the immediate velocity distribution line chart of the deflection that causes with respect to temperature or tension force, can reduce the longitudinal sliding motion of film by film by the relation of the relative velocity of many rollers is set to become.And then, in the painting process of the coating fluid that is used to form bonding modified layer described later, with regard to drying condition, initial stage in the dryer interval is finished drying, cool off before arriving outlet, film temperature with the dryer exit is controlled to be below 40 ℃ thus, can reduce the slip of the film that is caused by temperature variation thus.

In addition, if the tension force when film moves is low excessively, then curable grip can descend, slide (dislocation) appears, if and too high, its stress deformation meeting increases, also can occur sliding, so preferably regulate, so that reach 4.9～29.4MPa as the optimum tension scope with driven roller speed and tension adjustment member.In addition, film and the friction factor between the roller under the serviceability temperature when making by making are more than 0.2, can be suppressed at the slip of the film on roller surface.

And then, about the roller (free roll) of living, preferably adopt specific bearing, be set to have the following rotational resistance of 19.6N.About driven roller, preferably flutter is controlled at below 0.01%.

More than two-way pulling method one by one is illustrated, but also can use simultaneously to the double stretching method as drawing process.In addition, can also be the multistage stretching method.

[near infrared ray absorption layer]

The near infrared ray absorption layer of film of the present invention is formed as the composition of principal ingredient by containing the near infrared absorbing coloring matter and the resin that have very big absorption at wavelength 800～1200nm place.In near infrared ray absorption layer, the summation of near infrared absorbing coloring matter and resin is preferably more than the 80 quality %, more preferably more than the 85 quality %, more preferably more than the 90 quality %.

As the near infrared absorbing coloring matter that can be used for film of the present invention, so long as (wavelength 800～1200nm) has the pigment of very big absorption, just is not particularly limited near infrared range.But, near-infrared absorbing film of the present invention is suitable for display applications, particularly be suitable for the plasma display purposes, when requirement is preferably near infrared range and has bigger absorption, the transmitance of visible region is higher, from such viewpoint, recommend to select for use the high pigment of transmitance of visible region.Specifically, preferred compositions is used with Ji Yinmoni diimmonium (ジ イ Application モ ニ ウ system) the salt based compound of following general formula (III) expression and other near infrared absorbing coloring matter more than a kind.

(in the formula, R ¹～R ⁸Can be identical or different separately, expression hydrogen atom, alkyl, aryl, alkenyl, aralkyl, alkynyl.R ⁹～R ¹²Can be identical or different separately, expression hydrogen atom, halogen atom, amino, cyano group, nitro, carboxyl, alkyl, alkoxy.At R ¹～R ¹²In, can have substituting group in conjunction with substituent group.X ^-The expression negative ion.)。

R at above-mentioned general formula (III) ¹～R ⁸Under the situation for (a) alkyl, (b) aryl, (c) alkenyl, aralkyl, (d) alkynyl, respectively can the following group of illustration.

(a) alkyl: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, n-pentyl, n-hexyl, n-octyl, 2-hydroxyethyl, 2-cyanoethyl, 3-hydroxypropyl, 3-cyanogen propyl group, methoxy ethyl, ethoxyethyl group, butoxyethyl group etc.

(b) aryl: phenyl, fluoro phenyl, chlorphenyl, tolyl, diethylamino phenyl, naphthyl etc.

(c) alkenyl: vinyl, propenyl, butenyl group, pentenyl etc.

(d) aralkyl: benzyl, to fluoro benzyl, rubigan, phenylpropyl, naphthalene ethyl etc.

In addition, as the R of above-mentioned general formula (III) ⁹～R ¹²(e) halogen atom, (f) amino, (g) alkyl, (h) alkoxy, respectively can the following group of illustration.

(e) halogen atom: fluorine, chlorine, bromine etc.

(f) amino: lignocaine, dimethylamino etc.

(g) alkyl: methyl, ethyl, propyl group, trifluoromethyl etc.

(h) alkoxy: methoxyl, ethoxy, propoxyl group etc.

In addition, as the X in the above-mentioned general formula (III) ^-, for example can enumerate negative ion such as fluorine ion, chlorion, bromide ion, iodide ion, perchlorate ion, hexafluoro-antimonic acid ion, hexafluorophosphoric acid ion, tetrafluoro boric acid ion, two (fluoroform sulphonyl) acid imide acid ion.

Ji Yinmoni diimmonium salt based compound as with above-mentioned general formula (III) expression can use commercially available product.For example, be fit to use Kayasorb IRG-022, IRG-023, IRG-024 (more than, Japanese chemical drug corporate system), CIR-1080, CIR-1081, CIR-1083, CIR-1085 (more than, Japanese カ one リ Star ト corporate system) etc.

Above-mentioned Ji Yinmoni diimmonium salt based compound has following characteristics, i.e. the absorption of near infrared range is bigger, and the wavelength region may that can absorb is also wide, and then the transmitance of visible region is also high.But, Ji Yinmoni diimmonium salt based compound also has character as described below, at high temperature or easy sex change under the high humidity promptly, causes the absorption of near infrared range to reduce, perhaps the transmitance of the part of visible region descends, and tone changes easily.But, by being that the coating fluid of the above adhesiveness modified resin of 200 equivalents/t forms adhesiveness modified layer described later by containing acid number, even at the hot and humid down long-time film of placing, also can suppress the sex change of above-mentioned Ji Yinmoni diimmonium salt based compound.

Be at least more than 2 kinds in order to increase the absorption of near infrared range, preferably make the near infrared absorbing coloring matter kind that contains in the near infrared ray absorption layer.At this moment, preferred also with the pigment beyond above-mentioned Ji Yinmoni diimmonium salt based compound and this compound.This is because can guarantee wideer absorbing wavelength zone thus.

As can with above-mentioned Ji Yinmoni diimmonium salt based compound and other near infrared absorbing coloring matter of usefulness, can enumerate the phthalocyanine based compound, dithiol metal complex based compound, the cyanine based compound, naphthalene phthalocyanine (naphthalocyanine) based compound, Si Keali squalirium salt based compound, the pyralium salt based compound, sulfo-is trained sharp チ オ ペ リ リ ウ system based compound, Ke Laokeni Network ロ コ ニ ウ system based compound, indoaniline chelating system pigment, indigo naphthols chelating system pigment, azo is a pigment, azo chelating system pigment, amine salt is a pigment, quinone is a pigment, anthraquinone is a pigment, polymethine is a pigment, triphenylmethane is a pigment etc.

For example, can use commercially available product as above-mentioned phthalocyanine based compound.As the product that is fit to, specifically can enumerate Excolor IR-1, IR-2, IR-3, IR-4, IR-10, IR-10A, IR-12, IR-14, TXEX-805K, TXEX-809K,, TXEX-810K, TXEX-811K, TXEX-812K, TXEX-813K, TXEX-814K (more than, Japan's catalyst Co. system), MIR-369, MIR-389 (more than, the Mitsui Chemicals corporate system) etc.

In addition, as above-mentioned dithiol metal complex based compound, for example, be fit to use compound with following general formula (IV) expression.

(in the formula, R ¹³～R ¹⁶Can be identical or different separately, expression hydrogen atom, halogen atom, alkyl, alkoxy, aryl, aralkyl, amino.M represents nickel, copper, cobalt, palladium, platinum.)

R as above-mentioned general formula (IV) ¹³～R ¹⁶Object lesson, can enumerate halogen atoms such as fluorine, chlorine, bromine; Alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, n-pentyl, n-hexyl, n-octyl, 2-hydroxyethyl, 2-cyanoethyl, 3-hydroxypropyl, 3-cyanogen propyl group, methoxy ethyl, ethoxyethyl group, butoxyethyl group; Alkoxys such as methoxyl, ethoxy, propoxyl group, butoxy; Aryl such as phenyl, fluoro phenyl, chlorphenyl, tolyl, diethylamino phenyl, naphthyl; Benzyl, to aralkyl such as fluoro benzyl, rubigan, phenylpropyl, naphthalene ethyls; Amino such as dimethylamino, lignocaine, dipropyl amino, dibutylamino.

Dithiol metal complex based compound as above-mentioned general formula (IV) also is fit to use commercially available products such as for example Mitsui Chemicals system: SIR-128, SIR-130, SIR-132, SIR-159.

In addition,, be fit to use TZ-103, TZ-104, TZ-105, TZ-109, TZ-111, the TZ-114 of rising sun electrification system, the CY-9 of Japanese chemical drug system, CY-10, CY-20, CY-30, the IR-301 of hillside plot chemistry system etc. as the cyanine based compound.

In addition, when near-infrared absorbing film of the present invention being used for plasma display,, also can near infrared ray absorption layer, contain the complementary color pigment that can absorb the neon light that from plasma display, sends in order to improve colour balance with the front light filter.Specifically, preferably near infrared ray absorption layer, be contained in the complementary color pigment that has very big absorption in the scope of wavelength 550～620nm with specific amount, so that be 10～60%, and be below 20% in the transmitance of the light of the wavelength region may of 820nm～1100nm in the transmitance of the light of the wavelength region may of 550nm～600nm.

To using the complementary color pigment to be not particularly limited, be the following pigment of 60nm but preferably select the half-breadth value of absorption for use.The further preferred half-breadth value that absorbs is below the 50nm.In addition, preferably do not interact or interact little with above-mentioned near infrared absorbing coloring matter.As particularly preferred complementary color pigment, can enumerate the compound that constitutes by cyanine system, polymethine system, squalirium salt system, phthalocyanine system, naphthalene phthalocyanine system, quinone system, aza porphyrin system, azo system, azo chelating system, azurenium system, pyralium salt system, Network ロ コ ニ ウ system system, indoaniline chelating system, indigo naphthols chelating system, azo chelating system, dithiol metal complex system, methylene pyrrole system, azomethine system, cluck ton system, oxonol system etc.In the middle of these complementary color pigments, pigment with above-mentioned near infrared absorbing coloring matter identical type is arranged, can select the substituent kind that imported, be to use the pigment of having regulated chain length to make it have very big absorption in the scope of wavelength 550～620nm in the pigment at cyanine for example.

Near infrared ray absorption layer is preferably the form of having disperseed above-mentioned near infrared absorbing coloring matter in resin.Ji Yinmoni diimmonium salt based compound is preferably below the 7 quality % with respect to the content of resin, more preferably below the 5 quality %, more preferably below the 4 quality %.In addition, Ji Yinmoni diimmonium salt based compound is preferably 0.5 quality % with respect to the lower limit of the content of resin, is limited to 1 quality % under preferred, is limited to 1.5 quality % under further preferred.

When Ji Yinmoni diimmonium salt based compound surpassed above-mentioned scope with respect to the content of resin, the concentration of the near infrared absorbing coloring matter in the resin increased, and the distance between this pigment can further shorten.For this reason, each other, particularly occur easily between Ji Yinmoni diimmonium salt based compound and other pigments interacting near infrared absorbing coloring matter.When placing such near-infrared absorbing film under hot and humid, sex change can take place in pigment under above-mentioned interaction, occurs the variation of spectral characteristic or tone easily.Wherein, the content of the pigment except Ji Yinmoni diimmonium salt based compound is preferably 0.01～10 quality % with respect to resin, more preferably 0.05～8 quality %.

Wherein, when in forming resin, being dispersed with the near infrared ray absorption layer of form of near infrared absorbing coloring matter, for example, the preferred method that adopts is to be produced in the solvent dissolving or to be dispersed with after the coating fluid of near infrared absorbing coloring matter and resin, and it directly or by getting involved other layers is coated on the base film and carries out dry method.

The resin that is used for the near infrared absorbing coloring matter layer, the high resin of preferred glass temperature (Tg), the concrete resin that is fit to use Tg in the scope of 80～250 ℃ (more preferably 100～160 ℃).Using Tg to be lower than under 80 ℃ the situation of resin, near infrared absorbing coloring matter is movable easily down hot and humid, so be easy to generate interaction between this pigment, the sex change meeting of this pigment becomes remarkable.Therefore, the spectral characteristic of film or tone have the trend that changes easily.

In addition, for example, when using above-mentioned coating fluid to form near infrared ray absorption layer, if use Tg to surpass 250 ℃ resin, then by coating, dry formation near infrared ray absorption layer the time, the evaporation efficiency of solvent worsens, and residual quantity of solvent has the trend that increases in this layer.Its result, the thermotolerance or the moisture-proof of near infrared ray absorption layer descend sometimes.

The resin of using as near infrared ray absorption layer, for example can be from synthetic macromolecule resins such as polyester based resin, acrylic resin, polyamide-based resin, polyurethane series resin, polyolefin-based resins, polycarbonate-based resin, polystyrene resins, in natural polymer such as gelatin, the cellulose derivative resins etc., selection has the resin of the Tg of above-mentioned scope.In addition, can use have the fluorenes ring copolyester (for example, カ ネ ボ ウ system " O-PET "), nonpolar cyclic olefin polymer (for example, Japan's ゼ オ Application system " ZEONEX "), have at side chain polar group the norborene skeleton resin (for example, JSR system " ARTON "), ester ring type acrylic resin (for example, Japan's system of changing into " オ プ ト レ ッ Star ") etc.

In addition, in order to improve the photostability of film, near infrared ray absorption layer, can also contain above-mentioned ultraviolet light absorber.At this moment, for example, can adopt the method for interpolation ultraviolet light absorber in the above-mentioned coating fluid of near infrared ray absorption layer formation usefulness etc.

In the present invention, key is that the HLB that further contains 0.01～2.0 quality % near infrared ray absorption layer is 2～12 surfactant.Thus, for example, form near infrared ray absorption layer if use aforesaid near infrared ray absorption layer to form with coating fluid, then preferably in this coating fluid, further contain HLB and be 2～12 surfactant, and its content with respect to the solid state component of coating fluid is 0.01～2.0 quality %.

In the present invention, even mismatch surfactant, also can give full play to thermotolerance, the moisture-proof of near infrared ray absorption layer, but by adding surfactant, can improve the dispersiveness of near infrared absorbing coloring matter in resin, improve the appearance of film of this near infrared ray absorption layer, particularly improve by coming off of causing of little microvesicle, adhere to the depression that causes, the depression in drying process by foreign matter etc.And then the heating of surfactant when being coated with drying is exuded to the surface and goes up and localization, and thus, when adding the low surfactant of HLB, not only endurance quality is improved, and can also give sliding to the surface of near infrared ray absorption layer.For this reason, even without forming concave-convex surface, still has the advantage that the property handled coils into bobbin shape well, easily near infrared ray absorption layer or opposite one side.

Can suitably use the known material of kation system, negative ion system, nonionic system as above-mentioned surfactant, problems such as deterioration near infrared absorbing coloring matter, the preferred nonionic system that does not have polar group, outstanding silicone-based or the fluorine of the active ability of special preferred surface is surfactant.

As the silicone-based surfactant, can enumerate dimethyl silicone; amino silane; acryloyl group silane; the vinyl benzyl base silane; the vinyl benzyl amino silane; glycidoxy silane; hydrosulphonyl silane; dimethylsilane; dimethyl silicone polymer; poly-oxyalkylsiloxane; the hydrogenated diene modified siloxane; the vinyl modified siloxane; the hydroxyl modification siloxane; amino modified siloxane; carboxy-modified siloxane; the halogenation modified siloxane; epoxide modified siloxane; the methacryloxy modified siloxane; sulfhydryl modified siloxane; the fluorine modified siloxane; alkyl-modified siloxane; phenyl modified siloxane; alkylene oxide modified siloxane etc.

As fluorine is surfactant, can enumerate tetrafluoroethene, perfluoroalkyl ammonium salt, perfluoro alkyl sulfonic acid acid amides, perfluoro alkyl sulfonic acid sodium, perfluoroalkyl sylvite, perfluoroalkyl carboxylate, perfluoro alkyl sulfonic acid salt, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl leptodactyline, perfluoroalkyl sulfamate, perfluoroalkyl phosphate, perfluoroalkyl alkylate, perfluoroalkyl alkyl betaine, perfluoroalkyl halogenide etc.

With regard to the content of surfactant, containing in above-mentioned near infrared ray absorption layer more than the 0.01 quality % is important below the 2.0 quality %.Under the poor situation of surfactant, appearance of film or sliding are abundant inadequately sometimes.On the other hand, under the many situations of the content of surfactant, near infrared ray absorption layer is adsorption moisture sometimes, promotes the deterioration of pigment.Wherein,, then has the function that suppresses the pigment deterioration, so the suitable content range of energy enlarged surface activating agent if use adhesiveness modified layer described later.

In the present invention, the HLB of surfactant is 2-12, and the preferred lower limit of HLB is 3, more preferably 4.On the other hand, the preferred upper limit value of HLB is 11, more preferably 10.

Under the low situation of HLB, can make pigment deterioration surface-hydrophobicized and that inhibition is caused by moisture-proof heat, and, give easy sliding property easily, but under low excessively situation, can cause the deficiency of levelability by the deficiency of surfactivity ability.

On the contrary, under the high situation of HLB, not only sliding deficiency, and near infrared ray absorption layer absorbs moisture easily, and pigment is along with the stability of time becomes not good.

Wherein, the balance that HLB is meant the hydrophilic group that contains in W.C.Griffin called after Hydorophil Lyophile molecule Balance, with surfactant by the Atlas Powder company of the U.S. and lipophilic group is as characteristic value and the value of indexing, this value is low more, lipophilicity is high more, it is high more on the contrary, and water wettability is high more.

Surfactant is different because of the kind or the solvent of resin at the localization on the surface of near infrared ray absorption layer, but when the value of HLB is near 7, the easiest localization that causes, and, under the situation of the slow-drying at initial stage easily by localization.Surfactant is in the localization degree on the surface of near infrared ray absorption layer, and the amount of surfactant on the content that can be by the surfactant in the contrast near infrared ray absorption layer and the surface of near infrared ray absorption layer is confirmed.For example, if the silicone-based surfactant then can be undertaken quantitatively by the Si element of esca analysis to the surface of near infrared ray absorption layer.

When utilizing coating fluid to form under the situation of near infrared ray absorption layer, with regard to the solvent that can be used for this coating fluid,, just be not particularly limited as long as can dissolve or disperse above-mentioned each pigment and above-mentioned resin equably.For example can enumerate ketones such as acetone, methyl ethyl ketone, methylisobutylketone, cyclopentanone, cyclohexanone; Ester such as ethyl acetate, propyl acetate class; Alcohols such as methyl alcohol, ethanol, butanols, isopropyl alcohol; Cellosolve such as ethyl cellosolve, butyl cellosolve class; Benzene,toluene,xylenes etc. are aromatic hydrocarbon based; Furans such as tetrahydrofuran; Dimethoxy-ethane; Aliphatic hydrocarbon such as normal hexane, normal heptane; Halogen atom such as methylene chloride, chloroform hydro carbons; N, amide-types such as dinethylformamide; Water; Deng.Wherein, from environment or healthy aspect, preferably do not use above-mentioned halogen atom hydro carbons as far as possible.

In the middle of above-mentioned organic solvent, the preferred use ketone outstanding to the dissolubility of pigment, with respect to all organic solvent amounts that contain in the coating fluid, the amount of ketone is preferably below the above 80 quality % of 30 quality %.Organic solvent beyond the ketone can consider that the levelability of coating fluid or drying property select.

The boiling point of organic solvent is preferably more than 60 ℃ below 180 ℃.Under the low excessively situation of the boiling point of organic solvent, occur following problem sometimes: the solid component concentration of coating fluid changes easily in coating process, and applied thickness is difficult to stabilization.On the contrary, if the boiling point of organic solvent is too high, the residual solvent amount in the near infrared ray absorption layer increases easily, so the ageing stability of pigment has the trend of deterioration.

As the dissolving in organic solvent or the method for disperseing near infrared absorbing coloring matter, resin and surfactant, can adopt methods such as stirring under the heating, dispersion, pulverizing.By in when dissolving heating, can improve pigment and dissolving resin, can prevent the bad order that dissolved matter not causes.In addition, making it by dispersion in organic solvent or crushing resin and pigment is that graininess below the 0.3 μ m is scattered in the coating fluid with mean grain size for example, can form the outstanding near infrared ray absorption layer of the transparency.As dispersion machine or comminutor, can use known machine.Specifically, can enumerate bowl mill, sand mill, vertical ball mill, tumbling mill, stirrer, colloid mill, ultrasonic homogenizer, homogeneous mixer, crushing pearl machine, wet type airslide disintegrating mill, coating vibrator, butterfly mixer, planetary-type mixer, Henschel mixer etc.

With regard to the concentration of the above-mentioned coating fluid that is used to form near infrared ray absorption layer, solid component concentration in other adjuvants of comprising pigment, resin and surfactant, being added as required, be preferably 5.0～50 quality %, more preferably 10～40 quality %.12～25 quality % more preferably.When the solid component concentration of coating fluid is crossed when low, organic solvent amount in the coating fluid increases, so prolong the drying time when forming near infrared ray absorption layer, not only throughput rate worsens, and the increase of the residual solvent amount in the near infrared ray absorption layer, the ageing stability of pigment has degradating trend, particularly in hot and humid long-time down keeping (for example, 60 ℃, relative humidity 95%, 500 hours) time, the transmitance of film or the variation of tone have the trend of increase.On the other hand, when the solid component concentration of coating fluid was too high, the viscosity of coating fluid increased, the levelability deficiency, and the bad order of near infrared ray absorption layer happens occasionally.The viscosity of coating fluid is preferably 10～300cps.

When coating is used to form the coating fluid of near infrared ray absorption layer, can adopt known coating process.Detailed content as described later.

The coating weight of above-mentioned coating fluid is preferably counted 1.0～15.0g/m with dry mass (that is the quality after the formation near infrared ray absorption layer) ²2.0～12.0g/m more preferably ²When coating weight was lower than above-mentioned scope, if will obtain required uptake near infrared range, pigment increased with respect to the ratio of resin, as its result, causes the reduction of thermotolerance or moisture-proof sometimes.On the other hand, when coating weight surpassed above-mentioned scope, it was insufficient to occur drying easily, and the residual solvent amount increases, and thermotolerance or moisture-proof reduce (detailed content as described later) easily.In addition, when coating weight for a long time, be easy to generate the defective of appearance of films such as coating spot etc.

Wherein, utilize above-mentioned coating fluid to form under the situation of near infrared ray absorption layer, preferably selecting to make residual solvent amount in the near infrared ray absorption layer to become following, the more preferably following drying condition of 3 quality % of 5 quality %.

Usually under situation about applying, be necessary to carry out drying in case produce adhesion, at this moment, residual solvent concentration is roughly surpassing 5 quality % and the scope below the 7 quality %.That is, the residual solvent amount near infrared ray absorption layer is for surpassing under 5 quality % and the situation below the 7 quality %, and near infrared ray absorption layer has been finished drying on apparent, also do not produce adhesion.

But, when when hot and humid long-time down placement has the film of such near infrared ray absorption layer, under the influence of residual solvent, the apparent Tg of resin reduces, between resin one near infrared absorbing coloring matter, to interact appear each other and between residual solvent-this pigment in this pigment easily, sex change takes place in this pigment easily.Its result, the spectral characteristic or the tone of film change easily.

Wherein, the lower limit of the residual solvent amount in the near infrared ray absorption layer is preferably 0.01 quality %.When the residual solvent amount in the near infrared ray absorption layer during less than 0.01 quality %, although can highly be suppressed at the sex change of hot and humid down long-time near infrared absorbing coloring matter when placing film, but then, because the thermal treatment that need carry out in order to reduce the residual solvent amount, sex change takes place near infrared absorbing coloring matter sometimes.

In order in the sex change that suppresses near infrared absorbing coloring matter, to reduce the residual solvent amount, recommend to carry out above multistage heated-air drying operation of 2 stages.The detailed content of drying process as described later.

[middle layer]

In the near-infrared absorbing film of the present invention, on transparent base film, be laminated with near infrared ray absorption layer, but the middle layer preferably be set with the adhesiveness that improves transparent base and near infrared ray absorption layer or the transparency that improves transparent base.Wherein, when in transparent base film, not containing particle,, can when keeping the property handled, obtain the transparency of height when making film by the middle layer of containing particle is set simultaneously.

As the resin that constitutes above-mentioned middle layer, can enumerate polyester based resin, polyurethane series resin, polyester urethane resin, acrylic resin, melamine is resin etc., but importantly, its selection will make the good adhesion with base material and near infrared ray absorption layer, specifically, if constitute the resin of base material and near infrared ray absorption layer is ester system, preferred selected polyester system, polyester urethane system with similar structures.

In order to improve adhesiveness and water tolerance, in above-mentioned middle layer, can contain crosslinking chemical and form cross-linked structure.As crosslinking chemical, can enumerate urea system, epoxy system, melamine system, isocyanate-based.Particularly whiten under high temperature/high humidity or intensity when reducing when resin, the effect that is caused by crosslinking chemical is more remarkable.In addition, also can not use crosslinking chemical and the graft copolymerization resin that will have a self-crosslinking as resin.

In order to form the concavo-convex sliding that improves on the surface, in the middle layer, can contain various particles.As the particle that in the middle layer, contains, for example can enumerate inorganic particulates such as silicon dioxide, porcelain earth, talcum, lime carbonate, zeolite, aluminium oxide, acrylic acid series, PMMA, nylon, styrene, polyester, benzoguanamine-organic fillers such as formalin condensation product.Wherein, from the viewpoint of the transparency, preferred selective refraction rate and the approaching particle of resin.

And then, in order to give the middle layer various functions, can contain surfactant, antistatic agent, fluorescent dye, fluorescer, pigment, ultraviolet light absorber etc.

The middle layer can be an individual layer, can also stackedly become more than 2 layers as required.

With regard to the thickness in this middle layer, as long as have objective function, just be not particularly limited, be preferably below the above 5 μ m of 0.01 μ m.When thinner thickness, be difficult to embody function as the middle layer, on the contrary, when thickness was thicker, it is not good that the transparency becomes easily.

As the method that the middle layer is set, preferred rubbing method.As rubbing method, can use known coating processes such as photogravure coating (gravure coating) mode, kiss-coating (kiss coating) mode, impregnation method, spraying method, curtain coating mode, air knife blade coating mode, scraper plate application pattern, contrary roller coat mode for cloth, and be provided with by online coating (in linecoating) mode that coating layer is set in the manufacturing process of film, off-line coating (off line coating) mode that coating layer is set after making film.In these modes, online application pattern is not only outstanding aspect cost, and can make transparent base need not to contain particle by contain particle in coating layer, thereby can highly improve the transparency, so preferred.

[the 1st adhesiveness modified layer]

The 1st specific adhesiveness modified layer preferably is set between near infrared ray absorption layer and transparent base film, replaces above-mentioned middle layer.As the 1st adhesiveness modified layer, the preferred utilization with acid number is that the above adhesiveness modified resin of 200 equivalents/t (below, be called the 1st adhesiveness modified resin) is the adhesiveness modified layer of major component.Here, so-called " major component " is meant and is above-mentioned the 1st adhesiveness modified resin in the layer more than the 80 quality %.Wherein, as the composition beyond the resin, can enumerate inert particle described later or various adjuvant.

The inventor's etc. result of study shows, the stability of the near infrared absorbing coloring matter that near infrared ray absorption layer contained and be used to form between the acid number of the 1st adhesiveness modified resin of the 1st adhesiveness modified layer and have substantial connection.That is, be that the 1st adhesiveness modified resin of 200 equivalents/t more than forms under the situation of the 1st adhesiveness modified layer using acid number, can suppress the sex change of the near infrared absorbing coloring matter in the near infrared ray absorption layer, the spectral characteristic of inhibition film or the variation of tone.

Its reason is not determined as yet, but under the situation of using the 1st big adhesiveness modified resin of acid number, can improve the cross-linking density (aftermentioned) of the 1st adhesiveness modified layer, so can be with the near interface that only is suppressed at these layers that mixes of the composition of the composition of the 1st adhesiveness modified layer and near infrared ray absorption layer.Its result, the stability of near infrared absorbing coloring matter can be improved.If above the mixing of necessary degree takes place in the 1st adhesiveness modified layer composition and near infrared ray absorption layer composition, then because the 1st adhesiveness modified layer becomes branch to make near infrared ray absorption layer composition generation sex change, so the stability of near infrared absorbing coloring matter reduces.Particularly under high temperature, high humidity, such influence is bigger, so the stability of near infrared absorbing coloring matter further reduces.In the 1st adhesiveness modified layer of the present invention, because can suppress aforesaid phenomenon, so can realize the raising of the stability of near infrared absorbing coloring matter.

Thus, acid number at above-mentioned the 1st adhesiveness modified resin is lower than under the situation of 200 equivalents/t, when placing film for a long time under hot and humid, the stability of the near infrared absorbing coloring matter in the near infrared ray absorption layer reduces, and the spectral characteristic or the tone of film change.In addition, the 1st adhesiveness modified layer can be brought into play the effect as the adhesive linkage of base film and near infrared ray absorption layer, but when the acid number of the 1st adhesiveness modified resin was lower than 200 equivalents/t, the adhesiveness of this base film and near infrared ray absorption layer was abundant inadequately.The acid number of preferred the 1st adhesiveness modified resin is 500 equivalents/more than the t, more preferably 900 equivalents/more than the t.In addition, the acid number of the 1st adhesiveness modified resin is preferably 10000 equivalents/below the t.

Wherein, with regard to the acid number of the 1st adhesiveness modified resin, be under heating/decompression, the 1st adhesiveness modified resin to be carried out it being dissolved in the suitable solvent after the drying, in the presence of indicator, carry out titration with aqueous slkali, be converted into per 10 ⁶The equivalent of g resin (the 1t) (value of equivalent/t) obtain.Indicator as judging usefulness can use phenolphthalein etc.

The 1st above-mentioned adhesiveness modified resin can be by importing the unit contain acidic groups such as carboxyl and controlling that the ratio of components of the acidic group in the resin obtains in resins such as polyester based resin, acrylic resin, polyamide-based resin, polyurethane series resin, polystyrene resin.Wherein, be fit to use be in polyester based resin grafting to have the polyester that the acid anhydrides of at least one two key forms be graft copolymer.

With regard to above-mentioned polyester is graft copolymer, from graft copolymerization all polyester based resin molecules the form of above-mentioned acid anhydrides, the graft copolymerization molecule that forms to this acid anhydrides of grafting in polyester based resin and the form of the potpourri of the unreacted polyester based resin molecule of this acid anhydrides of grafting are not all included.

Above-mentioned polyester is in the graft copolymer, imports to be derived from the unit of above-mentioned acid anhydrides and to have formed cross-linked structure between the molecular resin by acting on of this unit in polyester based resin.That is, for example, when modulation is a graft copolymer when being the coating fluid of major component with above-mentioned polyester, the anhydride group in the resin becomes carboxyl because of hydrolysis etc. in said composition.Subsequently, it is first-class that coating fluid is coated on base film, carry out drying etc., form the 1st adhesiveness modified layer, by the thermal process that applies this moment, form anhydride group between the 1st adhesiveness modified resin molecule, the reactive hydrogen of perhaps removing other molecules and being had generates ester group or the like, forms cross-linked structure thus between the 1st adhesiveness modified resin molecule.

In the 1st adhesiveness modified layer, above-mentioned crosslinked by forming, can improve the water tolerance of this layer, its result can be improved with the stability of the near infrared absorbing coloring matter that near infrared ray absorption layer had of this layer adjacency.In addition, above-mentioned when crosslinked when in the 1st adhesiveness modified layer, forming, the near interface that only is suppressed at these layers that mixes of the 1st adhesiveness modified layer composition and near infrared ray absorption layer composition also can be able to be improved the stability of near infrared absorbing coloring matter thus.This be because, when mixing more than the necessary degree appearred in the 1st adhesiveness modified layer composition and near infrared ray absorption layer composition, the 1st adhesiveness modified layer became branch to impact near infrared absorbing coloring matter, the stability of this pigment can reduce sometimes.And then, above-mentioned crosslinked by forming, the adhering effect of also can be further enhanced near infrared ray absorption layer and base film.

As mentioned above, in being used to form the 1st adhesiveness modified resin of the 1st adhesiveness modified layer, the acidic group of anhydride group etc. can become crosslinked starting point, therefore by increasing the amount of these functional groups, can improve the cross-linking density of the 1st adhesiveness modified layer.If the amount of the acidic group in the 1st adhesiveness modified resin increases, then its acid number also increases, so in the present invention, by determining the acid number of the 1st adhesiveness modified resin, the cross-linking density of the 1st adhesiveness modified layer can be guaranteed degree in the sex change that can suppress near infrared absorbing coloring matter.

As being used for the polyester based resin that above-mentioned polyester is a graft polymer, can enumerate being the polyester based resin of primary structure unit by formed ester units of pure composition such as sour compositions such as known dicarboxylic acid (comprising acid anhydrides) and known glycol.

As above-mentioned dicarboxylic acid, can enumerate aromatic dicarboxylic acids such as terephthalic acid (TPA), m-phthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyl dicarboxylic acid; Aliphatic dicarboxylic acids such as succinic acid, hexane diacid, azelaic acid, decanedioic acid, dodecane two ketone acids (dodecanedionic acid), dimer acid; 1,4-cyclohexane diacid, 1,3-cyclohexane diacid, 1, alicyclic dicarboxylic acids such as 2-cyclohexane diacid and its acid anhydrides etc.These dicarboxylic acid can use a kind separately, perhaps mix more than 2 kinds and use.

In addition, can part also use trihemellitic acid (acid anhydride), pyromellitic acid (acid anhydride), benzophenone tetracid (acid anhydride), trimesic acid, ethylene glycol bis (trimellitic anhydride ester), glycerine three polyvalent carboxylic acids such as (trimellitic anhydride esters), or have the dicarboxylic acid of polymerism unsaturated double-bond.As dicarboxylic acid, can enumerate α such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, β-unsaturated dicarboxylic with polymerism unsaturated double-bond; 2,5-norbornene dicarboxylic acids acid anhydride, tetrahydrobenzene dicarboxylic acid anhydride etc. have the alicyclic dicarboxylic acid of unsaturated double-bond etc.

As above-mentioned diol component, can enumerate carbon number and be 2～10 fatty acid glycol, carbon number and be 6～12 alicyclic diol, contain the glycol of ehter bond etc.

As carbon number is 2～10 aliphatic diol, can enumerate ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl isophthalic acid, 5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butyl propylene glycol etc.In addition, be 6～12 alicyclic diol as carbon number, can enumerate 1,4 cyclohexane dimethanol etc.

As the glycol that contains ehter bond, can the illustration diglycol, the alkylene oxide addition product of triethylene glycol, dipropylene glycol, bisphenol compound or derivatives thereof [for example, 2, two (4-hydroxyl-oxethyl phenyl) propane of 2-etc.], polyglycol, polypropylene glycol, polytetramethylene glycol etc.

In addition, can also part also use polyvalent alcohols such as glycerine, trimethylolethane, trimethylolpropane, pentaerythrite.

Synthetic method to above-mentioned polyester based resin is not particularly limited, and can adopt conventional method to synthesize by melt polymerization with above-mentioned dicarboxylic acid or glycol.Wherein, in above-mentioned polyester based resin, in 100 moles of % of the composition that is derived from sour composition, preferred source is 30 moles more than the % from the composition of aromatic dicarboxylic acid.When the one-tenth component that is derived from aromatic dicarboxylic acid was lower than 30 moles of %, the water-disintegrable of polyester based resin became significantly, and As time goes on the adhesiveness of the 1st adhesiveness modified layer and base film can descend, so not preferred.

Wherein, when using above-mentioned dicarboxylic acid with polymerism unsaturated double-bond, in 100 moles of % of all sour compositions, be preferably 10 moles below the %.In addition, when using above-mentioned polybasic carboxylic acid or polyvalent alcohol, in 100 moles of % of all sour compositions, preferred polybasic carboxylic acid is 5 moles of % following (more preferably 3 moles of % are following), at all pure Cheng Chengzhong, polyvalent alcohol is 5 moles of % following (more preferably 3 moles of % are following).When the amount of the dicarboxylic acid with polymerism unsaturated double-bond or polybasic carboxylic acid, polyvalent alcohol surpasses above-mentioned scope, gelation takes place easily when polyester based resin generation polymerization or during graft reaction described later, not preferred.

As being used for " the acid anhydrides " that above-mentioned polyester is a graft copolymer, can enumerate α such as maleic anhydride, itaconic anhydride, the acid anhydrides of β-unsaturated dicarboxylic with at least 1 two key; 2,5-norbornene dicarboxylic acids, tetrahydrobenzene dicarboxylic acid anhydride etc. has the alicyclic dicarboxylic acid's of unsaturated double-bond acid anhydrides; Deng.In addition, be in the graft copolymer at above-mentioned polyester, except above-mentioned acid anhydrides, can also be grafted with other polymerism unsaturated monomers.

As other polymerism unsaturated monomers, can the illustration fumaric acid, the monoesters or the diester of fumaric acid such as monomethyl ester, DEF, dibutyl fumarate; The monoesters or the diester of maleic acids such as maleic acid, ethyl maleate, diethyl maleate, dibutyl maleate; The monoesters of itaconic acid, itaconic acid or diester; Maleimides such as phenyl maleimide etc.; Styrene and its derivants such as styrene, α-Jia Jibenyixi, t-butyl styrene, 1-chloro-4-methyl-benzene; Aromatic ethenyl compound such as vinyltoluene, divinylbenzene; Alkyl acrylate, alkyl methacrylate acrylic monomers such as (, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, 2-ethylhexyl, cyclohexyl, phenyl, benzyl, phenethyl etc. being arranged) as alkyl; Acrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, methacrylic acid 2-hydroxypropyl ethyl ester etc. contain the acrylic monomer of hydroxyl; Acrylamide, Methacrylamide, N-methyl acrylamide, N methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N, N-dihydroxymethyl acrylamide, N-methoxy acrylamide, N-methoxy Methacrylamide, N phenyl acrylamide etc. contain the acrylic monomer of amide group; Acrylic acid N, N-diethyl amino ethyl ester, methacrylic acid N, N-diethyl amino ethyl ester etc. contain amino acrylic monomer; Glycidyl acrylate, glycidyl methacrylate etc. contain the acrylic monomer of epoxy radicals; Acrylic acid, methacrylic acid and their salt (sodium salt, sylvite, ammonium salt) etc. contain the acrylic monomer of carboxyl or its salt; Deng.

In film of the present invention, the 1st adhesiveness modified layer is preferably used the coating fluid of the 1st above-mentioned adhesiveness modified resin, is formed on the base film by rubbing method.For forming the coating fluid that the 1st adhesiveness modified layer is used, preferably contain the 1st above-mentioned adhesiveness modified resin, and then with the mixed liquor of water or water and aqueous solvent as constituent.In this coating fluid, the 1st adhesiveness modified resin is dissolved state, perhaps exists as dispersion (so-called emulsion).

Wherein, the 1st adhesiveness modified resin amount (solid component concentration) in the coating fluid is preferably 3～35 quality %, more preferably 7～15 quality %.By using the coating fluid that contains the 1st adhesiveness modified resin in above-mentioned scope, can form the 1st adhesiveness modified layer well.

As above-mentioned aqueous solvent, be fit to use alcohols such as ethanol, isopropyl alcohol, benzylalcohol, can contain amount with respect to coating fluid less than 50 quality %, in addition, if less than 10 quality %, then can in the scope that can dissolve, mix the organic solvent beyond the above-mentioned alcohols with respect to the content of above-mentioned coating fluid.Wherein, the total amount of the organic solvent beyond alcohols in the coating fluid and the alcohols is preferably less than 50 quality %.

By containing the organic solvent that contains alcohols in above-mentioned scope, when coating fluid being coated on the base film and carrying out drying, can improve drying property, compare with the situation that only makes water simultaneously, have the effect of the outward appearance of improving the 1st adhesiveness modified layer.But, when the content of the organic solvent that contains alcohols surpassed above-mentioned scope, the velocity of evaporation of solvent was too fast, and the concentration of said composition can change in the coating process of coating fluid, and the viscosity of coating fluid rises, its result, and screening characteristics has the trend of reduction.Therefore, cause the bad order of the 1st adhesiveness modified layer easily.And then, from environment aspect or operator's healthy aspect, the dangerous aspect of fire, not preferred yet.

In addition, especially preferably contain following acid compound in the coating fluid.Have under the situation of the unit that is derived from acid anhydrides at the 1st adhesiveness modified resin, in coating fluid, anhydride group becomes carboxyl through hydrolysis, under the effect of this acid compound, when after the coating coating fluid, carrying out drying, can promote the acid anhydridesization or the ester group of the carboxyl between the 1st adhesiveness modified resin molecule to form reaction, can increase the cross-linking density of the 1st adhesiveness modified layer.Thus, can highly realize with the adhesiveness of base film or to the inhibition of the sex change of near infrared absorbing coloring matter.

As above-mentioned acid compound, compound shown in being preferably as follows, the easy generating gasification of heating during promptly by formation the 1st adhesiveness modified layer, the residual quantity in this layer is less, even and then, specifically recommend lower boiling carboxylic acid in that the also less material of its harmful effect under the residual situation is arranged.More specifically say, can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, enanthic acid etc.The use amount of these acid compounds is preferably 1～10 quality % with respect to the 1st adhesiveness modified resin.

In order to improve wetting state to base film, realize more uniform coating, can contain known negative ion in above-mentioned coating fluid in right amount is that surfactant or nonionic are surfactant.

In addition, from film being given other functional point of view such as the property handled, static electricity resistance, antibiotic property, in coating fluid, can contain adjuvants such as inorganic particulate, thermotolerance macromolecule particle, antistatic agent, ultraviolet light absorber, organic lubricant, antiseptic, photooxidation catalyst.Particularly when not containing inert particle in fact in the base film,, preferably in coating fluid, contain inorganic particulate and/or thermotolerance macromolecule particle, form concaveconvex structure on the 1st adhesiveness modified layer surface in order to improve the processing of film.And then as mentioned above, coating fluid is preferably the material of water system, so in order to improve the performance of film, can contain other water soluble resins, water-dispersed resin, emulsion etc. in above-mentioned composition.

As mentioned above, the 1st adhesiveness modified layer can be carried out drying and carries out (so-called off-line coating process) by coating fluid is coated on the base film.In addition, biaxially oriented film is being used under the situation of base film, can adopting the method (so-called online coating process) that is coated on coating fluid on not stretching or the monodirectional tension film and implements stretching, heat fixation in the stage that forms the 1st adhesiveness modified layer.Wherein, from the aspect of effect of the present invention, more preferably adopt the latter's online coating process.When the base film that will be coated with coating fluid guides to stenter when stretching (for example cross directional stretch), heat fixation, under the effect of this heat, further carry out cross-linking reaction, so can form the 1st more stable adhesiveness modified layer.Method as coating coating fluid on base film can adopt known coating process.Specifically, can enumerate contrary roller rubbing method, photogravure coating process, kiss-coating method, mouthful pattern rubbing method, roller brush method, spraying process, air knife knife coating, wire bar coating process, tubular type knife coating, infiltration coating process, the curtain coating method etc. used.These methods can be carried out separately, can also make up and carry out.

The coating weight of coating fluid is 0.01～1g/m in dry mass (that is, form after the 1st adhesiveness modified layer quality) preferably ²0.08～0.8g/m more preferably ²When the coating weight of coating fluid was lower than above-mentioned scope, the effect that the 1st adhesiveness modified layer is set was abundant inadequately sometimes.On the other hand, when the coating weight of coating fluid surpassed above-mentioned scope, the transmitance of film integral descended sometimes.

Below, the formation method of the 1st adhesiveness modified layer of online coating process is adopted in explanation as typical example.Do not stretch or unilateral stretching after base film on coating coating fluid and carry out drying.In online coating process, when carrying out its drying process, be necessary to select only not carry out the temperature and time of cross-linking reaction except that anhydrate equal solvent composition and the 1st adhesiveness modified layer.

Specifically, preferably making baking temperature is 70～140 ℃, and can regulate drying time according to interior perhaps its coating weight of coating fluid, for example baking temperature (℃) and drying time (second) long-pending being preferably below 3000.When above-mentioned long-pending when surpassing 3000, the 1st adhesiveness modified layer will begin to take place cross-linking reaction before stretching, and occurs the trend of crackle etc. in the 1st adhesiveness modified layer, so be difficult to realize purpose of the present invention.

After coating, drying coated liquid, implement to stretch.The stretching condition of this moment can suit according to the starting material of base film to select, and is under the situation of PET at starting material for example, can adopt the stretching condition of being recorded and narrated in the project of base film.

Usually the film after stretching is implemented about 2～10% tension and relaxation processing, in the present invention, preferably under the distortion less state of the 1st adhesiveness modified layer, promptly under the state of length of the Width of film being fixed, for example the 1st adhesiveness modified layer is heated by infrared heater.The heating of this moment preferably about 250～260 ℃, carry out in the short time, is promptly carried out about 0.5～1 second.By carrying out such operation, can further promote the 1st adhesiveness modified resin crosslinked in the 1st adhesiveness modified layer, the 1st adhesiveness modified layer becomes more firm, and the adhesiveness of the 1st adhesiveness modified layer and base film is better.

Wherein, heating-up temperature or heat time heating time when above-mentioned tension and relaxation is handled surpass under the situation of above-mentioned preferable range, and the crystalization or the fusion of base film take place easily, and be not preferred.On the other hand, when above-mentioned heating-up temperature or when being lower than above-mentioned preferable range above-mentioned heat time heating time, the crosslinked of the 1st adhesiveness modified layer becomes abundant inadequately sometimes, and the adhesiveness of the 1st adhesiveness modified layer and base film and near infrared ray absorption layer becomes abundant inadequately sometimes.

The 1st adhesiveness modified layer that is provided with on base film not only has good adhesiveness with near infrared ray absorption layer, also has good adhesiveness with various materials.In addition, be purpose with further raising adhesiveness, can implement surface treatments such as Corona discharge Treatment, flame treatment, electron ray irradiation to the 1st adhesiveness modified layer.

[anti-reflection layer]

On near-infrared absorbing film of the present invention, with the opposite one side that is arranged at the near infrared ray absorption layer on the transparent base film on, preferably be provided with anti-reflection layer.This anti-reflection layer has anti-reflective function, and said here " anti-reflective function " is meant preventing that surface reflection is can prevent the function of film " glittering " when improving light penetration.Unqualified to the method for giving anti-reflective function, can select arbitrarily, for example, at the different layer of the folded refractive index of the superficial layer of base film and to utilize reflected light to reduce the method for reflection in the interference of this bed interface more suitable.

In the present invention, when forming above-mentioned anti-reflection layer, preferably carry out processing as follows simultaneously, promptly give the hard processing of antisitic defect, give the antistatic finish of static electricity resistance, even give the function of preferably holding is given in the antifouling processing of adhering to or adhering to the function that also can easily wipe out etc. of dirts such as preventing fingerprint, sebum, sweat, cosmetics when as the near-infrared absorbing light filter manufacturing procedure.Particularly the market demands of hard processing are stronger, and the pencil hardness of preferred above-mentioned anti-reflection layer is more than the 1H.

Specifically, anti-reflection layer preferably has from the 3-tier architecture of face side [the opposite one side side of base film] according to the sequential cascade of low-index layer, high refractive index layer, hard conating.That is, can utilize the catoptrical interference on the interface of low-index layer and high refractive index layer, reduce surface reflection, prevent that by hard conating the near-infrared absorbing light filter from sustaining damage simultaneously.

As hard conating, what relatively be fit to is to make curing to take place and the layer that obtains the resin that solidifies the effect of electron ray or light (ultraviolet ray etc.) under (below, be called " light-cured resin ").

As light-cured resin, can use known epoxy acrylate (vinyl ester resin), polyester acrylate, urethane acrylate etc. that resin (oligomer or polymkeric substance) curing reaction, have (methyl) acryloyl group more than 2 in molecule can take place under the irradiation of electron ray or light (ultraviolet ray etc.).

Above-mentioned light-cured resin and reactive diluent can be used as Photocurable resin composition after mixing.In molecule, have the reactive group more than 1 in the reactive diluent, have the viscosity of regulating Photocurable resin composition effect, help curing reaction and improve effect with the adhesiveness of other layers or hardness etc.Specifically, can enumerate styrene, vinyltoluene, fragrant family monomer such as divinylbenzene, vinyl acetate, the N-vinyl pyrrolidone, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) EHA, (methyl) acrylic acid hexanediol ester, two (methyl) acrylic acid (two) glycol ester, two (methyl) acrylic acid propylene glycol ester, two (methyl) acrylic acid tripropylene glycol ester, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester, two (methyl) acrylic acid 1,6-hexanediol ester, (methyl) esters of acrylic acids such as two (methyl) acrylic acid DOPCP etc., they can use separately, can also mix more than 2 kinds and use.

Wherein, make under the situation of its curing, preferably in Photocurable resin composition, containing Photoepolymerizationinitiater initiater or light sensitizer by light (ultraviolet ray etc.).As Photoepolymerizationinitiater initiater, can use acetophenones, benzophenone, Mi Xileshi benzophenone formic ether, α one ア ミ ロ キ シ system ester, tetramethylthiuram monosulfide, thioxanthene ketone etc. as Photoepolymerizationinitiater initiater and by known compound.In addition, light sensitizer can use that also n-butylamine, triethylamine, three normal-butyls are seen etc. as light sensitizer and by known compound.

In order to carry out viscosity adjusting etc., can contain solvent in the Photocurable resin composition.Can enumerate hydro carbons such as toluene, dimethylbenzene, cellosolve such as cellosolve, butyl cellosolve etc., carbitol such as carbitol, butyl carbitol class, ester classes such as cellosolve acetate, carbitol acetate ester, propylene glycol methyl ether acetate, ketone such as hexone, methyl ethyl ketone, ethers such as diethylene glycol dimethyl ether, etc.

The formation of hard conating can be adopted method as follows, promptly directly or across other layers is coated with above-mentioned Photocurable resin composition and carries out drying on base film, and irradiation electron ray or light (ultraviolet ray etc.) make the method for its curing.For example, when adopting the electron ray curing method, can use from Cockcroft-Walton type, model Dege loudspeaker husband type, resonance transformation type, insulated wire cores transformer type, linear pattern, the electron ray etc. of energy of various electron ray accelerators radiation such as that rice (dynamitron) type, high-frequency type with 50～1000keV, preferred 100～300keV.In addition, when adopting the photocuring method, can utilize the ultraviolet ray of sending from light such as ultrahigh pressure mercury lamp, high-pressure sodium lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamps etc.Wherein, the thickness of hard conating is preferably 0.5～10 μ m.When the thickness of hard conating during less than 0.5 μ m, can't guarantee enough being coated with property firmly, when surpassing 10 μ m,, not preferred from the viewpoint of throughput rate.

Low-index layer and high refractive index layer are not particularly limited.Can be the layer of organic system, also can be the layer of inorganic system, can also be the layer of inorganic/organic potpourri.As its forming method, layer forming method as inorganic system, mainly can enumerate the method for piling up the compound that constitutes layer,, mainly can enumerate coating and contain the coating fluid of the compound (resin etc.) that constitutes layer and make its dry method as the layer forming method of organic system by vapour deposition method or sputtering method.

Starting material as constituting low-index layer for example preferably use CaF ₂, MgF ₂, NaAlF ₄, SiO ₂, ThF ₄, ZrO ₂, Nd ₂O ₃, SnO ₂, TiO ₂, CeO ₂, ZnS, In ₂O ₃In dielectric.Can use these starting material, by dry type coated techniques such as vacuum vapour deposition, sputtering method, CVD method, ion plating methods, or wet type coated techniques such as photogravure mode, reverse application pattern, mouthful pattern application pattern form low-index layer.

With regard to high refractive index layer, so long as the also high layer of the low-index layer that refractive index ratio forms on its surface, near infrared ray absorption layer, other functional layers (UV-absorbing layer, electromagnetic wave blocking layer, hard conating etc.) of giving can be held concurrently and be worked as high refractive index layer.Under the situation of inorganic system, for example, can adopt vapour deposition method or sputtering method to form ZnO, TiO ₂, CeO ₂, SnO ₂, ZrO ₂, ITO (for example, refractive index are more than 1.65) such as (indium-tin-oxides) layer.Under the situation of organic system, preferably use resin, for example, can enumerate polyester based resin, polyethers as preferred resin is that resin, acrylic resin, epoxy resin, carbamate are resin, polycarbonate-based resin, polystyrene resin.And then, also can in macromolecule resin, disperse inorganic particulate to improve refractive index.

In addition, also can make silane compound (organic silane compound) be hydrolyzed condensation and form low-index layer and high refractive index layer.That is, when coating contains the coating fluid of silane compound and makes it dry, make its hydrolytic condensation and cambium layer.Wherein, hydrolytic condensation can be carried out in coating fluid, can also be with the material of hydrolytic condensation as silane compound.As operable silane compound, can enumerate γ-An Bingjisanjiayangjiguiwan (and partial hydrolysis condensation product), tetraethoxysilane etc.Wherein, there is difference aspect the refractive index, can the kind of the silane compound that is used for each layer be changed in order to make low-index layer and high refractive index layer.For example, when in low-index layer, using γ-An Bingjisanjiayangjiguiwan (and partial hydrolysis condensation product), can in high refractive index layer, use tetraethoxysilane.

The mixed solvent of water, water and alcohols (methyl alcohol, ethanol, isopropyl alcohol etc.) etc. can be enumerated as the solvent that is used for coating fluid, acid (mineral acid such as hydrochloric acid etc.) can be added as required.After the coating coating fluid, carry out drying (and hydrolysis reaction), can form low-index layer and high refractive index layer.

From improving the viewpoint of traumatic resistance, anti-reflection layer preferably has higher hardness, and for example preferred the most surperficial pencil hardness (pencil hardness of measuring based on the regulation of JIS-K5400) is for more than the 1H.More preferably more than the 2H.As long as adopt above-mentioned illustrative each layer to constitute, just can guarantee this hardness.

In addition, the face side (on the face of low-index layer) at anti-reflection layer can be provided with known other functional layers.For example, can enumerate the antistatic backing that is used to guarantee static electricity resistance, or, even have stain-proofing layer that adheres to or adhere to the function that also can easily wipe out of dirts such as preventing fingerprint, sebum, sweat, cosmetics etc.

[intermediate-index layer] (having the layer that suppresses the interference fringe function)

Preferably between above-mentioned anti-reflection layer and base film, intermediate-index layer is set.Anti-reflection layer preferably adopts from face side and begins the structure that the order according to low-index layer, high refractive index layer, hard conating is laminated, but it is, therefore bigger with the refringence of base film (mylar) owing to hard conating is to make specific curable resin that the layer that obtains take place to solidify.Be provided with the near-infrared absorbing film of such anti-reflection layer, when the near-infrared absorbing that is applied to plasma display is used light filter, under the interference of light effect of the bed interface of light filter inside, rainbow shape color (interference fringe) can have occurred.The method that suppresses as appearance to the above-mentioned interference striped, the known method that the refringence that reduces hard conating and base film is arranged, and if will reach this point, be effective importing the layer of refractive index between the refractive index of the refractive index of hard conating and base film between these layers.

As above-mentioned intermediate-index layer; by containing the layer that coating fluid at least a and aqueous polyester resin in water-soluble titanium chelate, water miscible titanium acylate compound, water miscible zirconium chelate or the water miscible zirconium acylate compound forms; very effective aspect the appearance that suppresses the above-mentioned interference striped, and help to improve the adhesiveness of base film and anti-reflection layer.That is, requiring the near-infrared absorbing light filter to suppress under the situation of above-mentioned interference striped, between base film and anti-reflection layer, having above-mentioned intermediate-index layer (layer) in the preferred near-infrared absorbing film with the function that suppresses interference fringe.

Constitute the aqueous polyester resin of intermediate-index layer, be meant the aqueous solution that for example contains alcohol less than 50 quality %, alkyl cellosolve, ketone series solvent, ether series solvent etc. for water or water miscible organic solvent, have dissolubility or dispersed vibrin.In order to give water-based, can in polyester molecule, import hydrophilic groups such as hydroxyl, carboxyl, sulfonic group, phosphate, ether, but, preferably import sulfonic group from filming rerum natura and adhering viewpoint to vibrin.

When importing sulfonic group, can use to have sulfonic dicarboxylic acid etc. as the copolymer composition synthesizing polyester.Also can adopt in the importing of other hydrophilic groups to use and have the assign to method of synthesizing polyester of being copolymerized into of various groups.Have in use under the situation of sulfonic dicarboxylic acid, preferably in the scope of 1～10 mole of % of the total acid composition of the synthetic usefulness of polyester, use above-mentioned dicarboxylic acid.If it is very few to have the use amount of sulfonic dicarboxylic acid, vibrin self lacks the embodiment of water-based, also reduces with the chelate of water miscible titanium or zirconium or the mutual capacitive of acylate compound, so can't obtain even and transparent coating layer.In addition, if it is too much to have the use amount of sulfonic dicarboxylic acid, the moisture-proof of intermediate-index layer can descend.

As having sulfonic dicarboxylic acid, can enumerate sulfo group terephthalic acid (TPA), 5-sulfoisophthalic acid, 4-sulfo group naphthalene m-phthalic acid-2,7-dioctyl phthalate, 5-(4-sulfophenoxy) m-phthalic acid and their salt etc.

The glass temperature of aqueous polyester resin (Tg) is preferably more than 40 ℃.When Tg crosses when low, the moisture-proof of intermediate-index layer reduces.In addition, Tg is lower than the trend that 40 ℃ polyester exists refractive index to reduce on its structure, and the refractive index of intermediate-index layer also reduces, and reduces sometimes so interference fringe suppresses effect.

For synthetic vibrin,,, be major component preferably with aromatic dicarboxylic acids such as terephthalic acid (TPA), m-phthalic acid, naphthalenedicarboxylic acids as the polybasic carboxylic acid composition except being used to import the copolymer composition of above-mentioned hydrophilic group with aforesaid Tg.In addition, as polyvalent alcohol, preferred ethylene glycol, propylene glycol, 1, the fewer glycol of carbon number such as 4-butylene glycol, neopentyl glycol, the ethylene oxide adduct of bisphenol-A etc. contains the glycol of aromatic rings etc.In addition, as polyester raw material,, there is not special problem even in the scope that the rerum natura that does not make film reduces, use rigidity composition such as biphenyl or have the dicarboxylic acid or the glycol of the atom of highs index of refraction such as bromine, sulphur yet.

Another major component that constitutes intermediate-index layer is the chelate compound or the acylate compound of water miscible titanium or zirconium.Here " water-soluble " is meant relative water or the aqueous solution that contains less than the water-miscible organic solvent of 50 quality % has dissolubility.

As water miscible titanium chelate compound, can enumerate the ammonium salt, titanium ベ ロ キ ソ citric acid ammonium salt of two (acetyl acetone) titaniums of diisopropoxy, isopropoxy (2-ethyl-1, the 3-hexanediol closes (diolato)) titanium, two (triethanolamine closes (the aminato)) titaniums of diisopropoxy, two (triethanolamine closes) titaniums of two n-butoxies, two (lactic acid closes (the 1actato)) titaniums of hydroxyl, two (lactic acid closes) titaniums of hydroxyl etc.In addition, as water miscible titanium acylate compound, oxo titanium two (single ammonium oxalates) etc. is arranged.

As water miscible zirconium chelate compound, can enumerate tetrem acyl acetone zirconium, three butoxy diacetone zirconiums, zirconium acetate etc.In addition, as water miscible zirconium acylate compound, can enumerate three butoxy zirconium stearates etc.

In the scope of not damaging its effect, can and use vinyl resins such as alkyd resin, urethane resin, acryl resin, polyvinyl alcohol (PVA) etc. in intermediate-index layer.In addition, crosslinking chemical and be used in the effect that misaligns an index layer and cause in the dysgenic scope and be fine.As operable crosslinking chemical, can enumerate the addition product of urea, melamine, benzoguanamine etc. and formaldehyde, be the amino resins such as alkylether compounds that 1～6 alcohol constitutes by these addition products and carbon number; Multi-functional epoxy compound; Multi-functional isocyanate compound; Multi-functional blocked isocyanate compounds; Multi-functional aziridine cpd; Oxazoline compound etc.

As mentioned above; intermediate-index layer can use intermediate-index layer to form coating fluid and form; in this coating fluid; aqueous polyester resin and at least a mixing ratio (mass ratio) that is selected from water-soluble titanium chelate compound, water miscible titanium acylate compound, water miscible zirconium chelate compound or the water miscible zirconium acylate compound are preferably 90/10～5/95.

[the 2nd adhesiveness modified layer] (easily adhesive linkage)

In near-infrared absorbing film of the present invention, under the situation that does not require the generation that suppresses the above-mentioned interference striped, the layer conduct " the 2nd adhesiveness modified layer " that has the adhering effect that improves base film and anti-reflection layer but do not have the effect that suppresses interference fringe can be set.The 2nd adhesiveness modified layer can replace being arranged on above-mentioned the 1st adhesiveness modified layer between base film and the near infrared ray absorption layer.But, if will prevent that pigment from issuing changing property at hot and humid degree, preferably adopt the 1st adhesiveness modified layer.

As the resin that constitutes the 2nd adhesiveness modified layer, for example, can enumerate copolymer polyester resin, urethane resin, acrylic resin, styrene-maleic acid grafted polyester resin, acrylic acid series grafted polyester resin etc., preferably use wherein at least a.Wherein, copolyester is that resin, polyurethane series resin, styrene-maleic acid grafted polyester resin have outstanding adhesiveness, so preferred especially.

The 2nd adhesiveness modified layer forms with coating fluid and carries out drying after being coated on it on base film and form by modulating the 2nd adhesiveness modified layer.Below, be example with the system of using copolymer polyester resin and urethane resin, illustrate that the 2nd adhesiveness modified layer forms the modulator approach with coating fluid.

Above-mentioned copolymer polyester resin with branched glycol as constituent.As " branched glycol " here, for example can enumerate 2,2-dimethyl-1, ammediol, 2-methyl-2-ethyl-1, ammediol, 2-methyl-2-butyl-1, ammediol, 2-methyl-2-propyl group-1, ammediol, 2-methyl-2-isopropyl-1, ammediol, 2-methyl-2-n-hexyl-1, ammediol, 2,2-diethyl-1, ammediol, 2-ethyl-2-normal-butyl-1, ammediol, 2-ethyl-2-n-hexyl-1, ammediol, 2,2-di-n-butyl-1, ammediol, 2-normal-butyl-2-propyl group-1, ammediol, 2,2-di-n-hexyl-1, ammediol etc.

Branched glycol preferably is used with 10 moles of ratios more than the % in total polyvalent alcohol, further preferably is used with 20 moles of ratios more than the %.As the polyvalent alcohol beyond the branched glycol, most preferably ethylene glycol.If a small amount of, also can use diglycol, propylene glycol, butylene glycol, hexanediol, 1,4 cyclohexane dimethanol etc.

As the polybasic carboxylic acid that is used for synthetic above-mentioned copolymer polyester resin, most preferably terephthalic acid (TPA) and m-phthalic acid.If a small amount of, can also add diphenyl carboxylic acid, 2, aromatic dicarboxylic acids such as 6-naphthalene dicarboxylic acids etc. make it that copolymerization take place.Except above-mentioned polynary dicarboxylic acid,, preferably in the scope of 1～10 mole of %, use to have sulfonic dicarboxylic acid etc. in order to give water dispersible.As having sulfonic dicarboxylic acid, can illustration as the copolymer composition of the aqueous polyester resin of intermediate-index layer and illustrative all cpds.

Above-mentioned polyurethane series resin for example is meant the resin that contains the blocked isocyanate base, can enumerate terminal isocyanate group is sealed the thermal-reactive of (below, be called " end-blocking ") by hydrophilic group soluble polyurethane etc.As the end-blocking agent of isocyanate group, can enumerate the bisulfite salt, contain sulfonic phenols, alcohols, lactams, oximes, activity methene compound class etc.In above-mentioned end-blocking agent, as heat treatment temperature, heat treatment time suitably and can be at the industrial material that is widely used, preferred especially bisulfite salt.

Made carbamate prepolymer hydrophiling or water-solubleization by the isocyanate group of end-blockingization.In addition, when applying heat energy in drying when making film or the heat setting process, the end-blocking agent breaks away from from isocyanate group, therefore self-crosslinking takes place and form netted, and on this reticulate texture the fixing above-mentioned copolymer polyester resin that has mixed.In addition, also react with end group of copolymer polyester resin etc.

Form with in the modulated process of coating fluid in the 2nd adhesiveness modified layer, above-mentioned urethane resin possess hydrophilic property, so poor water resistance, but when finishing thermal response through coating, dry, heat setting, the hydrophilic group of urethane resin (being the end-blocking agent) is sloughed, so can form the good layer of water tolerance.

The carbamate prepolymer that can use in above-mentioned urethane resin is, makes that to have 2 active hydrogen atoms and molecular weight in the organic polyisocyanate that has the active hydrogen atom more than 2 in (1) molecule or the molecule be 200～20000 compound; With, the organic polyisocyanate that has the isocyanate group more than 2 in (2) molecule; The compound that reacts with, the chain elongation agent that has at least 2 active hydrogen atoms in (3) molecule and obtain wherein has terminal isocyanate group.

Compound as (1), usually be known that endways or contain in the strand compound of hydroxyl, carboxyl, amino or sulfydryl more than 2, as particularly preferred compound, can enumerate polyether polyol, polyester polyol, polyether ester type polyvalent alcohol etc.

As polyether polyol, alkylene oxides such as oxirane, epoxypropane are for example arranged, styrene oxide, the polymkeric substance of compounds such as chloropropylene oxide or their atactic polymers, their block polymer, these compounds are to the addition polymerization of polyvalent alcohol and the polymkeric substance that obtains.

As polyester polyol and polyether ester type polyvalent alcohol, mainly can enumerate the compound of straight or branched.Can obtain by making polybasic carboxylic acid class and polyalcohols generation condensation, wherein, as described polybasic carboxylic acid class, can enumerate the saturated or unsaturated carboxylic acid of multivalence such as succinic acid, hexane diacid, phthalic acid, maleic anhydride or the polybasic carboxylic acid classes such as acid anhydrides of these carboxylic acids; As polyalcohols, can enumerate ethylene glycol, diglycol, 1,4-butylene glycol, neopentyl glycol, 1, saturated or the undersaturated alcohols of multivalence such as 6-hexanediol, trimethylolpropane, the polyglycol that molecular weight is lower, the polyalkylene ether glycols classes such as polypropylene glycol that molecular weight is lower, perhaps potpourri of these alcohols etc.And then, as polyester polyol, can also enumerate the polyesters that obtains by lactone and alcohol acid.In addition, as the polyether ester type polyvalent alcohol, can also use addition of ethylene oxide or epoxypropane etc. in the polyesters of making in advance and the polyether ester class that obtains.

Organic polyisocyanate as above-mentioned (2), can enumerate the isomeride class of toluene support diisocyanate, 4, aromatic diisocyanate classes such as 4-methyl diphenylene diisocyanate, aromatic series aliphatic diisocyanate classes such as xylylene diisocyanate, isophorone diisocyanate, 4, ester ring type diisocyanates such as 4-dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate, 2,2, aliphatic diisocyanate classes such as 4-trimethyl hexamethylene diisocyanate, perhaps mix in these compounds one or more and make it and trimethylolpropane etc. carries out addition and polyisocyanate class of obtaining etc.

Chain elongation agent as above-mentioned (3), can enumerate ethylene glycol, diglycol, 1,4-butylene glycol, 1, glycolss such as 6-hexanediol, polyalcohols such as glycerine, trimethylolpropane, pentaerythrite, two amines such as ethylenediamine, hexamethylene diamine, piperazine, alkamines such as monoethanolamine, diethanolamine, dihydroxy two sulphur classes such as sulfo-diglycol, water etc.

For synthetic above-mentioned urethane polymer, single step or the multiple-step form isocyanates addition polymerization method by having used above-mentioned chain elongation agent usually below 150 ℃, preferably under 70～120 ℃ temperature, makes 5 minutes～a few hours of its reaction.As long as isocyanate group is more than 1 with respect to the ratio of active hydrogen atom, just can freely selects, but free isocyanate group is remained in the carbamate prepolymer that obtains.And then the content of free isocyanate group is below the 10 quality %, if but consider the stability of the urethane polymer aqueous solution after the end-blockingization, be preferably below the 7 quality %.

Use end-blocking agent (preferred hydrosulfite) carry out end-blockingization to the carbamate prepolymer that obtains.Under the situation of using hydrosulfite, mix with the bisulfite brine solution, in 5 minutes～1 hour it is reacted at abundant stir about.Temperature of reaction is preferably below 60 ℃.Subsequently, water dilutes and makes it reach suitable concentration, makes thermal-reactive water-soluble carbamate composition.When using said composition, can be adjusted to suitable concentration and viscosity.Above-mentioned composition is when being heated to 80～200 ℃ of front and back usually, the hydrosulfite of end-blocking agent dissociates, the active isocyanate group of regenerating, so pass through in the molecule of prepolymer or the polyaddition reaction of intermolecular generation, generate polyether polyols with reduced unsaturation, perhaps possess the character that can add to other functional groups.

As above-mentioned urethane resin with blocked isocyanate base, as typical example can illustration Di-ichi Kogyo Seiyaku Co., Ltd. system " ELASTRON (trade name) ".ELASTRON utilizes sodium bisulfite that isocyanate group is carried out the material of end-blocking, exists in molecular end to have the carbamyl sulfonate group of strongly hydrophilic, so have water-soluble.

The above-mentioned copolymer polyester resin (a) when modulating the formation of the 2nd adhesiveness modified layer with coating fluid and the mass ratio of above-mentioned urethane resin (b) are preferably (a): (b)=90: 10～10: 90, more preferably (a): (b)=80: 20～20: 80.

In the coating fluid that is used to form intermediate-index layer or the 2nd adhesiveness modified layer, can add catalyzer and promote the heat cross-linking reaction.As catalyzer, for example can use various chemical substances such as dead matter, salt, organic substance, alkaline matter, acidic materials or containing metal organic compound.In addition, in order to regulate the pH of aqueous solution, can add alkaline matter or acidic materials.

When adopting rubbing method to form intermediate-index layer or the 2nd adhesiveness modified layer on the base film surface, apply coating fluid equably in order to improve to the wetting state of base film, can add known negative ion or non-ionic tenside.

Form the solvent of using coating fluid with coating fluid and the formation of the 2nd adhesiveness modified layer as being used for intermediate-index layer, can enumerate water, the mixed solvent of water and alcohols (ethanol, isopropyl alcohol, benzylalcohol etc.) etc.Using under the situation of alcohols, its content is preferably less than 50 quality % of total coating fluid.And then, if less than 10 quality % in total coating fluid, then can be in the scope that can dissolve mixed alcohols organic solvent in addition.But, in coating fluid, the total amount of alcohols and other organic solvents is made as and is less than 50 quality %.

When containing the organic solvent of alcohols with the use of the amount below the above-mentioned higher limit, when carrying out drying after the coating coating fluid, drying property is improved, and compares the effect of the outward appearance of the coated film that can improve with the situation that only makes water simultaneously.When the organic solvent amount that contains alcohols surpasses above-mentioned higher limit, the velocity of evaporation of solvent is accelerated, so the concentration of coating fluid changes in coating process, coating fluid viscosity rises and causes screening characteristics to reduce, so might cause the bad order of coated film, and then might have danger such as fire.

In addition, form with regard to the solid component concentration (except the particle described later) in the coating fluid with coating fluid and the 2nd adhesiveness modified layer, be preferably below the 30 quality %, more preferably below the 10 quality % with regard to intermediate-index layer formation.

Also have, the solution viscosity of coating fluid is preferably below the 1.0Pas.If solution viscosity is excessive, the coating thickness spot of strip appears easily.

In order to give easy sliding property, preferably contain particle in intermediate-index layer and the 2nd adhesiveness modified layer as lubricant.As mentioned above, in the double orientation laminated polyester film, from improving the viewpoint of the transparency, the preferred formation that does not contain particle in fact that adopts.But if adopt such formation, processing such as the lubricity of base film or batching property can descend.In order addressing this problem, in intermediate-index layer and the 2nd adhesiveness modified layer, preferably to contain and be useful on the lubricant particle of giving easy sliding property, thereby form the projection of appropriateness at these laminar surfaces.

Thus, in forming with coating fluid with coating fluid and the 2nd adhesiveness modified layer, intermediate-index layer formation preferably contains the particle that becomes lubricant.Example as this particle, can enumerate inorganic particulates such as lime carbonate, calcium phosphate, silicon dioxide, porcelain earth, talcum, titania, aluminium oxide, barium sulphate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, organic fillers such as cross-linked polymer particle (for example crosslinked polymethylmethacrylaparticles particle), calcium oxalate.Wherein, with polyester with the situation that acts on the resin that constitutes intermediate-index layer or the 2nd adhesiveness modified layer under because with the refractive index ratio of polyester near and obtain high transparent easily, so preferred silicon dioxide.

The mean grain size of above-mentioned particle is generally 0.01～1.0 μ m, more preferably 0.01～0.5 μ m, more preferably 0.01～0.1 μ m.If mean grain size is excessive, intermediate-index layer or the 2nd adhesiveness modified layer surface be roughening too, and the transparency has the trend of reduction.On the other hand, when adopting the too small particle of mean grain size, can't fully guarantee easily sliding property sometimes.

In addition, intermediate-index layer forms with coating fluid or the 2nd adhesiveness modified layer and forms with the particle content in the coating fluid, usually be set as with the content in coating, the dried layer and count below the 60 quality %, more preferably below the 50 quality %, more preferably below the 40 quality %.When particle content is too much, damages the adhesiveness that intermediate-index layer or the 2nd adhesiveness modified layer bring sometimes and improve effect.

Above-mentioned particle can cooperate more than 2 kinds, can cooperate the different particle of the same race of mean grain size.In any case the mean grain size of particle integral body and total content preferably are adjusted to the amount that satisfies above-mentioned scope.

When coating intermediate-index layer formation on the stacked polyester of double orientation is used coating fluid with coating fluid and the formation of the 2nd adhesiveness modified layer, preferably by removing by filter the thick condensation product of the particle in the coating fluid.Type to filter materials is not particularly limited, and for example can enumerate fibril type, felt type, mesh-type.As long as the material of filter materials has above-mentioned performance and can not cause harmful effect to coating fluid, just be not particularly limited, for example, except above-mentioned stainless steel, can also enumerate tygon, polypropylene, nylon etc.

Form with in the coating fluid with coating fluid or the 2nd adhesiveness modified layer in intermediate-index layer formation, can in the scope of not damaging its effect, mix various adjuvants such as antistatic agent, pigment, organic filler, lubricant.And then, because coating fluid is a water-based, so in the scope of not damaging its effect,, can in coating fluid, add other water soluble resins, water dispersible branch, emulsion etc. in order further to improve performance.

Use coating fluid for coating intermediate-index layer on base film forms with coating fluid or the formation of the 2nd adhesiveness modified layer, can adopt known any method to carry out.For example, can enumerate against roller rubbing method, photogravure coating process, kiss-coating mode, roller brush method, spraying process, air knife knife coating, wire bar rod and be coated with method, tubular type knife coating, infiltration coating process, curtain coating method etc., these methods can be carried out separately, can also make up and carry out.

With regard to the opportunity of coating coating fluid, when base film is biaxially oriented film, can be after two-way stretch, finish heat fixation, finish the time point of Biaxially oriented film, but be more preferably in the manufacturing process of Biaxially oriented film.The further preferred stage before the crystal orientation of Biaxially oriented film is finished.At this moment, together with intermediate-index layer, the 2nd adhesiveness modified layer, the coating weight of coating fluid [to the adhesion amount of base film] is at every 1m ²In the double orientation laminated polyester film of just walking [perhaps, the intermediate product of double orientation laminated polyester film], be preferably 0.01～5g, more preferably 0.2～4g.

For example, making by two-way pulling method one by one under the situation of double orientation laminated polyester film, (one-way orientation film) is when being coated with each coating fluid after the unilateral stretching in the manufacturing process of double orientation laminated polyester film, one-way orientation film after the coating is directed in the stenter to stretch and heat fixation, and heat at this, therefore can make the base film that has formed stable tunicle (intermediate-index layer and the 2nd adhesiveness modified layer) by the heat cross-linking reaction.

Wherein, from the adhesiveness of the hard conating of further raising anti-reflection layer and intermediate-index layer or with the viewpoint of the adhesiveness (intermediate-index layer or the 2nd adhesiveness modified layer) of near infrared ray absorption layer, preferably after the coating coating fluid in the thermal treatment of enforcement more than 1 minute under the temperature more than 100 ℃.

In addition, form environment when being coated with, preferably will purify grade and be made as below 1000 grades, so that the adhering to of minimizing dust with coating fluid as middle index layer being formed with coating fluid or the 2nd adhesiveness modified layer.

[bonding coat]

Near-infrared absorbing film of the present invention is being used under the situation of near-infrared absorbing light filter, is preferably possessing bonding coat and go up and fix to be attached to plasma display surface or electromagnetic wave blocking layer (aftermentioned).For this reason, bonding coat is formed on the near infrared ray absorption layer surface.The clear binder that is used for this bonding coat is not particularly limited, can uses known bonding agent in this technical field.For example can enumerate acrylic adhesives such as butyl acrylate, rubber is bonding agent, is bonding agent etc. based on the TPE of SEBS (styrene-ethylene-butadiene-styrene), SBS thermoplastic elastomers (TPE) such as (s-B-Ss).Wherein, preferably use the surface of known isolated film (having implemented the PET film of silicone-treated etc.) protection bonding coat, till using bonding coat.

[characteristic of near-infrared absorbing film]

Then, the preferred characteristics to near-infrared absorbing film of the present invention describes.Wherein, these characteristics can adopt above-mentioned formation to guarantee by making film of the present invention.

As mentioned above, near-infrared absorbing film of the present invention is required that the absorption of near infrared range is bigger, the transmitance of luminous ray is higher simultaneously, specifically, the transmitance of the light of the wavelength region may of preferred 450～650nm is more than 55%, more preferably more than 60%, and, the transmitance of the light of the wavelength region may of 820～1100nm is preferably below 20%, more preferably below 15%.

Use in the light filter of front at the plasma display that has used near-infrared absorbing film of the present invention, as previously mentioned, use has the complementary color pigment of very big absorption in the scope of wavelength 550～620nm, optionally absorb specific wavelength so that make transmitance in the wavelength region may of 550nm～600nm in 10～60% scope, and the transmitance that makes the wavelength region may of 820nm～1100nm is below 20%, and also can improve with the display thus is the colour balance of the image of representative.The transmitance of the wavelength region may of 550nm～600nm more preferably 15～50% is preferably 18～45% especially.In addition, the transmitance of the wavelength region may of 820nm～1100nm is more preferably below 15%.

Particularly under the situation of using the 1st adhesiveness modified layer,, specifically, has characteristic as follows even near-infrared absorbing film of the present invention also can suppress the variation of its spectral characteristic or tone very effectively hot and humid long-time placement the down.

About spectral characteristic, preferably using the maximal value of variable quantity V (%) of the transmitance of following formula (1) expression is below 7%, more preferably below 5%.

V＝100×|T _0(WL)-T _1(WL)|/T _0(WL) …………(1)

Here, T _{0 (WL)}And T _{1 (WL)}Be the transmitance of the film at wavelength WL place, be meant at 60 ℃ of temperature, 95% time keeping of relative humidity (T before 100 hours _{0 (WL)}) and should keeping back (T _{1 (WL)}) value measured, WL represents each wavelength of 450nm～1100nm.

Promptly, this means, for in temperature: 60 ℃, relative humidity: time 95%: when the film under 500 hours the condition before and after the keeping was measured the transmitance of light of each wavelength of 450～1100nm, the variable quantity V at the wavelength place of the variation maximum of transmitance was below 7%.When the maximal value of variable quantity V surpassed above-mentioned higher limit, when comparing film before and after keeping, the variation of tone had significant more trend.

About tone, preferably use the L of following formula (2) expression ^*a ^*b ^*The chromaticity coordinates b of colour system ^*Difference Δ b ^*For more than-3, below 3, more preferably-2 above, below 2.

Δb ^*＝b ^* ₁-b ^* ₀ …………(2)

Here, b ^* ₁And b ^* ₀Be b by the film of obtaining through light ^*, be to be illustrated in 60 ℃ of temperature, 95% time keeping of relative humidity (b before 500 hours ^* ₀) and this keeping back (b ^* ₁) value measured." L wherein ^*a ^*b ^*The chromaticity coordinates b of colour system ^*" be meant 1976 (L by CIE ^*a ^*b ^*The color space) definite b ^*

As Δ b ^*In the time of outside above-mentioned scope, when in the keeping front and back film being compared, the variation of tone has significant more trend.Wherein.b ^*Negative value BigBlue is dark more more, dark more on the occasion of big more yellow.

[characteristic of near-infrared absorbing film volume]

Then, the near-infrared absorbing film of the length more than the long 100m of the present invention, more than the wide 0.5m is batched the near-infrared absorbing film that forms and involve in the row explanation.

With regard to the long film that is coiled into this volume, the maximal value of the aberration Δ E (MD) of the length direction (MD) of the film of obtaining by following determination method (A) is below 2.0.

(A) when measuring the tone of above-mentioned film, on the length direction (MD) of this film, one end in the constant zone that the film rerum natura is stable is as the 1st end, with the other end during as the 2nd end, carry out primary mensuration at the inboard 2m of the 1st end with interior, in addition, carry out last mensuration with interior at the inboard 2m of the 2nd end, once measure every about 10m from primary locating simultaneously, calculate at the aberration Δ E (MD) that respectively locates with following formula (3) definition.

ΔE(MD)＝[(L _a-L _m) ²+(a _a-a _m) ²+(b _a-b _m) ²] ^1/2 ……(3)

Here, L _m, a _m, b _mBe meant tone L, a, the b that respectively locate, L _a, a _a, b _aBe meant all tone L, a that locate, the mean value of b.

In addition, the Width of the film of obtaining by following determination method (B) (with the direction of the length direction quadrature of film: the maximal value of the aberration Δ E (TD) TD) is below 1.0.

(B) when measuring the tone of above-mentioned film, on the Width (TD) of this film, one end in the constant zone that the film rerum natura is stable is as the 1st end, with the other end during as the 2nd end, carry out primary mensuration at the inboard 0.1m of the 1st end with interior, in addition, carry out last mensuration at the inboard 0.1m of the 2nd end with interior, simultaneously between primary the locating to the end of locating, measure the aberration Δ E (TD) that calculates at this 5 place with following formula (4) definition roughly uniformly-spaced to carry out 3 places.

ΔE(TD)＝[(L _a-L _m) ²+(a _a-a _m) ²+(b _a-b _m) ²] ^1/2 ……(4)

Here, L _m, a _m, b _m, L _a, a _a, b _aIdentical with the situation of above-mentioned (A).

Carry out the reasons are as follows of tone mensuration in the constant zone of film: as described later, film of the present invention is to be coated with to be used to form after the coating fluid of near infrared ray absorption layer on transparent base, through its dry operation is formed, before the operation of the painting process of this coating fluid or drying process stable, the film rerum natura changes sometimes.The aberration Δ E (MD) of technical conceive of the present invention and the film that obtains when not lying in the fluctuation of service that is implemented in above-mentioned painting process or the drying process or the homogenising of Δ E (TD), and be the stable operation in these operations and make in the stable film of the rerum natura that obtained when having entered steady state, than the homogenising that realizes the aberration Δ on the higher in the past level.

Wherein, the quantity of the constant zone that the film rerum natura is stable in a film usually (making the film portion that has obtained when having entered steady state) has only a place (having the situation at a place to be included in the film total length).But, also can have many places, so tone was only measured and got final product in constant zone this moment according to Manufacturing Status.In addition, above-mentioned constant zone for example can be estimated with the value of aberration Δ E.That is, can be below 2 with the aberration Δ and stable part is considered as constant zone.

Can use colour difference meter (Japanese electric look industry system in the mensuration of tone, ZE-2000 etc.), and with standard light as the D65 light source, with angle of visibility be made as 10 the degree conditions under, carry out rayed to the near-infrared absorbing side, obtain L value, a value, the b value of Lab display system.The assay method of tone is not limited at the above-mentioned excision working sample that respectively locates these samples is carried out the tone method for measuring, under the situation that the tone that carries out length direction is measured, can use the on-line determination method, promptly, film batched form after the film rolling, pull out film and coiling into other volumes from this film rolling on one side, Yi Bian measure.

The aberration Δ E (MD) of length direction can obtain by following determination method.

At first, the tone that carries out film is measured.Tone mensuration is that carry out in the stable constant zone of film rerum natura on the length direction of film, when a end that will this constant zone is made as the 1st end, when the other end is made as the 2nd end, carry out primary mensuration at the inboard 2m of the 1st end with interior, in addition, carry out last mensuration at the inboard 2m of the 2nd end with interior, once measure every about 10m from the primary beginning that locates simultaneously.

Wherein, as the mensuration position of the film in respectively locating, preferably keep the position of Width of film consistent.For example, when in primary locating, carrying out tone when measuring, in for the second time later locating, all be that central portion in the thin-film width direction carries out tone and measures at the central portion of thin-film width direction.This be because, if the mensuration position of the tone of thin-film width direction is inconsistent, the then correctly variation of the tone of evaluation length direction.

The L value is the index of expression brightness, and the big more blackout degree of numerical value is just few more, and brightness is just high more.The a value is the index of the red degree of expression, and numerical value large red more is strong more, and is strong more in the big more green of numerical value of a negative side.The b value is the index of the yellow degree of expression, and the big more yellow of numerical value is strong more, and BigBlue is strong more more at the numerical value of a negative side.

In respectively locating, obtain L value, a value, b value, calculate the aberration Δ E (MD) that respectively locates by above-mentioned formula (3).So obtain in the middle of the aberration Δ E (MD) that respectively locates, maximal value is necessary for below 2.0.

Maximal value at aberration Δ E (MD) surpasses in the film of above-mentioned higher limit, variation at the tone of the length direction of film is bigger, use in the light filter at a plurality of plasma displays that obtain by this film, the tone of (between the light filter) there are differences between product, is difficult to provide the plasma display light filter of stay in grade.The maximal value of aberration Δ E (MD) is more preferably below 1.0, more preferably below 0.5.

As the tone of film, for example, preferred above-mentioned a value is more than-10.0+below 10.0, above-mentioned b value is more than-10.0+and below 10.0.If a value and b value are within such scope, even being used for plasma display with under the situation of light filter, also can become natural (natural) look.The adjustment of such tone can be based on the kind of near infrared absorbing coloring matter, the near infrared absorbing coloring matter concentration in the unit area and reach with mixing of other pigments in the vertical view of near infrared ray absorption layer.Wherein, as described later, film of the present invention in its front and/or the back side other optical thin films or bonding coat etc. can be set and make the plasma display light filter, but, preferably carry out the adjustment of tone so that comprise them and all be natural color being provided with under the situation of such layer etc.

The L value is high more preferred more.The L value is high more, when the making plasma display is used light filter, can provide bright plasma display.The L value is preferably more than 80, more preferably more than 85.

In addition, in thin-film width direction (TD), the maximal value of the aberration Δ E (TD) that obtains by said determination method (B) is below 1.0.More preferably below 0.5.Wherein, the end in said determination method (B) is meant the end of Width.

So long as the aberration Δ E (TD) of Width is the film below the above-mentioned higher limit when the tonal variation of length direction is suppressed, then use in the light filter at a plurality of plasma displays that obtain by this film, the tone spot of (between the light filter) can be inhibited between product, the tone spot can be subjected to highly suppressing in each product, and more high-quality plasma display light filter can be provided.That is, when the film that surpasses above-mentioned higher limit with the aberration Δ E (TD) of thin-film width direction was made plasma display and used light filter, it became the reason that color spot appears in display picture sometimes.

The variation of such tone is suppressed (promptly, it is following that the maximal value of the aberration Δ E (MD) of the length direction of film and the aberration Δ E (TD) of thin-film width direction is controlled in above-mentioned higher limit) near-infrared absorbing film, can obtain by following manufacture method.

[manufacture method of near-infrared absorbing film and film rolling]

Then, the preferable production process to film rolling that near-infrared absorbing film of the present invention and long film are formed by coiling describes.

In order to make near-infrared absorbing film, for example, can adopt method as described below, promptly by on transparent base film, being coated with the operation that the near infrared ray absorption layer that contains near infrared absorbing coloring matter, resin, surfactant and organic solvent is used coating fluid continuously, and the operation of carrying out drying continuously, on transparent base film (below, be called transparent base sometimes merely), form near infrared ray absorption layer continuously.Wherein, can be arranged on the layer (the 1st adhesiveness modified layer etc.) between transparent base and the near infrared ray absorption layer, can before forming near infrared ray absorption layer, form by the formation method of in the explanation of relevant each layer, having recorded and narrated.

After above-mentioned drying process, the tone of film and/or the light penetration of specific wavelength are carried out on-line determination, adjust the coating condition and/or the drying condition of coating fluid according to this measurement result, can obtain the repressed film of variation of tone on the length direction of film thus, the maximal value that is about to the aberration Δ E (MD) that obtains by said determination method (A) is controlled at the film below the above-mentioned higher limit.

As the coating condition, can enumerate the coating weight of coating fluid.The coating weight of coating fluid can impact the L value of film, so monitor the tone of the film in the manufacture process at any time and change by online, so that when the L value is higher, the coating weight of coating fluid is increased, on the other hand, the coating weight of coating fluid is reduced.If tone (L value) variation is controlled after the change, then continue to make film, otherwise carry out the change of coating weight once more with this coating weight.

For example under situation about being coated with reverse photogravure applying device described later, rotational speed G by the change gravure roll is with respect to the velocity ratio G/F of the speed of travel F of film, scraper contact pressure or the contact angle with respect to gravure roll, the coating weight that can regulate coating fluid.That is, if will increase coating weight, can to increase G/F, reduce the contact pressure of scraper, the direction that reduces contact angle is regulated, if will reduce coating weight, then can to reduce G/F, increase the contact pressure of scraper, the direction that increases contact angle is regulated.When regulating the coating weight of coating fluid, can change any one condition and carry out, can change a plurality of conditions and carry out.

In addition, as drying condition, can enumerate drying efficiency.If drying efficiency changes, will a value and the b value of film be impacted, so the tone by online film in monitor making at any time when a value or b value change, carries out the adjusting of drying efficiency.As the method for regulating drying efficiency, can take to control the speed of travel (drying time) of film, the temperature of dry wind, the method for air quantity (wind speed).That is,, can control to the temperature of the speed of travel that reduces film, rising dry wind, the direction of increase air quantity if will further carry out drying.On the other hand, if will further reduce dry degree, can control to the direction of the speed of travel that improves film, the temperature that reduces dry wind, minimizing air quantity.Can change any one condition when regulating drying efficiency and carry out, also can change a plurality of conditions and carry out.For example,, can regulate, on the other hand,, can regulate with the reduction drying efficiency under the low situation of a value and/or under the high situation of b value to improve drying efficiency under the high situation of a value and/or under the low situation of b value.

Wherein, during the tone when making film is measured, can adopt the identical method of tone mensuration with the aberration Δ E that is used to calculate film.

In addition, under the situation of the management when making film with the light penetration of specific wavelength, by the online transmitance that monitors the light of this specific wavelength at any time,, then can control coating condition and/or drying condition so that its stabilization if aspect transmitance, find to change.For example, under the situation that the direction that increases to light penetration changes, can change, under the situation of the direction change that reduces to light penetration, can change to the direction of the coating weight that reduces coating fluid to the direction of the coating weight that increases coating fluid.As the coating weight of coating fluid or the control method of drying efficiency, can adopt the method that in the situation of online monitoring tone, has illustrated.

The light penetration of specific wavelength for example can use spectrophotometer (Da mound electronics system, MCPD-3000 etc.), from the light of near infrared ray absorption layer side irradiation specific wavelength, the transmitance of indoor air is measured as reference point (blank).

Method as coating coating fluid on transparent base, for example, can adopt above-mentioned illustrative the whole bag of tricks, but preferably the coating process by the photogravure application pattern carries out, particularly suitable is to utilize the gravure roll of reverse rotation to gather together (scrape up) coating fluid from the feed flow dish, by the flatten coating process of " oppositely photogravure application pattern " of (scrape down) unnecessary coating fluid of scraper.By adopting such photogravure mode, particularly adopt reverse photogravure application pattern, can finish more uniform coating.In addition, as described later,, be fit to use the kiss-coating mode for evenly coating on Width.Fig. 1 has represented to adopt the device (oppositely photogravure/kiss-coating device) of reverse photogravure application pattern.Also have, near infrared ray absorption layer is successive layers in itself.Thus, even adopt the photogravure application pattern, near infrared ray absorption layer also can become successive layers.

In above-mentioned reverse photogravure applying device, preferably use diameter to be the gravure roll below the 80mm.Under the bigger situation of diameter, ridge shape striped appears on the direction of travel of film easily.As the scraper that in reverse photogravure applying device, uses, can use known scraper, but the surface of the part that contacts with gravure roll [the point of a knife part that contacts with coating fluid on the gravure roll] is the scraper of ceramic at least, because of it is difficult for being worn and makes the coating weight stabilization of coating fluid easily, so preferred the use.Certainly, also preferred whole scraper all is a ceramic.In addition, for example, the scraper (part that is equivalent to contact with gravure roll is the scraper of nickel system) of nickel plating has been implemented on the surface of Sweden's formula steel, although poorer than the scraper of ceramic, because it is difficult for being worn, so also be fit to use.

In reverse photogravure applying device,, as mentioned above, can enumerate gravure roll with respect to pushing of the rotating speed of the speed of travel of film, the angle that is contacted with scraper, scraper etc. as the principal element that is used to control coating weight.In order to increase coating weight, preferably improve the rotating speed of gravure roll.From the transfer printing of photogravure lattice, coating defective or coating weight viewpoint, preferably the rotational speed G (m/ minute) of gravure roll is controlled at more than 0.8 below 1.5 than G/F with respect to the speed of the speed of travel F (m/ minute) of film along with the stability of time.In addition, more preferably speed is limited to 0.9 than the following of G/F.Favor speed is than being limited to 1.2 on the G/F, and more preferably 1.1.When speed was more too small than G/F, the transfer printing amount reduced, and the photogravure lattice are not coated with flat and residual easily.On the other hand, when speed was more excessive than G/F, except coating such as the horizontal spot of easy appearance, strip bubble defective, scraper was worn easily, and perhaps the ageing stability of coating weight becomes bad frequency and can increase.Wherein, the rotational speed F of gravure roll (m/ minute) be in gravure roll rotating speed (rotating speed/minute: multiply by the girth [circular constant * roller diameter (mm)] of gravure roll rpm), and became calculate in m/ minute unit conversion.

As making scraper be contacted with the angle of the coating fluid on the gravure roll, be preferably 20～70 ° in interior angle.Under the situation (pressing the situation of pressing gravure roll with the scraper tripe) of angle too small, the power of scraping of the coating fluid on gravure roll surface reduces, coating weight increases, in addition, although be difficult to occur the wearing and tearing of scraper, but also occur vibration etc. easily on scraper, the outward appearance of near infrared ray absorption layer worsens easily.On the other hand, under the bigger situation of angle (scraper being pricked the into situation of gravure roll), the power of scraping of the coating fluid on gravure roll surface increases, and coating weight reduces, although also be difficult to occur the vibration etc. of scraper, easy wear problems can occur.

With regard to the contact pressure of scraper,, preferably be adjusted to the degree of this blade slight curvature from the viewpoint of the coating weight homogenising that makes the thin-film width direction.

In addition, for the variation that suppresses the thin-film width direction and the aberration Δ E (TD) that makes this Width below above-mentioned higher limit, preferably be used to form the coating of the coating fluid of near infrared ray absorption layer by kiss-coating, with the length direction Tension Control in the coating part of transparent base at 0.5N/mm ²Above 1.2N/mm ²Below (1.0N/mm more preferably ²Below).

When being coated with by the kiss-coating mode, a face (coated face) that has only transparent base contacts with the applicator roll that is used to be coated with coating fluid, and other faces are free state (not being contacted with the state of any material).When the coating coating fluid, if the opposing face of the coated face of transparent base is contacted with roller etc., then when foreign matter attached to this roller surface on the time, when perhaps being formed with microspike on this roller surface, sometimes also can the outward appearance of near infrared ray absorption layer be impacted, if but adopted the kiss-coating mode, such influence could be avoided, so can make the outward appearance of near infrared ray absorption layer more even.

In order to adopt kiss-coating mode stable coating coating fluid on transparent base, front and back at the coating part of transparent base are provided with roller, length direction at transparent base applies tension force, to keep the planarity of coating part, pass through this moment Tension Control in above-mentioned scope, can on the Width of transparent base, be coated with coating fluid equably, highly suppress the tonal variation of thin-film width direction.If mentioned strain is low excessively, the walking of transparent base is bad, occurs easily crawling etc., and the coating homogeneity of coating fluid is destroyed on the thin-film width direction, is easy to generate tonal variation on the thin-film width direction.On the other hand, when mentioned strain is too high, transparent base can be near the central portion of roller (roller before and after the coating part), produce the ripple of the tinned sheet iron shape parallel with direction of travel (length direction), on the Width of transparent base, the homogeneity that contacts of kiss roll (kiss roll, applicator roll) and transparent base is damaged, so the tonal variation of thin-film width direction increases sometimes on the contrary.

The tension force of the length direction in the coating part of transparent base can be controlled by the balance of the rotating speed that is arranged on the roller before and after this coating part is regulated.In addition, the mentioned strain during the film walking for example, can adopt by the conventional method of the load on the measuring cell mensuration roller and measure.

As mentioned above, in the manufacturing of film of the present invention, as the mode of coating coating fluid on transparent base film, preferred oppositely photogravure application pattern from the viewpoint of the tonal variation that suppresses the thin-film width direction, is fit to use the kiss-coating mode simultaneously.Thus, as coating method, the most preferred reverse photogravure/kiss-coating mode that is to use reverse photogravure/kiss-coating device shown in Figure 1.

Coating weight to coating fluid is not particularly limited, and in dried amount, is preferably 1g/m ²More than, 3g/m more preferably ²More than, and be 50g/m ²Below, 30g/m more preferably ²Below.When coating weight was very few, near infrared receptivity was not enough sometimes.For this reason, be necessary to increase the concentration of the per unit area under the overlooking of near infrared ray absorption layer, near infrared receptivity is adjusted to target level, but this moment, because the distance between the pigment shortens, interaction between the pigment strengthens, and the deterioration of pigment etc. appears in its result easily, and ageing stability has the trend of reduction.

On the other hand, when coating weight is too much, though enough near infrared receptivities are arranged, but the transmitance in the visible region reduces, the transparency has the trend of reduction, so in the plasma display of using such near-infrared absorbing film, brightness reduces sometimes.If will avoid this point, can reduce the pigment concentration under the overlooking of near infrared ray absorption layer, elongate the distance between the pigment, improve transmitance in the visible region, but must increase the thickness of near infrared ray absorption layer for this reason, occur dry insufficient easily in coating fluid coating back.Its result, residual solvent amount in the near infrared ray absorption layer increases, pigment through the time (after after a while) stability worsen, particularly (for example in hot and humid long-time down keeping, 60 ℃, relative humidity 95%, 500 hours) situation under, the transmitance of film or the variation of tone have the trend of increase.On the other hand, make drying condition strict if improve temperature when dry or time expand etc., planarity bad of the transparent base that caused by heat appears in for example heat labile pigment (Ji Yinmoni diimmonium salt compound etc.) sex change easily easily.

With regard to the drying after the coating coating fluid, can adopt heated-air drying, utilize the known drying means such as drying of infrared heater, but be fit to use the fast heated-air drying of rate of drying.In addition, if reduce the residual solvent amount when will suppress the sex change of near infrared absorbing coloring matter, then preferably carry out above multistage heated-air drying operation of 2 stages.

In the drying process (constant rate of drying operation) in the 1st stage, hot blast speed, drying time, wind speed are important.Specifically, preferably making baking temperature is 20～80 ℃.If baking temperature less than 20 ℃, then occurs dry insufficient easily.Therefore, more preferably 30 ℃ of the lower limits of the baking temperature in the drying process in the 1st stage are preferably 35 ℃ especially.On the other hand, when baking temperature surpassed 80 ℃, the solvent evaporation in filming was inhomogeneous, so occur the coating spot easily.Therefore, more preferably 75 ℃ of the upper limits of the baking temperature in the drying process in the 1st stage are preferably 70 ℃ especially.

In addition, preferably making drying time in the drying process in the 1st stage is more than 10 seconds below 120 seconds.When drying time during less than 10 seconds, in the drying process of after-stage, the evaporation capacity of solvent increases, and the solvent evaporation in filming is inhomogeneous, so occur the coating spot easily.On the other hand, when surpassed 120 seconds drying time, the evaporation of solvent was suppressed, and filming in the forming process is maintained at has fusible state.For this reason, can adhere to foreign matter on filming, outward appearance worsens easily.

And then preferably making wind speed in the drying process in the 1st stage is the 0.5m/ second of above 30m/ below second.If wind speed is less than 0.5m/ second, rate of drying slows down, and drying needs the long period, so throughput rate reduces.Preferred wind speed is that 2m/ is more than second.On the other hand, when wind speed surpasses 30m/ during second, the solvent evaporation in filming is inhomogeneous, so occur the coating spot easily.

In the drying process in the 2nd stage, the drying process that baking temperature is the highest (falling rate of drying operation), be that the residual solvent amount that is used for reducing near infrared ray absorption layer makes it to drop to the operation that 5.0 quality % are following, be preferably the following particular importance of 3.0 quality %, above-mentioned residual solvent amount can be controlled with hot blast temperature, drying time, wind speed, preferably satisfies following formula (5)～(7) simultaneously.Wherein, in following formula (5)～(7), the unit of wind speed is m/ second, and the unit of hot blast temperature is ℃, and the unit of drying time is minute that the unit of applied thickness is μ m.

Wind speed * (hot blast temperature-20) * baking temperature/applied thickness＞48 ... (5)

Hot blast temperature: 80～180 ... (6)

Drying time: 0.083～60 ... (7)

Hot blast temperature in the highest drying process of baking temperature preferably is higher than the hot blast temperature in the drying process in the 1st stage, is the scope below 180 ℃ more than 80 ℃.More preferably 100 ℃ of lower limits, more preferably 120 ℃.More preferably 170 ℃ of higher limits.In addition, above-mentioned hot blast temperature is preferably more than the glass temperature of the resin that constitutes near infrared ray absorption layer especially.Cross when low when the temperature of wind, the residual solvent amount in the near infrared ray absorption layer is difficult to reduce.When baking temperature surpasses 180 ℃, following problems appears easily, and promptly the deterioration of pigment is remarkable, and the distortion of base film increases, and hot fold occurs and cause planarity bad etc. easily on base material.Be preferably the drying time of this operation more than 5 seconds below 60 minutes.Lower limit is 10 seconds more preferably, are preferably for 20 seconds especially.On the other hand, higher limit more preferably 30 minutes is preferably 15 minutes especially.

In addition, the hot blast speed in the highest drying process of baking temperature is preferably 0.5～40m/ second.Lower limit is 1.0m/ second more preferably, is preferably 2.0m/ second especially.On the other hand, higher limit is 30m/ second more preferably, is preferably 20m/ second especially.

By adopting such multi stage drying operation, can in the sex change that suppresses near infrared absorbing coloring matter, reduce the residual solvent amount.Promptly, in the constant rate of drying operation in the 1st stage, under the condition of relatively gentle (mild), carry out drying, so solvent can form with the evenly evaporation of filming near infrared ray absorption layer, surfactant is at the film coated surface localization, so can form the near infrared ray absorption layer with uniform outer surface simultaneously.Its result can obtain applying the few film of spot.

(temperature of rising wind increases air quantity) is difficult to occur the localization of surfactant in film coated surface when carrying out the 1st stage dry under exacting terms.Its result, the effect that not only improves permanance or give sliding are difficult to occur, and occur being derived from tiny flaws such as the small holiday of the bubble that coating fluid comprises, small depression, crackle near infrared ray absorption layer easily.

On the contrary, when the initial stage drying of making excessively is under the gentle condition (hot blast temperature is low, and the air quantity of hot blast is little), though the outward appearance of filming is good, but drying time is long, is not only expending existing problems aspect the cost, and is occurring scratch brushing problems such as (brushing) easily.

In near-infrared absorbing film, especially obvious when deep or light differing greatly in narrow area with regard to the coating spot of near-infrared absorbing layer, so wish to obtain the few film of coating spot.Wherein, the evaluation of coating spot is carried out by the following method, is that the square of 15cm cuts out the square that is cut into 5cm behind the film sample again with the length of side from long near-infrared absorbing film promptly, therefore the sample that amounts to 9 points is measured L ^*a ^*b ^*The L of colour system ^*, according to the L of 9 points ^*The maximal value of measured value and the difference of minimum value estimate.Wherein, L ^*Difference more little, the coating spot few more.In the present invention, as long as L ^*Difference less than 2.0, just can be in practicality, but more preferably below 1.5, be preferably below 1.0 especially.In addition, in the highest falling rate of drying operation of baking temperature,, can further improve the humidity resistance of the near infrared absorbing coloring matter in the resin by reducing the residual solvent amount.

Preferably carry out refrigerating work procedure subsequently.Refrigerating work procedure is the final operation of drying process.In this operation, cool off with the wind of temperature below the Tg of resin (resin in the near infrared ray absorption layer), preferably under the smooth state of film, make below the Tg of temperature at resin of transparent base.The temperature of preferred wind is below Tg-5 ℃, more preferably below Tg-10 ℃.Under the situation of from drying oven, coming out under the state of film at high temperature, when the near infrared ray absorption layer surface the not good situation of sliding can occur when being contacted with roller with the film walking before being batched, occur damage easily at this laminar surface, in addition, on film, occur sometimes curling etc.In refrigerating work procedure, preferably making wind speed for example is 2～50m/ second, and in addition, preferably making cool time for example is 5～120 seconds.

In drying process, preferably control so that drying regime is stable in the film total length.If drying regime changes, for example, the position that the residual solvent amount near infrared ray absorption layer is many, deterioration takes place in pigment easily, so on the length direction of film, tone changes sometimes.Particularly at the coating initial stage, the evaporating solvent amount in the drying oven increases gradually, and its amount slowly settles out afterwards, therefore from begin to be coated to apply about 500m before, drying efficiency changes easily.In order to make the drying efficiency stabilization, air quantity (wind speed) that can be by regulating baking temperature, wind (hot blast), drying time etc. are controlled.

Baking temperature with respect to design temperature for example preferably be controlled in ± 2 ℃ scope in, carrying out the temperature controlled while with high precision, after the actual temperature in the drying oven reaches design temperature, for example, preferably place more than 30 minutes, after making the baking temperature stabilization, carry out thin film fabrication.In order to carry out the control of temperature or air quantity with high precision, can high well heater or the fan blower of service precision, about drying time, can the high drive unit of service precision.

Go up the near-infrared absorbing film that winding obtains by above-mentioned manufacture method at volume core (cores of paper web or metal tube etc.), the volume that is rolled into drum is exactly a near-infrared absorbing film volume of the present invention.Certainly, under the situation that possesses near-infrared absorbing film, can utilize the method for the formation that is fit to each layer suitably stacked on above-mentioned film with near infrared ray absorption layer layer in addition.

[the stacked formation of near-infrared absorbing film]

The stacked configuration example of near-infrared absorbing film of the present invention is shown in Fig. 2～4.Wherein, in Fig. 2～4,10 expression base films, 20 expressions the 1st adhesiveness modified layer, 30 expression near infrared ray absorption layer.As Fig. 2 or shown in Figure 3, near infrared ray absorption layer 30 can be at least one deck, there is no need to be provided with on the film two sides.For example, as shown in Figure 3, the 1st adhesiveness modified layer 20 is set on the two sides of base film 10, on the surface of the 1st adhesiveness modified layer 20 of one deck, form near infrared ray absorption layer 30, on the 1st adhesiveness modified layer 20 of another layer, can functional beyond the near infrared ray absorption layer is set give layer (for example, UV-absorbing layer, electromagnetic wave blocking layer, an anti-reflection layer etc.) (these functional give layer not shown) by getting involved the bonding coat (not shown) that is provided with in addition as required.In addition, the 1st adhesiveness modified layer 20 that intermediate-index layer or the 2nd adhesiveness modified layer replace the downside of base film 10 can be set, anti-reflection layer be set at its downside.

About other functional layers of giving that can on near-infrared absorbing film of the present invention, further form, enumerate typical example and describe.For example, be applied at film of the present invention in order to remove the unwanted electromagnetic wave of emitting, conductive layer can be set under the situations such as display applications as the electromagnetic wave blocking layer from display etc.As conductive layer, can enumerate wire netting or transparent conductive film.

Adopting under the situation of wire netting, preferably using numerical aperture is wire netting more than 50%.Under the less situation of the numerical aperture of wire netting, though electromagnetic wave blocking is good, the luminous ray transmitance is insufficient sometimes.As the object lesson of wire netting, can enumerate electric conductivity high metal forming is carried out etch processes and formed netted wire netting, used the wire netting of the fabric form that adopts plating method etc. to make the fiber that metal forms attached to the surface of metal fibre or macromolecular fibre etc.With regard to the metal that can be used for wire netting, as long as electric conductivity is high and have good stability, just be not particularly limited, can use any metal, but from the viewpoint of processability or cost, preferably copper, nickel, tungsten etc.

Under the situation that adopts transparent conductive film, so long as can guarantee to guarantee the film of the transparency and the electric conductivity of sufficient luminous ray transmitance, just be not particularly limited the preferred film that forms by tin oxide, indium oxide, zinc paste, titanium dioxide, bismuth oxide, ITO (In-Sn composite oxides), FTO metal oxides such as (tin oxide of the fluorine that mixed) that uses.

The thickness of transparent conductive film is 100

More than, 1000

Below, more preferably 500

Below.When the thickness of transparent conductive film is lower than above-mentioned scope, can't fully guarantee to use the effect of bringing based on the layer of this film sometimes.On the other hand, when the thickness of transparent conductive film surpassed above-mentioned scope, because this film is painted, the tone of film had the trend that changes.

Also have,, preferably become the stepped construction more than 3 layers of metal oxide/metal/metal oxide and so on when the conductance that improves above-mentioned transparent conductive film and when being applied to film of the present invention.By in inscape, containing metal, can when keeping high visible line transmitance, guarantee outstanding electric conductivity.From improving the viewpoint of electric conductivity, the compound that stacked metal is suitably for gold, silver and contains them.The gross thickness of the transparent conductive film of this moment is preferably in the preferred thickness range of above-mentioned transparent conductive film.In addition, the thickness of stacked metal is 50

More than, below 200, more preferably 100

Below.When the thickness of metal is lower than above-mentioned scope, can't fully guarantee stacked its effect, on the other hand, surpassing under the situation of above-mentioned scope, the luminous ray transmitance of film reduces.

When making transparent conductive film become stepped construction as described above, for example becoming under 5 layers of situations such as structure of metal oxide/metal/metal oxide/metal/metal oxide and so on, the thickness of metal oxide that preferably makes the center is greater than the thickness of other metal oxides.By forming such lit-par-lit structure, can improve the luminous ray transmitance of transparent conductive film integral body.

[purposes of near-infrared absorbing film]

Near-infrared absorbing film of the present invention for example when being arranged on the front of plasma display as the near-infrared absorbing light filter, can absorb the otiose near infrared ray from this display radiation.Thus, the telepilot of using at the operation plasma display is under the situation of near infrared ray mode, can prevent the faulty operation by the caused telepilot of otiose near infrared ray that radiates from this display.

[near-infrared absorbing light filter]

More than Shuo Ming near-infrared absorbing film of the present invention can be used as the near-infrared absorbing light filter.In this near-infrared absorbing light filter of the present invention, above-mentioned conductive layer is set preferably.This conductive layer is configured between the near infrared ray absorption layer and plasma display of film.For example, be preferred embodiment by getting involved bonding coat stacked in the near infrared ray absorption layer side.Can on light filter the most surperficial, be provided for light filter is attached to the bonding coat of plasma display.

Embodiment

Below, describe the present invention in detail according to experimental example.But, following experimental example does not limit the present invention, and the change of implementing in the scope that does not break away from the front/rear purport of stating is also included within the technical scope of the present invention.The acid number of the resin that wherein obtains in this experimental example and the evaluation method of film are as follows.The molecular weight of each resin of measuring in this experimental example in addition, all is the value (polystyrene conversion value) by gel permeation chromatography.

[coating fluid viscosity]

At 20 ℃ of modulated coating fluids, use the Brookfield viscometer (BL) of Tokyo gauge system, measure with 60rpm rotor speed.

[total light transmittance, turbidity]

(Japanese electric look industry system NDH2000), is measured total light transmittance and turbidity to use nephelometer.

[light penetration]

Use spectrophotometer (Hitachi's system, U-3500 type), in the scope of wavelength 200～1100nm,, the transmitance of room air is measured as reference point (blank) from the light of near infrared ray absorption layer side irradiation specific wavelength.Light penetration near infrared range is estimated with the mean value of the light penetration at wavelength 900～1100nm place, transmitance in neon light (neon orange light) zone is estimated with the mean value of the light penetration at wavelength 570～600nm place, light penetration in the visible region is estimated with the mean value of the light penetration at wavelength 450～700nm place, and ultraviolet ray transmissivity is estimated with the light penetration at wavelength 380nm place.

[tone]

When measuring tone, (Japanese electric look industry system, ZE-2000), as the D65 light source, making angle of visibility is 10 degree, carries out near infrared ray absorption layer side irradiates light, obtains L value, a value, the b value of Lab display system with standard light to use colour difference meter.

(ageing stability)

In the atmosphere of 60 ℃ of temperature, humidity 95%, placed the near-infrared absorbing light filter 500 hours, measure above-mentioned light penetration, tone then.

At first, by following formula (8), obtain the mean value of transmitance of near infrared range and visible region transmitance mean value through the time variable quantity before and after handling, attached according to following criterion with grade.

◎: the variation of transmitance is less than 5%

Zero: being changed to more than 5% and of transmitance less than 10%

△: being changed to more than 10% and of transmitance less than 20%

*: being changed to more than 20% of transmitance

Variable quantity (%)=(| the transmitance after the transmitance-processing before handling | the transmitance the before/processing) * 100 ... (8)

Then, obtain with the tone of following formula (9) definition through the time variable quantity before and after handling, attached according to following criterion with grade.

◎: the variation of transmitance is less than 1

Zero: being changed to more than 1 and of transmitance less than 2

△: being changed to more than 2 and of transmitance less than 4

*: being changed to more than 4 of transmitance

Variable quantity (%)=[(a value before handling-processing back a value) ²+ (b value one is handled back b value before handling) ²] ^1/2(9)

[appearance of film]

(1) tiny flaw

At the light filter of placing on the white film after forming near infrared ray absorption layer [light filter before bonding coat is set], following evaluation is carried out in visualization under the fluorescent light of 3 wavelength.

Wherein, with regard to tiny flaw, measure every 100m ²The number of the defective of the above size of 300 μ m of area, attached according to following criterion with grade.

◎: tiny flaw is less than 1

Zero: tiny flaw is more than 1 and less than 5

△: tiny flaw is more than 5 and less than 10

*: tiny flaw is more than 10

(2) coating is bad

About whether having coatings such as coating spot, striped bad, near-infrared absorbing film is placed on the white film, visualization near infrared ray absorption layer face under the fluorescent light of 3 wavelength, attached according to following criterion with grade.

◎:, do not see that also coating is bad even in mobile near-infrared absorbing light filter, observe

Zero: when when at mobile near-infrared absorbing light filter the time, observing, have some coatings bad

△: when when at mobile near-infrared absorbing light filter the time, observing, have coating bad as can be known

*: even make near-infrared absorbing film be in static state, also there is coating bad as can be known

[coiling characteristic]

Under winding tension: 200/m, speed: 20m/ minute condition, the near-infrared absorbing filter roll that will have anti-reflection layer, base film and near infrared ray absorption layer is on 6 inches paper webs, according to following criterion, attached with grade to the coiling degree of misalignment after reeling.

◎: the dislocation of reeling is less than 1mm

Zero: the dislocation of reeling is for more than the 1mm and less than 2mm

△: the dislocation of reeling is for more than the 2mm and less than 4mm

*: the dislocation of reeling perhaps can't be batched for more than the 4mm

[photostability]

For the near-infrared absorbing film that in above-mentioned, obtains, carried out sunproof accelerated test.In the black panel temperature is that 63 ℃, humidity are 50%, illumination is 50W/m ², irradiation time is under 24 hours the condition, (ス ガ testing machine corporate system XL-75) has been carried out exposure experiment, has measured the transmitance at very big absorbing wavelength place of the near infrared range of the sample before and after this test to utilize ultraviolet self-discoloration meter.Transmitance before the test is made as T, the transmitance after the test is made as T ₁, obtain near-infrared absorbing ability survival rate R (%) from following formula (10).During this is estimated, adopted by get involved bonding coat be attached to test sample on the SUS plate that thickness is 2mm after from the method for anti-reflection layer side irradiation ultraviolet radiation.

R(％)＝(T/T ₁)×100 ……(10)

[reflectivity of anti-reflection layer]

Using spectrophotometer (Hitachi's system, U-3500 type), is benchmark with JIS-R3106, has measured 5 ° of normal reflections of anti-reflection layer side, obtains the minimum reflectance under wavelength 380～700nm.Wherein, about the sample of stacked anti-reflection layer not, measured the above-mentioned reflectivity on the surface of base film.

[skin hardness]

About the surface of anti-reflection layer, estimate with the pencil scratch hardness with anti-reflective function.In temperature is that 25 ℃, relative humidity are under 60% the condition, sample is carried out measure after 2 hours the humidity regulation.With regard to the pencil scratch hardness, use the test pencil as benchmark with JIS-S6006, be that benchmark is implemented with JIS-K5400.Pencil hardness as evaluation result is not have the pencil hardness of damage under the load of 9.8N fully.About the sample of stacked anti-reflection layer not, the surface of base film is measured.

[anti-reflection layer and near infrared ray absorption layer are for the adhesiveness of base film]

Employing is obtained adhesiveness with the test method that is recited as the basis among the 8.5.1 of JIS-K5400.Promptly, use the tool guide of clearance gap as 2mm, do out respectively that 100 from two surfaces to base film rise bucket-shaped cut wound, with viscose paper adhesive strip (ニ チ バ Application system, No. 405,24mm is wide) be attached on the bucket-shaped cut wound face of liter, carry out wiping with acrylic panel (Sumitomo Chemical system, ス ミ ペ Star Network ス) it is adhered to fully, to avoid residual bubble or to adhere to bad part, situation when visualization is vertically peeled off is then obtained adhesiveness (%) by following formula (11).Wherein, rise in the bucket at 1 that a part is stripped from, what be considered as being stripped from rises bucket.

Adhesiveness (%)=(quantity that rises bucket of the quantity/evaluation that rises bucket that 1-has been stripped from) * 100

……(11)

Experiment 1

Experiment 1-1

1. the manufacturing of base film

With limiting viscosity is that the pet resin of 0.62dl/g is put in the double screw extrusion machine, melt extrudes from the T die head under 290 ℃, applies static on cooling rotating metallic roller, it is adhered to solidify, and thin slice is not stretched.

Then, with the roller drawing machine this thin slice that do not stretch is heated to 90 ℃, is longitudinally stretched to 3.5 times, afterwards, the middle layer that has the composition shown in the following table 1 in the two sided coatings of this vertical oriented film is with coating fluid A and to make dried coating weight be 0.5g/m ², make wind speed be 10m/ second, 120 ℃ hot blast by 20 seconds, form the middle layer.And then, be heated to 140 ℃ with stenter after 3.7 times of cross directional stretchs, heat-treat and obtain film on width (laterally) direction, making it loose 5% under 235 ℃ then.With regard to the two-way stretch pet film with middle layer that obtains, thickness is 100 μ m, and total light transmittance is 90.2%, and turbidity is 0.5%.

Table 1

2. near infrared ray absorption layer is stacked

Use the oblique line photogravure of diameter, adopt reverse manner on above-mentioned middle layer, apply the coating fluid N1-1 of the near infrared ray absorption layer formation usefulness shown in the following table 2, and to make dried coating weight be 8.5g/m as 60cm ², and the hot blast that makes 40 ℃ and 5m/ second is by 20 seconds, the hot blast that makes 150 ℃ and 20m/ second is by 20 seconds, and then the hot blast that makes 90 ℃ and 20m/ second made its drying by 10 seconds, makes near-infrared absorbing film.The near-infrared absorbing film that obtains, as shown in table 4, strong in the absorption of near infrared region, the transmitance height in the visible region, and then ageing stability, appearance of film are also good.

(near infrared ray absorption layer forms the coating fluid N1-1 of usefulness)

Mix each composition with the composition shown in the following table 2, at heating (40 ℃) down dissolving pigment and resin, using the nominal filtering accuracy is that the filtrator of 1 μ m removes not that dissolved matter makes coating fluid.The solid component concentration of coating fluid N1-1 is 17 quality %, and viscosity (viscosity that adopts above-mentioned determination method to obtain) is 40cps.

Table 2

Experiment 1-2

Except the surfactant in the coating fluid that near infrared ray absorption layer is formed usefulness become HLB be 11 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2105) outside, 1-1 has obtained near-infrared absorbing film in the same manner with experiment.Because become the high surfactant of water wettability, so the deterioration slightly of the ageing stability under the high temperature/high humidity.In addition, by the effect deficiency that localization is given sliding to the surface, some coiling dislocation have appearred.All be in realistic scale.

Experiment 1-3

Except the surfactant in the coating fluid that near infrared ray absorption layer is formed usefulness become HLB be 3 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2136) outside, 1-1 has obtained near-infrared absorbing film in the same manner with experiment.Because become the high surfactant of hydrophobicity, so a small amount of tiny flaw has appearred in levelability deterioration a little.

Experiment 1-4

Containing with respect to resin in the coating fluid that forms usefulness near infrared ray absorption layer is the surfactant of 0.02 quality %, and 1-1 has obtained near-infrared absorbing film in the same manner with experiment.Because reduced the content of surfactant, so a small amount of tiny flaw has appearred in levelability deterioration a little.

Experiment 1-5

Containing with respect to resin in the coating fluid that forms usefulness near infrared ray absorption layer is the surfactant of 1.5 quality %, and 1-1 has obtained near-infrared absorbing film in the same manner with experiment.Because increased the content of surfactant, so that ageing stability has slightly is bad.

Experiment 1-6

The coating fluid drying condition afterwards that the coating near infrared ray absorption layer is formed usefulness is made as, hot blast with 100 ℃ and 5m/ second ventilated 20 seconds, hot blast with 150 ℃ and 20m/ second ventilated 20 seconds, and then ventilated 10 seconds with the hot blast of 90 ℃ and 20m/ second, in addition, obtained near-infrared absorbing film in the same manner with experiment 1-1.Because make initial stage drying condition strictness, so tiny flaw more or less increases.

Experiment 1-7

The coating fluid drying condition afterwards that the coating near infrared ray absorption layer is formed usefulness is made as, hot blast with 40 ℃ and 5m/ second ventilated 20 seconds, hot blast with 130 ℃ and 20m/ second ventilated 20 seconds, and then ventilated 10 seconds with the hot blast of 90 ℃ and 20m/ second, in addition, obtained near-infrared absorbing film in the same manner with experiment 1-1.Because the film actual temperature in the drying oven descends to some extent, the residual solvent amount increases, and ageing stability exists a little bad.

Experiment 1-8

Except applying with wire bar, 1-1 has obtained near-infrared absorbing film in the same manner with experiment.The thin longitudinal stripe that caused by wire bar has appearred.

Experiment 1-9

Except using diameter applies with reverse manner as the oblique line photogravure of 300mm, 1-1 has made near-infrared absorbing film in the same manner with experiment.The striped that has occurred the ridge shape in a longitudinal direction.

Experiment 1-10

Except adopting following mode to be provided with the near infrared ray absorption layer, 1-1 has made near-infrared absorbing film in the same manner with experiment.

(near infrared ray absorption layer stacked)

Use the oblique line photogravure of diameter, adopt reverse manner on above-mentioned middle layer, apply the coating fluid N1-2 of the near infrared ray absorption layer formation usefulness shown in the following table 3, and to make dried coating weight be 9.3g/m as 60cm ², the hot blast that makes 40 ℃ and 5m/ second is by 20 seconds, and the hot blast that makes 150 ℃ and 20m/ second is by 20 seconds, and then the hot blast that makes 90 ℃ and 20m/ second made its drying by 10 seconds, makes near-infrared absorbing film.

(near infrared ray absorption layer forms the coating fluid N1-2 of usefulness)

Mix each composition with the composition shown in the following table 3, at heating (40 ℃) down dissolving pigment and resin, using the nominal filtering accuracy is that the filtrator of 1 μ m removes not that dissolved matter makes coating fluid.The solid component concentration of coating fluid N1-2 is 21 quality %, and viscosity is 30cps.

Table 3

Experiment 1-11

Except not adding the surfactant in the coating fluid of near infrared ray absorption layer formation usefulness, 1-1 has obtained near-infrared absorbing film in the same manner with experiment.Because do not add surfactant, tiny flaw occurs in a large number.In addition, sliding is bad, is difficult to coil into drum.

Experiment 1-12

Surfactant in the coating fluid that makes near infrared ray absorption layer formation usefulness reaches the 3 quality % with respect to the content of resin, and 1-1 has obtained near-infrared absorbing film in the same manner with experiment.Because the content of surfactant is more, ageing stability is bad.

Experiment 1-13

Except the surfactant in the coating fluid that near infrared ray absorption layer is formed usefulness become HLB be 1 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2110) outside, 1-1 has obtained near-infrared absorbing film in the same manner with experiment.Because used the surfactant beyond the constitutive requirements of the present invention, so a large amount of tiny flaws have appearred in the levelability deficiency.In addition, because the sliding on surface is strong excessively, so the dislocation of reeling occurred.

Experiment 1-14

Except the surfactant in the coating fluid that near infrared ray absorption layer is formed usefulness become HLB be 14 silicone-based surfactant (Tokyo silicon system, TSF4440) outside, 1-1 has obtained near-infrared absorbing film in the same manner with experiment.Because used the surfactant beyond the constitutive requirements of the present invention, so a large amount of tiny flaws have appearred in the levelability deficiency.In addition, because the sliding on surface is not enough a little, the dislocation of reeling has appearred.

Table 4

Experiment 2

Experiment 2-1

Use has the base material in the middle layer identical with above-mentioned experiment 1-1, and uses the near infrared ray absorption layer coating fluid N2-1 with the composition shown in the following table 5, in addition, has made near-infrared absorbing film in the same manner with above-mentioned experiment 1-1.The near-infrared absorbing film that obtains is as shown in table 7, and is strong in the absorption of near infrared range, the transmitance height in the visible region, and then ageing stability, appearance of film are also good.

(near infrared ray absorption layer forms the coating fluid N2-1 of usefulness)

Mix each composition with the composition shown in the following table 5, at heating (40 ℃) down dissolving pigment and resin, using the nominal filtering accuracy is that the filtrator of 1 μ m removes not that dissolved matter makes coating fluid.The solid component concentration of coating fluid N1-1 is 17 quality %, and viscosity (viscosity that adopts above-mentioned determination method to obtain) is 40cps.

Table 5

Experiment 2-2

Except the surfactant in the coating fluid that near infrared ray absorption layer is formed usefulness become HLB be 11 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2105) outside, 2-1 has obtained near-infrared absorbing film in the same manner with experiment.The evaluation result of the near-infrared absorbing film that obtains is as shown in table 7.Because become the high surfactant of water wettability, so the deterioration a little of the ageing stability under the high temperature/high humidity.In addition, by the effect deficiency that localization is given sliding to the surface, some coiling dislocation have appearred.But, all be in realistic scale.

Experiment 2-3

Except the surfactant in the coating fluid that near infrared ray absorption layer is formed usefulness become HLB be 3 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2136) outside, 2-1 has obtained near-infrared absorbing film in the same manner with experiment.The evaluation result of the near-infrared absorbing film that obtains is as shown in table 7.Because become the high surfactant of hydrophobicity, so a small amount of tiny flaw has appearred in levelability deterioration a little.

Experiment 2-4

Containing with respect to resin in the coating fluid that forms usefulness near infrared ray absorption layer is the surfactant of 0.02 quality %, and 2-1 has obtained near-infrared absorbing film in the same manner with experiment.The evaluation result of the near-infrared absorbing film that obtains is as shown in table 7.Because reduced the content of surfactant, so a small amount of tiny flaw has appearred in levelability deterioration a little.

Experiment 2-5

Containing with respect to resin in the coating fluid that forms usefulness near infrared ray absorption layer is the surfactant of 1.5 quality %, and 2-1 has obtained near-infrared absorbing film in the same manner with experiment.The evaluation result of the near-infrared absorbing film that obtains is as shown in table 7.Because increased the content of surfactant, so ageing stability is bad slightly.

Experiment 2-6

Surfactant in the coating fluid that near infrared ray absorption layer is formed usefulness changes into the 2.5 quality % with respect to the concentration of solid state component, and 2-1 has obtained near-infrared absorbing film in the same manner with experiment.The evaluation result of the near-infrared absorbing film that obtains is as shown in table 7.Because the content of the surfactant in the near infrared ray absorption layer is more, so ageing stability is not good.

Experiment 2-7

Except adopting following mode to be provided with the near infrared ray absorption layer, 2-1 has made near-infrared absorbing film in the same manner with experiment.

(near infrared ray absorption layer stacked)

Use the oblique line photogravure of diameter, adopt reverse manner on above-mentioned middle layer, to apply following coating fluid N2-2, and to make dried coating weight be 9.3g/m as 60cm ², the hot blast that makes 40 ℃ and 5m/ second is by 20 seconds, and the hot blast that makes 150 ℃ and 20m/ second is by 20 seconds, and then the hot blast that makes 90 ℃ and 20m/ second made its drying by 10 seconds, makes near-infrared absorbing film.The evaluation result of the near-infrared absorbing film that obtains is as shown in table 7.

(near infrared ray absorption layer forms the coating fluid N2-2 of usefulness)

Mix each composition with the composition shown in the following table 6, at heating (40 ℃) down dissolving pigment and resin, using the nominal filtering accuracy is that the filtrator of 1 μ m removes not that dissolved matter makes coating fluid.The solid component concentration of coating fluid is 21 quality %, and viscosity is 30cps.

Table 6

Table 7

Experiment 3

Experiment 3-1

Experiment 3-1-1

1. the making of base film

(1) contains the modulation of the masterbatch pellet of ultraviolet light absorber

Mixing dry cyclic imide acid esters is ultraviolet light absorber (サ イ テ Star Network system, CYASORB UV3638; 2,2 '-(1, the 4-phenylene) two (4H-3,1-benzoxazines-4-ketone)) 10 mass parts and do not contain polyethylene terephthalate (PET) resin of particle (Japan's weaving system, ME553) 90 mass parts use mixing extruder to make masterbatch pellet.The extrusion temperature of this moment is 285 ℃, and finding time is 7 minutes.

(2) the 2nd adhesiveness modified layer (easily adhesive linkage) form the modulation with coating fluid

Dimethyl terephthalate (DMT) 95 mass parts, dimethyl isophthalate 95 mass parts, ethylene glycol 35 mass parts, neopentyl glycol 145 mass parts, zinc acetate 0.1 mass parts and antimony trioxide 0.1 mass parts are put in the reaction vessel, carried out ester exchange reaction with 3 hours time down at 180 ℃.Then, add 5-sulfoisophthalic acid sodium 6.0 mass parts, carry out esterification with 1 hour time down, carry out polycondensation reaction then, obtained vibrin at 240 ℃.

Mix the gained vibrin 30 quality % aqueous dispersions, 6.7 mass parts, contain 20 quality % aqueous solution (the first industrial pharmacy system, ELASTRON H-3), 40 mass parts, ELASTRON of self-cross linking type urethane resin of isocyanate group of useful sodium bisulfite end-blocking with catalyzer (Cat64) 0.5 mass parts, water 47.8 mass parts and isopropyl alcohol 5 mass parts.And then, in this coating fluid, add anionic surfactant 1 quality %, spherical colloidal silica particles (daily output chemical industry system, ス ノ one テ Star Network ス OL) 5 quality %, as coating fluid.

(3) the system film of base film

Under 135 ℃, be that (Japan's weaving system, ME553) masterbatch pellet 10 mass parts of 90 mass parts, making in above-mentioned (1) were carried out drying under reduced pressure (1Torr) 6 hours, offered extruder then for 0.62dl/g and the PET particle that does not contain particle to limiting viscosity.Making from extruder fusing department, kneading part, polymer pipe, gear-type pump, to the resin temperature of filtrator is 280 ℃, is 275 ℃ in polymer pipe subsequently, is extruded into laminar from tube head.Wherein, these PET use the filter materials (nominal filtering accuracy: block the particle 95% more than the 10 μ m) of stainless steel sintered body to filter respectively in melt stage.In addition, making the resin temperature in the flat-die is 275 ℃.

Use static to apply casting, make to be melted to be extruded into laminar resin to stick to surface temperature be that cooling curing makes non-stretched film simultaneously on 30 ℃ the casting roller (roller diameter: 400mm Φ, Ra:0.1 μ m is following).The spray volume of this moment is 48kg/hr, the wide 300mm of the non-stretched film that obtains, thick 1400 μ m.

Then, use the roller group and the infrared heater that have heated, above-mentioned non-stretched film is heated to 100 ℃, goes up 3.5 times (the longitudinal stretching film) that stretch by the roller group that has difference at length direction (direction of travel) subsequently, obtained monodirectional tension film.Wherein, about all rollers that use when making film, the surfaceness of pair roller is controlled and made its Ra is below the 0.1 μ m, is provided with the roller clearer on the roller of the preheating inlet that is positioned at stretching process and chill roll.Roller diameter in the longitudinal stretching operation is 150mm, has adopted adhering apparatus such as utilizing suction roll, static adhesion, part clamp to make film stick to method on the roller.

Adopt the reverse rollers method, on the two sides of above-mentioned one-way orientation film, being coated with filtered particles size (initial stage filtration efficiency 95%) is the felt type polypropylene filter made of 25 μ m has carried out secondary filter with material the 2nd adhesiveness modified layer formation coating fluid.Subsequently, then, grip the end of film and guide to the hot blast district that is heated to 130 ℃ with anchor clamps, dry back stretches 4.0 times on the thin-film width direction, 230 ℃ of 5 seconds of following thermal treatment, in this heat treatment step, on Width, carry out 3% tension and relaxation processing, obtained on two faces, being laminated with the base film of the 2nd adhesiveness modified layer.The thickness of the base film that obtains is 100 μ m, and with regard to the 2nd adhesiveness modified layer, its dried coating weight is 0.01g/m on a face ²

2. the formation of anti-reflection layer

Adopt reverse coating process, on the 2nd adhesiveness modified layer surface of above-mentioned base film, be coated with ultraviolet hardening coating (big day the system of refining, セ イ カ PVC one system EXF-01B) firmly, and to make dried thickness be 5 μ m.Then, after dry solvent, by high voltage mercury lamp radiation 800mJ/cm ²Ultraviolet ray, make the resin solidification in the coating, form hard conating.

Then, the coating fluid that modulation is made of partial hydrolysis condensation product 5 mass parts, methyl alcohol 30 mass parts, ethanol 30 mass parts, isopropyl alcohol 35 mass parts of γ-An Bingjisanjiayangjiguiwan, it is coated on the hard coating surface, and to make dried thickness be 0.02 μ m, under 140 ℃, after dry 20 seconds, form high refractive index layer.

Then, in tetraethoxysilane 24 mass parts, add ethanol 50 mass parts, water 20 mass parts, hydrochloric acid 4 mass parts, make the tetraethoxysilane hydrolysis, the modulation coating fluid.This coating fluid is coated on the high index of refraction laminar surface and makes dried thickness is 0.09 μ m, forms low-index layer 140 ℃ of following dryings 1 minute.

And then, will be with the perfluoro hexane by C ₃F ₇-(OC ₃F ₆) ₃₄-O-(CF ₂) ₂-C ₂H ₄-O-CH ₂Si (OCH ₃) ₃The silane coupling agent that contains the perfluoro polyether base that constitutes is diluted to 0.5 quality % and makes coating fluid, and aforesaid coating fluid is coated on the above-mentioned low-refraction laminar surface, and drying is 1 minute under 120 ℃, and forming thickness is the stain-proofing layer of 8nm.

Thus, on the 2nd adhesiveness modified layer surface of base film, formed anti-reflection layer by the sequential cascade of hard conating/high refractive index layer/low-index layer/stain-proofing layer.

3. the formation of near infrared ray absorption layer

On in the base film that forms anti-reflection layer and the 2nd adhesiveness modified layer surface anti-reflection layer opposition side, be coated on the near infrared ray absorption layer used among the above-mentioned experiment 2-1 and form the coating fluid N2-1 (table 5) of usefulness, and to make dried coating weight be 8.5g/m ²Coating is to be that the oblique line gravure roll reverse rotation of 60cm is carried out by making diameter.Subsequently, the hot blast that makes 40 ℃ and 5m/ second is by 20 seconds (the 1st drying process), and the hot blast that makes 150 ℃ and 20m/ second is by 20 seconds (the 2nd drying process), and then the hot blast that makes 90 ℃ and 20m/ second was by 10 seconds (refrigerating work procedure), make its drying, make the near-infrared absorbing light filter.

4. the formation of bonding coat

Adopt the spot printing method, on the surface of the near infrared ray absorption layer of above-mentioned near-infrared absorbing light filter, the stacked clear binder that constitutes by n-butyl acrylate (78.4 quality %), 2-EHA (19.6 quality %) and acrylic acid (2 quality %) as acrylate copolymer, and to make dried thickness be 0.025mm.And then the PET system isolated film that the stacked thickness of silicone-treated having been implemented on its surface is 0.038mm has obtained having the near-infrared absorbing light filter of bonding coat and the complex of isolated film.

With regard to above-mentioned near-infrared absorbing light filter, the result who carries out above-mentioned each evaluation is as shown in table 8.Evaluation beyond the light fastness test is that the near-infrared absorbing light filter that bonding coat is not set is carried out, and light fastness test is that the near-infrared absorbing light filter that bonding coat is set is carried out.

As shown in Table 8, the near-infrared absorbing light filter that obtains is bigger in the absorption near infrared region and neon light zone, and the transmitance of visible region is also bigger.In addition, the coiling characteristic of the appearance of film of near infrared ray absorption layer or light filter is also good.And then owing to use ultraviolet light absorber, the absorption of ultraviolet range is very big, and ageing stability (light transmission rate, tone) and photostability are outstanding.

Also have, estimate in the hurdle in the adhesiveness of table 8, (A) layer refers to anti-reflection layer, and (B) layer refers to base film, and (C) layer refers near infrared ray absorption layer.

And then also the anti-reflection layer to the near-infrared absorbing light filter has carried out the soil resistance evaluation.Soil resistance is to estimate according to the wiping of oil pen's wiping and fingerprint.When estimating oil pen's wiping, use the oil pen in the line of anti-reflection layer surface and with nonwoven fabrics (Asahi Chemical Industry's system of cellulose system, ベ Application コ Star ト Application M-3) this line of wiping, in addition, when estimating the wiping of fingerprint with nonwoven fabrics (Asahi Chemical Industry's system of cellulose system, ベ Application コ Star ト Application M-3) wiping is attached to the fingerprint on anti-reflection layer surface, its wiping of visual judgement.It found that and can both wipe out fully.

In addition, the gross thickness of the near-infrared absorbing light filter that obtains in this experiment 3-1-1 (anti-reflection layer/base film/near infrared ray absorption layer/bonding coat) is 0.14mm, extremely thin, comprehensively has aforesaid outstanding characteristic on this basis, so after peeling off the isolated film of above-mentioned complex, utilize the cohesive of bonding coat, for example can easily be attached on the adherends such as plasma display.As mentioned above, with regard to this near-infrared absorbing light filter, more known light filter was thin than in the past for its thickness, so its adhesion operation is outstanding.

Experiment 3-1-2

Ultraviolet light absorber is become macromolecular ultraviolet light absorber (Mitsubishi Chemical's system, Novapex U-110), and to make its use level be 20 mass parts, in addition, made near-infrared absorbing light filter in the same manner with experiment 3-1-1 with anti-reflection layer, base film and near infrared ray absorption layer.And then, also using this near-infrared absorbing light filter, 3-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 8.As shown in table 8, have and the equal characteristic of near-infrared absorbing light filter that in experiment 3-1-1, obtains.In addition, also carried out the soil resistance evaluation in the same manner with experiment 3-1-1, wiping of oil pen's wiping, fingerprint is all good as a result for it.

Experiment 3-1-3

Except the surfactant that will use near infrared ray absorption layer forms with coating fluid becomes HLB is 11 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2105) outside, 3-1-1 has made the near-infrared absorbing light filter with anti-reflection layer, base film and near infrared ray absorption layer in the same manner with experiment.And then, also using this near-infrared absorbing light filter, 3-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 8.Because used the surfactant of HLB than the near-infrared absorbing light filter big (water wettability height) that in experiment 3-1-1, obtains, so the ageing stability under high temperature/high humidity is deterioration a little, the sliding near infrared ray absorption layer surface is deterioration slightly also, has occurred some coilings dislocation thus.In addition, also carried out the soil resistance evaluation in the same manner with experiment 3-1-1, wiping of oil pen's wiping, fingerprint is all good as a result for it.

Experiment 3-1-4

Except the surfactant that will use near infrared ray absorption layer forms with coating fluid becomes HLB is 3 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2136) outside, 3-1-1 has made the near-infrared absorbing light filter with anti-reflection layer, base film and near infrared ray absorption layer in the same manner with experiment.And then, also using this near-infrared absorbing light filter, 3-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 8.Because used the surfactant of HLB than the near-infrared absorbing light filter little (hydrophobicity height) that obtains in experiment 3-1-1, so the levelability when forming near infrared ray absorption layer is poor slightly, tiny flaw also increases a little.In addition, also carried out the soil resistance evaluation in the same manner with experiment 3-1-1, wiping of oil pen's wiping, fingerprint is all good as a result for it.

Experiment 3-1-5

In experiment 3-1-1, change according to following (1)～(3), in addition, 3-1-1 has obtained the near-infrared absorbing light filter of this experiment 3-1-5 in the same manner with experiment.The characteristic of the near-infrared absorbing light filter that obtains in this experiment 3-1-5 is as shown in table 8.

(1) cooperation of the ultraviolet light absorber of cancellation in base film.

(2) the 2nd adhesiveness modified layer stacked to base film all cancelled on the two sides.

(3) cancellation forms the cooperation of using the surfactant in the coating fluid near infrared ray absorption layer.

With regard to regard to the near-infrared absorbing light filter that obtains among this experiment 3-1-5, its ultraviolet permeability height, photostability is poor so the deterioration that is caused by photoconduction of near infrared absorbing coloring matter increases.In addition, because do not form the 2nd adhesiveness modified layer, so the poor adhesion of anti-reflection layer or the relative base film of near infrared ray absorption layer.And then, forming with the cooperation in the coating fluid near infrared ray absorption layer because cancelled surfactant, the tone of the disconnected usefulness of near infrared absorbing coloring matter or neon photoresistance is regulated with the dispersed deterioration of pigment in resin, so the appearance of film of near infrared ray absorption layer is poor.

Experiment 3-1-6

In the method for experiment 3-1-1, change according to following (4)～(6), in addition, 3-1-1 has obtained the near-infrared absorbing light filter of this experiment 3-1-6 in the same manner with experiment.

(4) cancellation anti-reflection layer stacked to base film.

(5) the 2nd adhesiveness modified layer stacked to base film all cancelled on the two sides.

(6) the cancellation surfactant forms the cooperation of using coating fluid near infrared ray absorption layer.

The characteristic of the near-infrared absorbing light filter that obtains in this experiment 3-1-6 is as shown in table 8.With regard to regard to the near-infrared absorbing light filter that obtains among this experiment 3-1-6, because not compound anti-reflection layer, surface reflectivity and skin hardness are that the character of surface of base film is estimated.

With regard to regard to the near-infrared absorbing light filter that obtains among this experiment 3-1-6, because not compound anti-reflection layer, so surface reflectivity and skin hardness are poor.In addition, the soil resistance on surface is also poor, and in above-mentioned evaluation, it still has residual after line that wiping is described with the oil pen or fingerprint.In addition, because do not form the 2nd adhesiveness modified layer, near infrared ray absorption layer is with respect to the poor adhesion of base film.And then, forming the cooperation of using coating fluid because cancelled surfactant near infrared ray absorption layer, the tone of the disconnected usefulness of near infrared absorbing coloring matter or neon photoresistance is regulated with the bad dispersibility of pigment to resin, so the appearance of film of near infrared ray absorption layer is poor.

Experiment 3-1-7

In the method for experiment 3-1-1, except cancellation near infrared ray absorption layer stacked, adopt and test the identical method of 3-1-1, obtained the light filter of this experiment 3-1-7.Wherein, in this experiment 3-1-7,, formed bonding coat on the base film surface because cancelled the stacked of near infrared ray absorption layer.The characteristic of the light filter that obtains in this experiment 3-1-7 is as shown in table 8.With regard to regard to the light filter that obtains among this experiment 3-1-7, because not stacked near infrared ray absorption layer, the transmitance of near infrared range is high and do not have a basic function as the near-infrared absorbing light filter.In addition, be not endowed the complementary color function.

Experiment 3-1-8

In experiment 3-1-1, change according to following (7)～(10), in addition, 3-1-1 has obtained the near-infrared absorbing light filter in the same manner with experiment.

(7) cooperation of cancellation ultraviolet light absorber in base film.

(8) the 2nd adhesiveness modified layer stacked to base film all cancelled on the two sides.

(9) the cancellation surfactant forms the cooperation of using coating fluid near infrared ray absorption layer.

(10) cooperating benzotriazole in bonding coat is that (Chiba Specialtychemicals system, TINUVIN386) 3 quality % and hindered phenol are antioxidant (Chiba Specialty chemicals system, IRGANOX1010) 1 quality % to ultraviolet light absorber.

The characteristic of the near-infrared absorbing light filter that obtains in this experiment 3-1-8 is as shown in table 8.With regard to regard to the near-infrared absorbing light filter that obtains among this experiment 3-1-8, ultraviolet light absorber is by the near infrared ray absorption layer more close adherend side of compound position than the cooperation near infrared absorbing coloring matter, so do not occur improving sunproof effect, be in low-level.In addition, owing to do not form the 2nd adhesiveness modified layer, near infrared ray absorption layer is with respect to the poor adhesion of base film.And then, forming the cooperation of using coating fluid because cancelled surfactant near infrared ray absorption layer, the tone of the disconnected usefulness of near infrared absorbing coloring matter or neon photoresistance is regulated with the bad dispersibility of pigment to resin, so the appearance of film of near infrared ray absorption layer is poor.

Table 8

^*At the base film of the ultraviolet range of testing 3-1-5 and the transmitance of duplexer is 0%

Experiment 3-2 (making of plasma display)

Unload plasma display (Fuji Tsu's system, PDS4211J-H) front panel, attach experiment 3-1-1 respectively to testing the near-infrared absorbing light filter of making among the 3-1-8 (light filter of bonding coat has been set) by getting involved bonding coat, and carried out various functional evaluation.In the plasma display that has used the near-infrared absorbing light filter that obtains by experiment 3-1-1, experiment 3-1-2, experiment 3-1-3 and experiment 3-1-4, can confirm following effect.

(1),, reduced appearing before one's eyes of the fluorescent light that in room lighting, uses so external light reflection has obtained inhibition because given antireflection to the surface.

(2) skin hardness height is so be difficult to sustain damage.

(3) because given soil resistance, adhere to fingerprint so promptly use hand to touch, also can eliminate simply by wiping.

(4) have the disconnected characteristic of neon photoresistance, tone is improved, so improved colorrendering quality.Specifically, having sneaked into orange redness becomes pure redly, and having green blueness becomes gorgeous indigo plant, and feeling to have yellow white becomes pure white.

(5) because of being endowed the near-infrared absorbing effect, so can prevent maloperation at the infrared remote controller of periphery setting.

(6) because photostability or ageing stability are outstanding, so even long-time the use, the function of above-mentioned (5) also is stable.

In addition-and the aspect, with regard to regard to the near-infrared absorbing light filter that obtains among the experiment 3-1-5, because the appearance of film of near infrared ray absorption layer is poor, so caused the picture quality reduction by this defective.In addition, because photostability is poor,, the damage of the infrared remote controller that is provided with at periphery is increased so use by long-time.

With regard to the near-infrared absorbing light filter that obtains among the 3-1-6 in experiment, because the surface reflectivity height, so external light reflection is high and the problem that exists the identification of the appearing before one's eyes of the fluorescent light that is used for room lighting, picture to reduce.In addition, skin hardness is low, because be not endowed soil resistance, thus sustain damage easily, and the wiping of the fingerprint that adheres to when touching with hand is poor.And then the appearance of film of near infrared ray absorption layer is poor, so caused the picture quality reduction by this defective.

With regard to regard to the near-infrared absorbing light filter that obtains among the experiment 3-1-7, because there is not the near-infrared absorbing ability, so taken place for the damage that is arranged on its peripheral infrared remote controller.In addition, because do not give neon light barrier, the colorrendering quality of image is poor.

With regard to regard to the near-infrared absorbing light filter that obtains among the experiment 3-1-8, because the recombination site of ultraviolet light absorber is than the more close plasma display side of near infrared ray absorption layer that has cooperated near infrared absorbing coloring matter, do not occur improving effect at the photostability of outer light, so the same with the near-infrared absorbing light filter that obtains among the 3-1-5 in experiment, the damage of the infrared remote controller that is provided with at periphery is increased.In addition, the appearance of film of near infrared ray absorption layer is poor, so caused the picture quality reduction by this defective.

In addition, with regard to regard to the near-infrared absorbing light filter that obtains among experiment 3-1-5,3-1-6 and the 3-1-8, the poor adhesion at the interface of base film and functional embodied layers.For this reason, the part that the interface has taken place after long-time the use is peeled off, and the quality of image reduces.

With regard to the near-infrared absorbing light filter that obtains among the 3-1-4 in experiment 3-1-1, experiment 3-1-2, experiment 3-1-3 and experiment, thinner thickness and be compounded with bonding coat.Therefore, when under the state on wetting plasma display surface, carrying out the attaching of this light filter, can suppress sneaking into and attaching well of bubble with isopropyl alcohol.Has utmost point good working.

Experiment 3-3

With the near-infrared absorbing laminar surface as the plasma display side, and use tackifier that optics uses to be attached to plasma display (Fuji Tsu's system to testing the near-infrared absorbing light filter (light filter of bonding coat is not set) that 3-1-8 obtains by experiment 3-1-1, PDS4211J-H) on the front panel, carry out various functional evaluation.Obtained same result with experiment 3-2.

Experiment 3-4 (making) with near-infrared absorbing light filter of electromagnetic wave blocking function

By experiment 3-1-1 to testing on the near-infrared absorbing light filter (light filter of bonding coat has been set) that 3-1-8 obtains, attach conductive mesh [electromagnetic wave blocking layer] by getting involved bonding coat.Above-mentioned conductive mesh is, has 135 density to carry out adopting electroless plating method plated nickel and copper to form on the fabric web that track and column braiding forms with every 2.54cm at the fiber that with line directly is 0.03mm.

(Fuji Tsu's system, front panel PDS4211J-H) use tackifier to attach each the near-infrared absorbing light filter with conductive mesh, carry out various functional evaluation to unload plasma display.Except confirmed effect in above-mentioned experiment 3-2, can also confirm to bring into play the electromagnetic wave blocking effect.

Experiment 4

Wherein, in this experimental example, except above-mentioned mensuration, evaluation method, following mensuration, evaluation method have also been adopted.

[the surface damage evaluation of base film]

Diaphragm to 16 250mm * 250mm is estimated.This evaluation is to carrying out through the film after 24 hours after beginning to make film.The fluorescent light of 400mm place configuration 20W * 2 lamps is as Projecting Lamp below XY worktable, is being arranged on the mask that fracture width on the XY worktable is 10mm mounting as the test film of determination object.When making light incident under the angle of the line that connects Projecting Lamp and photoreceptor and the vertical direction on test film surface is 12 ° condition, damage if exist on the test film of incoming position, then this part is luminous.With the ccd image sensing camera that is configured in 500mm place, XY worktable top the light quantity of this part is transformed into electric signal, and amplifies this electric signal,, itself and critical value (threshold value) are compared, export the detection signal of optical defect with comparator through differential.In addition, use ccd image sensing camera, the image of input damage, the vision signal of the image that the step analysis by regulation is transfused to is measured the size of optical defect, shows the position that the above defective of 50 μ m exists.The detection of the optical defect by this method is to carry out on the two sides of test film.

Partly select the defective that causes by damage from the optical defect that said method, detects.The part that adopts said method to be judged as damage is cut into suitable size, gathers shape observation test film.About this test film, (the MICROMAP system TYPE550), is observed the surface that detects defective of test film from vertical direction, measures the size of damage to use 3 dimension shape measuring apparatus.Wherein, when being film surperficial from vertical direction viewing test sheet, contiguous 50 μ m are considered as with-damage with interior damage concavo-convex.Cover the rectangular length of outermost minimum area of these damages and width length and width as damage.The degree of depth (damaging the difference in height in the highest place and minimum place) and the length of these damages have been measured.According to its result, obtaining the degree of depth is that 1 μ m is above and the number damage that length dimension 3mm is above is (individual/m ²), and judge by following benchmark.

◎: 30/m ²Below;

Zero: 31～50/m ²

△: 51～100/m ²

*: 100/m ²More than

[the foreign matter evaluation on base film surface]

From adopt the optical defect that the method described in the above-mentioned damage evaluation detects, select the defective that causes by foreign matter, the test film of this part is taken a sample.The face that detects defective to this test film carries out the Al evaporation, and (the MICROMAP system is TYPE550) from vertical direction viewing film face to use the coarse meter of non-contact 3-D.The number of obtaining maximum gauge and be the above foreign matter of 20 μ m is (individual/m ²), judge by following benchmark.

◎: 2/m ²Below;

Zero: 3～5/m ²

△: 6～100 ÷/m ²

*: 11/m ²More than

[ultraviolet light absorber on the thickness direction of base film partially in the property evaluation]

Adopt following method, the characteristic absorption of having measured the ultraviolet light absorber in the top layer of base film by FT-IR with respect to the absorbance of the characteristic absorption of polyester than the characteristic absorption of the ultraviolet light absorber of X and the central portion on the thickness direction of base film with respect to the absorbance of the characteristic absorption of polyester than Y, represent with X/Y.Be worth more little, ultraviolet light absorber high more in property partially.

Above-mentioned X can adopt following method to obtain.At first, the IR spectrum (I) on the top layer of mensuration blank sample (pet film that does not contain ultraviolet light absorber) and the top layer IR spectrum (II) of base film.Then, get (I) and differential spectra (II), the 1505cm that obtains the absorbance characteristic of the ultraviolet light absorber (absorb) at 1700～1800cm-1 place and itself and obtain from the IR spectrum of (II) ^-1The absorbance of the absorption (absorption of polyethylene terephthalate) at place is than (1700～1800cm ^-1/ 1500cm ^-1), as X.

In addition, cut at thickness direction base film gross thickness 50%, the face of peeling off out (central portion of film thickness direction) is carried out the mensuration identical with above-mentioned X, obtain the absorbance ratio, as Y.

Wherein, IR spectrum is measured with following method.

FT-IR device: Digilab system, FTS-7000e

1 secondary reflection ATR device: Thermo Spectra-Tech system

“Thunderdome”

IRE：Ge

Incident angle: 45 °

Resolution characteristic: 8cm ^-1

Cumulative frequency: 128 times

Experiment 4-1 (making of near-infrared absorbing light filter)

Experiment 4-1-1

1. the making of base film

Masterbatch pellet that contains ultraviolet light absorber that use is modulated in above-mentioned experiment 3-1 and the 2nd adhesiveness modified layer (easily adhesive linkage) form and use coating fluid, according to following step, make base film.

(1) making of base film

The double orientation laminated polyester film of base film is made into 3-tier architecture.As base material middle layer formation raw material, (Japan's weaving system, ME553) masterbatch pellet 10 mass parts of 90 mass parts and making in above-mentioned (1) are carried out 6 hours (1Torr:1.33 * 10 of drying under reduced pressure to not containing the PET particle that particle and limiting viscosity are 0.62dl/g under 135 ℃ ²Pa), offer the 2nd extruder then.Form as two top layers and use raw material, (Japan's weaving is made, and ME553) carries out 6 hours (1Torr:1.33 * 10 of drying under reduced pressure to the particle of the PET that do not contain particle under 135 ℃ ²Pa), offer the 1st extruder then.In the 1st extruder and the 2nd extruder, making the resin temperature up to extruder fusing department, kneading part, polymer pipe, gear-type pump, filtrator is 280 ℃, be 275 ℃ in polymer pipe subsequently, bonding (block) 3 laminated streams, stacked two top layers and base material middle layer, and be extruded into laminar from tube head.Wherein, use the filter materials (nominal filtering accuracy: block the particle 95% more than the 10 μ m) of stainless steel sintered body to filter for these PET respectively in melt stage.In addition, the resin temperature in the flat-die is made as 275 ℃.

Use static to apply casting, make to be melted to be extruded into laminar resin to stick to surface temperature be that cooling curing makes non-stretched film simultaneously on 30 ℃ the curtain coating drum (roller diameter: 400mm Φ, Ra:0.1 μ m is following).The spray volume of this moment is 48kg/hr, the wide 300mm of the non-stretched film that obtains, thick 1400 μ m.In addition, the spray volume of each extruder is regulated so that the ratio of the thickness on two top layers is respectively 10% with respect to gross thickness.

Then, use the roller group and the infrared heater that have heated, above-mentioned non-stretched film is heated to 100 ℃, utilize the roller group that has difference to go up 3.5 times (the longitudinal stretching film) that stretch subsequently, obtain monodirectional tension film at length direction (direction of travel).Wherein, about all rollers that use when making film, the surfaceness of pair roller is controlled so that its Ra is below the 0.1 μ m, on the roller of the preheating inlet that is positioned at stretching process and chill roll the roller clearer is set.Roller diameter in the longitudinal stretching operation is 150mm, and has adopted by adhering apparatus such as suction roll, static adhesion, part clamps and make film stick to method on the roller.

Adopt the reverse rollers method, on the two sides of above-mentioned one-way orientation film, being coated with by filtered particles size (initial stage filtration efficiency 95%) is that the 2nd adhesiveness modified layer that the felt type polypropylene filter made of 25 μ m has carried out secondary filter with material forms and uses coating fluid.Subsequently, grip the end of film and guide to the hot blast district that is heated to 130 ℃ with anchor clamps, dry back stretches 4.0 times on the thin-film width direction, 230 ℃ of 5 seconds of following thermal treatment, in this heat treatment step, on Width, carry out 3% tension and relaxation processing, obtain on two faces, being laminated with the base film of the 2nd adhesiveness modified layer.

The thickness of the base film that obtains is 100 μ m, and with regard to the 2nd adhesiveness modified layer, its dried coating weight is 0.01g/m on each face ²The evaluation result of surface appearance is as shown in table 9, even long-time production also can be suppressed the appearance of surface imperfection such as surface damage Superficial Foreign Body alive, can stably produce high-quality laminate film.

2. the formation of anti-reflection layer

Adopt reverse coating process, coating ultraviolet hardening coating (big day the system of refining, セ イ カ PVC one system EXF-01B) firmly on the 2nd adhesiveness modified layer surface of above-mentioned base film, and to make dried thickness be 5 μ m.Then, after dry solvent, by high voltage mercury lamp radiation 800mJ/cm ²Ultraviolet ray, make the resin solidification in the coating, form hard conating.

Then, the coating fluid that modulation is made of partial hydrolysis condensation product 5 mass parts, methyl alcohol 30 mass parts, ethanol 30 mass parts, isopropyl alcohol 35 mass parts of γ-An Bingjisanjiayangjiguiwan, it is coated on hard coating surface, and to make dried thickness be 0.02 μ m, under 140 ℃, after dry 20 seconds, form high refractive index layer.

Then, in tetraethoxysilane 24 mass parts, add ethanol 50 mass parts, water 20 mass parts, hydrochloric acid 4 mass parts, make the tetraethoxysilane hydrolysis, the modulation coating fluid.This coating fluid is coated on the high index of refraction laminar surface and makes dried thickness is 0.09 μ m, after dry 1 minute, forms low-index layer under 140 ℃.

And then, will be with the perfluoro hexane by C ₃F ₇-(OC ₃F ₆) ₃₄-O-(CF ₂) ₂-C ₂H ₄-O-CH ₂Si (OCH ₃) ₃The silane coupling agent that contains the perfluoro polyether base that constitutes is diluted to 0.5 quality % becomes coating fluid, and aforesaid coating fluid is coated on the above-mentioned low-refraction laminar surface, and drying is 1 minute under 120 ℃, and forming thickness is the stain-proofing layer of 8nm.

Thus, formed the stacked in this order anti-reflection layer of hard conating/high refractive index layer/low-index layer/stain-proofing layer on the 2nd adhesiveness modified layer surface of base film.

3. the formation of near infrared ray absorption layer

On the base film that forms anti-reflection layer and the 2nd adhesiveness modified layer surface anti-reflection layer opposition side, the near infrared ray absorption layer identical with above-mentioned experiment 2-1 coating fluid N2-1 (table 5 is formed in coating, solid component concentration: 17 quality %, viscosity: 40cps), and to make dried coating weight be 8.5g/m ²Coating is to be that the oblique line gravure roll reverse rotation of 60cm is carried out by making diameter.Subsequently, the wind that makes 40 ℃ and 5m/ second is by 20 seconds (the 1st drying process), and the wind that makes 150 ℃ and 20m/ second is by 20 seconds (the 2nd drying process), and then the wind that makes 90 ℃ and 20m/ second was by 10 seconds (refrigerating work procedure), make its drying, made the near-infrared absorbing light filter.

4. the formation of bonding coat

Adopt the spot printing method, on the surface of the near infrared ray absorption layer of above-mentioned near-infrared absorbing light filter, the stacked clear binder that constitutes by n-butyl acrylate (78.4 quality %), 2-EHA (19.6 quality %) and acrylic acid (2 quality %) as acrylate copolymer, and to make dried thickness be 0.025mm.And then the PET system isolated film that the stacked thickness of silicone-treated having been implemented on its surface is 0.038mm has obtained having the near-infrared absorbing light filter of bonding coat and the complex of isolated film.

Above-mentioned near-infrared absorbing light filter carries out above-mentioned each evaluation, and its result is as shown in table 9.Evaluation beyond the light fastness test is that the near-infrared absorbing light filter that bonding coat is not set is carried out, and light fastness test is that the near-infrared absorbing light filter that bonding coat is set is carried out.As shown in Table 9, the near-infrared absorbing light filter that obtains is bigger in the absorption near infrared region and neon light zone, and the transmitance of visible region is also bigger.In addition, the absorption of ultraviolet range is very big, and ageing stability (light transmission rate, tone) and photostability are outstanding.And then the coiling characteristic of the outward appearance of near infrared ray absorption layer or light filter is also good.

And then also the anti-reflection layer to the near-infrared absorbing light filter has carried out the soil resistance evaluation.Soil resistance is to estimate with the wiping of oil pen's wiping and fingerprint.When estimating oil pen's wiping, use the oil pen in the line of anti-reflection layer surface and with nonwoven fabrics (Asahi Chemical Industry's system of cellulose system, ベ Application コ Star ト Application M-3) this line of wiping, in addition, when estimating the wiping of fingerprint with nonwoven fabrics (Asahi Chemical Industry's system of cellulose system, ベ Application コ Star ト Application M-3) wiping is attached to the fingerprint on anti-reflection layer surface, its wiping of visual judgement.It found that and can both wipe out fully.

In addition, the gross thickness of the near-infrared absorbing light filter that obtains in the present embodiment (bonding coat on the surface from the most surperficial anti-reflection layer to the display side) is 0.14mm, extremely thin, also has aforesaid outstanding characteristic on this basis, so after peeling off the isolated film of above-mentioned complex, utilize the cohesive of bonding coat, can easily be attached on the adherends such as plasma display.As mentioned above, with regard to this near-infrared absorbing light filter, more known light filter was thin than in the past for its thickness, so its adhesion operation is outstanding.

Experiment 4-1-2

In the double orientation laminated polyester film that constitutes base film, the thickness on two top layers is made as 5% of gross thickness respectively, in addition, made near-infrared absorbing light filter in the same manner with experiment 4-1-1 with anti-reflection layer, base film and near infrared ray absorption layer.And then, also using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 9.As shown in table 9, have and the equal characteristic of near-infrared absorbing light filter that in experiment 4-1-1, obtains.In addition, also carried out the soil resistance evaluation in the same manner with experiment 4-1-1, wiping of oil pen's wiping, fingerprint is all good as a result for it.

Experiment 4-1-3

The condition of the extruder in the making non-stretched film stage during about the manufacturing base film, the temperature of polymer pipe behind the filtrator and flat-die is changed so that resin temperature is 285 ℃, in addition, made near-infrared absorbing light filter in the same manner with experiment 4-1-1 with anti-reflection layer, base film and near infrared ray absorption layer.And then, also using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 9.

As shown in table 9, have and the roughly equal characteristic of near-infrared absorbing light filter that in experiment 4-1-1, obtains.But the ultraviolet light absorber on the thickness direction in base film is poor a little in degree partially, and the effect that the distillation of ultraviolet light absorber suppresses or the migration in film suppresses reduces a little.In addition, along with the change to the condition of the extruder of non-stretched film production phase, the surface appearance of base film also worsens a little.And then, also having carried out the soil resistance evaluation in the same manner with experiment 4-1-1, wiping of oil pen's wiping, fingerprint is all good as a result for it.

Experiment 4-1-4

Except the surfactant that will use near infrared ray absorption layer forms with coating fluid becomes HLB is 11 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2105) outside, 4-1-1 has made the near-infrared absorbing light filter with anti-reflection layer, base film and near infrared ray absorption layer in the same manner with experiment.And then, also using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 9.Because used the surfactant of HLB than the near-infrared absorbing light filter big (water wettability height) that in experiment 4-1-1, obtains, so the ageing stability under high temperature/high humidity is poor a little, the sliding near infrared ray absorption layer surface is also poor slightly, has occurred some coiling dislocation (still being " ◎ " but estimate rank) thus.In addition, also carried out the soil resistance evaluation in the same manner with experiment 4-1-1, wiping of oil pen's wiping, fingerprint is all good as a result for it.

Experiment 4-1-5

Except the surfactant that will use near infrared ray absorption layer forms with coating fluid becomes HLB is 3 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2136) outside, 4-1-1 has made the near-infrared absorbing light filter with anti-reflection layer, base film and near infrared ray absorption layer in the same manner with experiment.And then, also using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 9.Because used the surfactant of HLB than the near-infrared absorbing light filter little (hydrophobicity height) that obtains in experiment 4-1-1, so the levelability when forming near infrared ray absorption layer is poor slightly, tiny flaw also increases a little.In addition, also carried out the soil resistance evaluation in the same manner with experiment 4-1-1, wiping of oil pen's wiping, fingerprint is all good as a result for it.

Experiment 4-1-6

In base film, do not cooperate ultraviolet light absorber, in addition, two sides at base film does not all form the 2nd adhesiveness modified layer, and then in forming with coating fluid, near infrared ray absorption layer do not add surfactant, in addition, made near-infrared absorbing light filter in the same manner with experiment 4-1-1 with anti-reflection layer, base film and near infrared ray absorption layer.And then, also using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 10.

With regard to these near-infrared absorbing light filters, as shown in table 10, its ultraviolet ray transmissivity height, the UV degradation of near infrared absorbing coloring matter is serious, and photostability is poor.In addition, there is not the 2nd adhesiveness modified layer, thus between anti-reflection layer and the base film, the adhesiveness between base film and the near infrared ray absorption layer, poor than the near-infrared absorbing light filter of experiment 4-1-1.And then, because near infrared ray absorption layer forms with coating fluid, do not add surfactant, the tone of the disconnected usefulness of near infrared absorbing coloring matter or neon photoresistance is adjusted the bad dispersibility of pigment to resin, and the outward appearance of near infrared ray absorption layer is compared relatively poor with the near-infrared absorbing light filter of experiment 4-1-1.The sliding near infrared ray absorption layer surface is poor in addition, is difficult to coil into drum.

Experiment 4-1-7

Except not forming the anti-reflection layer, 4-1-1 has made the near-infrared absorbing light filter with base film and near infrared ray absorption layer in the same manner with experiment.And then, also using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 10.With regard to these near-infrared absorbing light filters, because do not have anti-reflection layer, so as shown in table 10, surface reflectivity or skin hardness are poor.In addition, also carried out the soil resistance evaluation in the same manner with experiment 4-1-1, its result still has residual after wiping with line or the fingerprint that the oil pen describes.

Experiment 4-1-8

Except not forming the near infrared ray absorption layer, 4-1-1 has made the light filter with anti-reflection layer and base film in the same manner with experiment.And then, also using this light filter, 4-1-1 has made the light filter with bonding coat in the same manner with experiment.The evaluation result of these light filters is as shown in table 10.With regard to these light filters, because do not have near infrared ray absorption layer, so as shown in table 10, the transmitance height of near infrared region does not have the basic function as the near-infrared absorbing light filter.In addition, do not have complementary color function (receptivity of neon light) yet.Thus, ocular estimate and the coiling evaluating characteristics of ageing stability test, light fastness test, near infrared ray absorption layer have been cancelled.

Experiment 4-1-9

In base film, do not cooperate ultraviolet light absorber, on two faces of base film, all do not form the 2nd adhesiveness modified layer, in forming with coating fluid, near infrared ray absorption layer do not add surfactant, in addition, made near-infrared absorbing light filter in the same manner with experiment 4-1-1 with anti-reflection layer, base film and near infrared ray absorption layer.And then, use this near-infrared absorbing light filter, cooperating benzotriazole in bonding coat is ultraviolet light absorber (Chiba Specialty chemicals system, TINUVIN386) 3 quality % and hindered phenol are antioxidant (Chiba Specialtychemicals system, IRGANOX1010) under the condition of 1 quality %, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 10.As shown in Table 10, compare with layer [bonding coat] with ultraviolet light absorber, near infrared ray absorption layer is configured to more close light (from the light of outside) light incident side, therefore can not embody the effect of being brought by ultraviolet light absorber that prevents the near infrared absorbing coloring matter deterioration, and photostability is in low-level.In addition, owing to there is not the 2nd adhesiveness modified layer, the adhesiveness between anti-reflection layer and the base film, between base film and the near infrared ray absorption layer, poorer than the near-infrared absorbing light filter of experiment 4-1-1.And then, because near infrared ray absorption layer forms with coating fluid, do not add surfactant, the tone of the disconnected usefulness of near infrared absorbing coloring matter or neon photoresistance is adjusted the bad dispersibility of pigment to resin, and the outward appearance of near infrared ray absorption layer is compared relatively poor with the near-infrared absorbing light filter of experiment 4-1-1.The sliding near infrared ray absorption layer surface is also poor in addition, is difficult to coil into drum.Wherein, as shown in table 10, the transmitance of the ultraviolet range of near-infrared absorbing light filter [no bonding coat] is 95%, but also has in the embodiment of bonding coat, and the transmitance of ultraviolet range is 0%.

Experiment 4-1-10

In base film, use the double orientation mylar of individual layer, on two faces of base film, all do not form the 2nd adhesiveness modified layer, in forming with coating fluid, near infrared ray absorption layer do not add surfactant, in addition, made near-infrared absorbing light filter in the same manner with experiment 4-1-1 with anti-reflection layer, base film and near infrared ray absorption layer.And then, using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 10.With regard to this near-infrared absorbing light filter, because base film is a single layer structure, so the distillation of ultraviolet light absorber inhibition effect or inhibition are from the weak effect that oozes out of film inside, the film surface that has occurred being caused by ultraviolet light absorber pollutes or the device of film making process pollutes, thus, as shown in table 10, the damage on base film surface or foreign matter increase, and steady production is poor for a long time.

In addition, owing to there is not the 2nd adhesiveness modified layer, the adhesiveness between anti-reflection layer and the base film, between base film and the near infrared ray absorption layer, poorer than the near-infrared absorbing light filter of experiment 4-1-1.And then, because do not form and add surfactant with coating fluid near infrared ray absorption layer, the tone of the disconnected usefulness of near infrared absorbing coloring matter or neon photoresistance is adjusted the bad dispersibility of pigment to resin, and the outward appearance of near infrared ray absorption layer is compared relatively poor with the near-infrared absorbing light filter of experiment 4-1-1.The sliding near infrared ray absorption layer surface is poor in addition, is difficult to coil into drum.

Experiment 4-1-11

Except the surfactant that will use near infrared ray absorption layer forms with coating fluid becomes HLB is 1 silicone-based surfactant (Japanese ユ ニ カ one system, FZ-2110) outside, 4-1-1 has made the near-infrared absorbing light filter with anti-reflection layer, base film and near infrared ray absorption layer in the same manner with experiment.And then, also using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 10.In these near-infrared absorbing light filters, because used the surfactant of HLB very little (hydrophobicity height), so the levelability when forming near infrared ray absorption layer is poor, it is a lot of etc. that tiny flaw increases, and the outward appearance of near infrared ray absorption layer worsens.In addition, because the sliding near infrared ray absorption layer surface is good excessively, so the dislocation of reeling when coiling into drum, occurred.

Experiment 4-1-12

Except the surfactant that will use near infrared ray absorption layer forms with coating fluid becomes HLB is 14 silicone-based surfactant (Tokyo silicon system, TSF4440) outside, 4-1-1 has made the near-infrared absorbing light filter with anti-reflection layer, base film and near infrared ray absorption layer in the same manner with experiment.And then, also using this near-infrared absorbing light filter, 4-1-1 has made the near-infrared absorbing light filter with bonding coat in the same manner with experiment.The evaluation result of these near-infrared absorbing light filters is as shown in table 10.In these near-infrared absorbing light filters, because used the very surfactant of big (water wettability height) of HLB, so that tiny flaw increases is a lot of etc., the outward appearance of near infrared ray absorption layer worsens.In addition, the dislocation of reeling has appearred when coiling into drum.

Table 9

^*(A) layer: anti-reflection layer, (B) layer: base film, (C) layer: near infrared ray absorption layer

Table 10

^*(A) layer: anti-reflection layer, (B) layer: base film, (C) layer: near infrared ray absorption layer

Experiment 4-2 (making of plasma display)

Unload plasma display (Fuji Tsu's system, PDS4211J-H) front panel, attach experiment 4-1-1 respectively to testing the near-infrared absorbing light filter of making among the 4-1-12 (light filter of bonding coat has been set) by getting involved bonding coat, carry out various functional evaluation.Having used by experiment 4-1-1 to the plasma display of the near-infrared absorbing light filter of testing 4-1-5, can confirm following effect.

(1),, reduced appearing before one's eyes of the fluorescent light that in room lighting, uses so external light reflection has obtained inhibition because given antireflection to the surface.

(2) skin hardness height is so be difficult to sustain damage.

(3) because given soil resistance, adhere to fingerprint so promptly use hand to touch, also can eliminate simply by wiping.

(4) have the disconnected characteristic of neon photoresistance, tone is improved, so improved colorrendering quality.Specifically, having sneaked into orange redness becomes pure redly, and having green blueness becomes gorgeous indigo plant, and feeling to have yellow white becomes pure white.

(5) because of being endowed the near-infrared absorbing effect, so can prevent maloperation at the infrared remote controller of periphery setting.

(6) because photostability or ageing stability are outstanding, so even long-time the use, the function of above-mentioned (5) also is stable.

Relative therewith, in the plasma display of each the near-infrared absorbing light filter that has used comparative example, can see following unfavorable condition.With regard to the display panel of near-infrared absorbing light filter in having used experiment 4-1-6, because the appearance of film of near infrared ray absorption layer is poor, so picture quality reduces.In addition, because photostability is poor, so after long-time the use, the frequency that occurs faulty operation at the infrared remote controller of periphery setting has increase.

With regard to the display panel of the near-infrared absorbing light filter that used experiment 4-1-7, because the surface reflectivity height, so external light reflection is high and the problem that exists the identification of the appearing before one's eyes of the fluorescent light that is used for room lighting, picture to reduce.In addition,, sustain damage easily, and then be not endowed soil resistance, so the wiping of the fingerprint that adheres to when touching with hand is poor because skin hardness is low.

With regard to the display panel that has used the near-infrared absorbing light filter of testing 4-1-8, because there is not the near-infrared absorbing ability, on the infrared remote controller of periphery setting faulty operation has appearred.In addition, because do not give neon light barrier, the colorrendering quality of image is poor.

With regard to the display panel that has used the near-infrared absorbing light filter of testing 4-1-9, because ultraviolet light absorber the position is set than the more close plasma display side of near infrared ray absorption layer, the photostability of failing to embody at outer light [from the incident light of anti-reflection layer side] improves effect, by long use, the frequency that occurs faulty operation at the infrared remote controller of periphery setting has increase.In addition, the appearance of film of near infrared ray absorption layer is poor, so picture quality reduces.

Just used with regard to the display panel of the near-infrared absorbing light filter that obtains among the experiment 4-1-10, particularly under the situation of film as base film of after use begins to make film, producing through back more than 24 hours, the surface imperfection of this base film is more, so can see the reduction of the picture quality that is caused by this defective.

With regard to the display panel that has used experiment 4-1-11 and the near-infrared absorbing light filter of experiment 4-1-12, the appearance poor of near infrared ray absorption layer, the picture quality of plasma display reduces.In addition, in the near-infrared absorbing light filter of experiment 4-1-12, because photostability is poor, so, can see the further reduction of picture quality by using for a long time.

In addition, with regard to used experiment 4-1-6, experiment 4-1-9 and experiment 4-1-10 the display panel of near-infrared absorbing light filter with regard to, the poor adhesion at the interface of base film and functional embodied layers [anti-reflection layer and near infrared absorption layer], so by using for a long time, the part that the interface occurs is peeled off, and picture quality reduces.

Also have, with regard to experiment 4-1-1 to the near-infrared absorbing light filter of testing 4-1-5, thinner thickness and be compounded with bonding coat.Therefore, when under the state on wetting plasma display surface, carrying out the attaching of this light filter, can suppress sneaking into and attaching well of bubble, have utmost point good working with isopropyl alcohol.

Experiment 4-3

With the near-infrared absorbing laminar surface as the plasma display side, and the tackifier that uses optics to use will be attached to plasma display (Fuji Tsu's system to testing the near-infrared absorbing light filter (light filter of bonding coat is not set) that obtains among the 4-1-5 by experiment 4-1-1, PDS4211J-H) on the front panel, carry out various functional evaluation.Obtained same result with experiment 4-2.

Experiment 4-4 (making) with near-infrared absorbing light filter of electromagnetic wave blocking function

By testing 4-1-1, attach conductive mesh [electromagnetic wave blocking layer] by getting involved bonding coat to testing on the near-infrared absorbing light filter of making among the 4-1-5 (light filter of bonding coat has been set).Above-mentioned conductive mesh is, with line directly for the fiber of 0.03mm with the density that has 135 among every 2.54cm carry out that track and column braiding forms online, adopt electroless plating method plated nickel and copper to form.

(Fuji Tsu's system, front panel PDS4211J-H) use tackifier to attach each the near-infrared absorbing light filter with conductive mesh, carry out various functional evaluation to unload plasma display.Except confirmed effect in above-mentioned experiment 4-2, can also confirm to bring into play the electromagnetic wave blocking effect.

Experiment 5

In experimental example shown below (experiment 5 is to experiment 8), except above-mentioned mensuration, evaluation method, following mensuration, evaluation method have also been adopted.

[length direction (MD direction) of aberration Δ E-film]

About the length that obtains in each experimental example described later is the film of 500m, from the 1st end (thin film fabrication begins the end of side) of film to the 2nd end (thin film fabrication finishes the end of side), at 10m is 51 positions at interval, substantial middle portion in the thin-film width direction, according to above-mentioned tone determination method L value, a value, b value are measured, calculate the aberration Δ E that the following formula of the usefulness that respectively locates (12) defines by L value, a value, b value, maximal value wherein is made as the aberration Δ E of the length direction of film.

Wherein, in the film of each experimental example described later, aberration Δ E (MD) is below 2, can confirm that whole film total length is equivalent to constant zone.

ΔE(MD)＝[(L _a-L _m) ²+(a _a-a _m) ²+(b _a-b _m) ²] ^1/2 ……(12)

[length direction (TD direction) of aberration Δ E-film]

Width (TD) about the film that in each experimental example described later, obtains, one side's end is made as the 1st end, the opposing party's end is made as the 2nd end, with these two ends as locating, simultaneously between these two ends, 3 places uniformly-spaced are set to locate, according to above-mentioned tone determination method the L value, a value, the b value that respectively locate are measured, calculate the aberration Δ E that the following formula of the usefulness that respectively locates (13) defines by L value, a value, b value, maximal value wherein is made as the aberration Δ E of the Width of film.

ΔE(TD)＝[(L _a-L _m) ²+(a _a-a _m) ²+(b _a-b _m) ²] ^1/2 ……(13)

1. the making of base film

With limiting viscosity is that 0.62dl/g and the pet resin that does not contain particle are put in the double screw extrusion machine, under 290 ℃, melt extrude from the T die head, apply static to cooling rotating metallic roller on one side, be solidificated on this metallic roll Yi Bian resin is adhered to, thin slice is not stretched.Then, this thin slice that do not stretch is heated to 90 ℃, after longitudinally stretch (length direction stretching) 3.5 times, on this film, is coated on the middle layer of using among the above-mentioned experiment 1-1 with coating fluid A (table 1) and make dried coating weight be 0.5g/m with the roller drawing machine ², make wind speed be 10m/ second, temperature be 120 ℃ hot blast by 20 seconds, form the middle layer.And then, on Width, stretch 3.7 times after being heated to 140 ℃ with stenter, loose 5% on width (laterally) direction under 235 ℃, heat-treat simultaneously then.The base film (two-way stretch PET film) that the two sides that so obtains is had the length in middle layer coils into drum.With regard to the base film that obtains, thickness is 100 μ m, and total light transmittance is 90.2%, and turbidity is 0.5%.Wherein, total light transmittance and turbidity are that benchmark is measured with JIS-K7136.

2. near infrared ray absorption layer forms the making with coating fluid

Be blended in each composition that the near infrared ray absorption layer of using among the above-mentioned experiment 1-1 forms the coating fluid N1-1 (table 2) of usefulness, dissolve pigment and resin down in heating (40 ℃), use nominal filtering accuracy is that the filtrator of 1 μ m is removed not dissolved matter, has obtained coating fluid.The solid component concentration of coating fluid is 17 quality %, and viscosity (viscosity that adopts above-mentioned determination method to obtain) is 40cps.

Experiment 5-1

By being that 50 degree and contact pressure are to be contacted with oblique line gravure roll (diameter: 60cm, line number: 45 lines/2.54cm, the degree of depth: 290 μ m, unit volume: 139cm under the condition of 0.3Mpa with its angle with the ceramic scraper ³/ m ²) and with this oblique line gravure roll reverse rotation, near infrared ray absorption layer formation is coated on the long base film continuously with coating fluid N1-1.Subsequently, be incorporated in the drying oven, making them in 20 seconds is that 40 ℃ and wind speed are the 5m/ dry section of second (the 1st drying process) by temperature, then, making them in 20 seconds is that 150 ℃ and wind speed are the 20m/ dry section of second (the 2nd drying process) by temperature, and then making them in 10 seconds is that 90 ℃ and wind speed are the 20m/ cooling zone of second (refrigerating work procedure) by temperature, makes its drying.

Also have, drying oven be exported to the batching between the place of near-infrared absorbing film, be provided with online colour difference meter (Da mound electronics system, MCPD-3000).The rotational speed G of gravure roll slowly is changed to 0.94 than G/F from 0.90 with respect to the speed of film speed of travel F, so that the L value constant that utilizes this online colour difference meter to measure, and make baking temperature slowly be changed to 152 ℃ from 150 ℃, so that a value and b value are constant.So, when the tone of film length direction is controlled, made long near-infrared absorbing film continuously, and coiled into drum.The evaluation result of this near-infrared absorbing film is as shown in table 11.

Experiment 5-2

In experiment 5-1, by regulating the contact angle (interior angle) of scraper and gravure roll, controlled the long near-infrared absorbing film of continuous manufacturing the time L value, and make this contact angle from 50 degree to the slowly variation of 46 degree.In addition make long near-infrared absorbing film in the same manner continuously with experiment 5-1, and coiled into drum.The evaluation result of this near-infrared absorbing film is as shown in table 11.

Experiment 5-3

In experiment 5-1, the tonal variation with a value and b value during to the long near-infrared absorbing film of continuous manufacturing is managed, and in order to make these constants, the interior wind speed of drying oven that makes baking temperature set 150 ℃ for slowly changes to 23m/ from 20m/ second second.Condition except that these process control methods and condition has been made long near-infrared absorbing film continuously with experiment 5-1 ground, and coils into drum.The evaluation result of this near-infrared absorbing film is as shown in table 11.

Experiment 5-4

In experiment 5-1, the material of scraper is altered to Sweden's formula steel, and with online colour difference meter management L value, make simultaneously speed than G/F from 0.90 to 1.2 slowly variations.In addition make long near-infrared absorbing film in the same manner continuously with experiment 5-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 11.

Experiment 5-5

In experiment 5-1, when making long near-infrared absorbing film continuously, coating condition and drying condition are remained unchanged.In addition make long near-infrared absorbing film in the same manner continuously with experiment 5-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 11.

Experiment 5-6

In experiment 5-1, the material of scraper is altered to Sweden's formula steel, and when making long near-infrared absorbing film continuously, coating condition and drying condition is remained unchanged.In addition make long near-infrared absorbing film in the same manner continuously with experiment 5-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 11.

Table 11

As shown in Table 11, with regard at experiment 5-1 to testing with regard to the near-infrared absorbing film that obtains among the 5-4, the transmitance of near infrared region is low, the transmitance height in the visible region.And then aberration Δ E (MD) is less in the maximal value of the length direction of near-infrared absorbing film, and tone has been subjected to inhibition in the variation of the length direction of film.In addition, the appearance of film of near infrared ray absorption layer is also very good.

Also have, with regard to regard to the near-infrared absorbing film that obtains among the experiment 5-4, compare with the near-infrared absorbing film that obtains in experiment 5-1, the tonal variation when making continuously is bigger., speed significantly need be changed than G/F, the tonal variation of final near-infrared absorbing film is also big slightly for this reason.And then, owing to also set final speed for bigger value (1.2) than G/F, close on more and make the later stage, laterally the thickness spot of grade is big more.

Relative therewith, with regard to the near-infrared absorbing film that obtains among the 5-5 in experiment, because the tonal variation when making continuously increases, so the tonal variation of the length direction of near-infrared absorbing film also increases.In addition, close on more and make the later stage, the spot of striated is big more in the appearance of film of near infrared ray absorption layer.And then with regard to regard to the near-infrared absorbing film that obtains among the experiment 5-6, the tonal variation of length direction is also bigger than the near-infrared absorbing film that obtains in experiment 5-5, and the outward appearance of near infrared ray absorption layer also worsens.This is because because the wearing and tearing of scraper, variation has taken place the coating weight of coating fluid.

Experiment 6

The base film of the length that use is made in above-mentioned experiment 5 and the near infrared ray absorption layer of using in above-mentioned experiment 2-1 form with coating fluid N2-1 (table 5), according to following step, make long near-infrared absorbing film continuously, and coiled into drum.

Experiment 6-1

By being that 50 degree and contact pressure are to be contacted with oblique line gravure roll (diameter: 60cm, line number: 45 lines/2.54cm, the degree of depth: 290 μ m, unit volume: 139cm under the condition of 0.3MPa with its angle with the ceramic scraper ³/ m ²) and with this oblique line gravure roll reverse rotation, near infrared ray absorption layer formation is coated on the long base film continuously with coating fluid N2-1.Subsequently, be incorporated in the drying oven, making them in 20 seconds is that 40 ℃ and wind speed are the 5m/ dry section of second (the 1st drying process) by temperature, then, making them in 20 seconds is that 150 ℃ and wind speed are the 20m/ dry section of second (the 2nd drying process) by temperature, and then making them in 10 seconds is that 90 ℃ and wind speed are the 20m/ cooling zone of second (refrigerating work procedure) by temperature, makes its drying.

Also have, drying oven be exported to the batching between the place of near-infrared absorbing film, be provided with online colour difference meter (Da mound electronics system, MCPD-3000).The rotational speed G that makes gravure roll slowly changes from 0.90 to 0.94 than G/F with respect to the speed of film speed of travel F, so that pass through the L value constant that this online colour difference meter is measured, and baking temperature is slowly changed from 150 ℃ to 152 ℃, so that a value and b value are constant.When as described above the tone of film length direction being controlled, make long near-infrared absorbing film continuously, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 12.

Experiment 6-2

In testing 6-1, by the contact angle (interior angle) of adjusting scraper and gravure roll, the L value during continuous manufacturing of the long near-infrared absorbing film of control makes this contact angle spend slow the variation from 50 degree to 46.In addition make long near-infrared absorbing film in the same manner continuously with experiment 6-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 12.

Experiment 6-3

In experiment 6-1, the tonal variation when using a value and b value to the long near-infrared absorbing film of continuous manufacturing manages, and in order to make these constants, the wind speed that baking temperature has been set in 150 ℃ the drying oven slowly changes to 23m/ from 20m/ second second.Except that these process control methods and condition, make long near-infrared absorbing film in the same manner continuously with experiment 6-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 12.

Experiment 6-4

In experiment 6-1, not with tone but to use online spectrophotometer (big mound electronics system, MCPD-3000) transmitance of the light of the wavelength 585nm of Ce Lianging, carry out the process management when making long near-infrared absorbing film continuously, and speed is slowly changed from 0.90 to 0.95 than F/G, so that this transmitance constant.Except that these process control methods and condition, make long near-infrared absorbing film in the same manner continuously with experiment 6-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 12.

Experiment 6-5

In experiment 6-1, the material of scraper is altered to Sweden's formula steel, and with online colour difference meter management L value, make simultaneously speed than G/F from 0.90 to 1.2 slowly variations.In addition, make long near-infrared absorbing film in the same manner continuously with experiment 6-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 12.

Experiment 6-6

In experiment 6-1, the material of scraper is altered to nickel, and with online colour difference meter management L value, make simultaneously speed than G/F from 0.90 to 1.13 slowly variations.Except that this condition, make long near-infrared absorbing film in the same manner continuously with experiment 6-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 12.

Table 12

As shown in Table 12, with regard at experiment 6-1 to testing with regard to the near-infrared absorbing film that obtains among the 6-6, near infrared region and to have the transmitance of visible region (neon light zone) of orange wavelength low, the transmitance height of the visible region beyond orange-colored light.And then aberration Δ E (MD) is less in the maximal value of the length direction of film, and tone has been subjected to inhibition in the variation of the length direction of film.In addition, the appearance of film of near infrared ray absorption layer is also very good.

Wherein,, compare the tonal variation during manufacturing bigger (in experiment 6-6, big slightly) with the near-infrared absorbing film that in experiment 6-1, obtains with regard to regard to the near-infrared absorbing film that obtains among experiment 6-5 or the experiment 6-6.For this reason, need significantly change velocity ratio G/F, the tonal variation of final film also increases a little.And then because final speed (is tested 6-5:1.2, experiment 6-6:1.13) also greatly than G/F, the manufacturing later stage that horizontal spot equal thickness spot closes on long near-infrared absorbing film more is big more.

Experiment 7

1. the making of base film

The long substrate film that has the middle layer on the two sides that use is made in above-mentioned experiment 5 on the TD of this base film direction, cuts from the width of central portion with 1.3m, is used to make the thin volume of near-infrared absorbing.

2. near infrared ray absorption layer forms the making with coating fluid

The near infrared ray absorption layer that use is used in above-mentioned experiment 2-1 forms with coating fluid N2-1 (table 5), according to following step, makes long near-infrared absorbing film continuously, and coils into drum.

Experiment 7-1

Use reverse photogravure/kiss-coating device, the coating near infrared ray absorption layer forms and uses coating fluid N2-1 on base film.The device that is used to be coated with is oblique line gravure roll (diameter: 60cm, a line number: 45 lines/2.54cm, the degree of depth: 290 μ m, unit volume: 139cm ³/ m ²).Make the scraper of ceramic be contacted with this roller, and make the gravure roll reverse rotation and be coated with.The speed of travel F that makes base film is 20m/ minute, and the rotational speed of gravure roll is 18m/ minute (speed is 0.9 than G/F), and also making kiss-coating length is 10mm, is 0.7N/mm at the tension force of the MD direction of the coating part of base film ²

After the coating coating fluid, be incorporated in the drying oven, making them in 20 seconds is that 40 ℃ and wind speed are the 5m/ dry section of second (the 1st drying process) by temperature, then, making them in 20 seconds is that 150 ℃ and wind speed are the 20m/ dry section of second (the 2nd drying process) by temperature, and then making them in 10 seconds is that 90 ℃ and wind speed are the 20m/ cooling zone of second (refrigerating work procedure) by temperature, makes its drying.Thus, make the near-infrared absorbing film of width (TD direction) continuously, and coil into drum for the length of 1.275m.The evaluation result of this near-infrared absorbing film is as shown in table 13.

Experiment 7-2

Except the tension force with the MD direction of the coating part of base film becomes 1.0N/mm ²Outside, make long near-infrared absorbing film in the same manner continuously with experiment 7-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 13.

Experiment 7-3

Except the tension force with the MD direction of the coating part of base film becomes 1.2N/mm ²Outside, make long near-infrared absorbing film in the same manner continuously with experiment 7-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 13.

Experiment 7-4

Except the tension force with the MD direction of the coating part of base film becomes 0.5N/mm ²Outside, make long near-infrared absorbing film in the same manner continuously with experiment 7-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 13.

Experiment 7-5

Except the material with scraper becomes Sweden's formula steel, make long near-infrared absorbing film in the same manner continuously with experiment 7-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 13.

Experiment 7-6

Form with in the coating fluid near infrared ray absorption layer, equivalent increases cyclopentanone and toluene so that solid component concentration becomes 15 quality %, and speed is become 1.6 than the G/F change, in addition, make long near-infrared absorbing film in the same manner continuously with experiment 7-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 13.

Experiment 7-7

Except the contact angle change with scraper becomes 75 degree, speed is become 0.8 than the G/F change, make long near-infrared absorbing film in the same manner continuously with experiment 7-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 13.

Table 13

As shown in Table 13, with regard at experiment 7-1 to testing with regard to the near-infrared absorbing film that obtains among the 7-7, near infrared region and to have the transmitance of visible region (neon light zone) of orange wavelength low, the transmitance height of the visible region beyond orange-colored light.And then aberration Δ E (TD) is less in the maximal value of the TD of film direction, and tone has been subjected to inhibition in the variation of the TD of film direction.In addition, the outward appearance of near infrared ray absorption layer is also very good.

Experiment 8

1. the making of base film

The long substrate film that has the middle layer on the two sides that use is made in above-mentioned experiment 5 on the TD of this base film direction, cuts from the width of central portion with 1.3m, is used to make the thin volume of near-infrared absorbing.

2. near infrared ray absorption layer forms the making with coating fluid

The near infrared ray absorption layer that use is used in above-mentioned experiment 1-1 forms with coating fluid N1-1 (table 2), according to following step, makes long near-infrared absorbing film continuously, and coils into drum.

Experiment 8-1

Use reverse photogravure/kiss-coating device, the coating near infrared ray absorption layer forms and uses coating fluid on base film.The device that is used to be coated with is oblique line gravure roll (diameter: 60cm, a line number: 45 lines/2.54cm, the degree of depth: 290 μ m, unit volume: 139cm ³/ m ²).Make the scraper of ceramic be contacted with this roller, and make the gravure roll reverse rotation and be coated with.The speed of travel F that makes base film is 20m/ minute, and the rotational speed of gravure roll is 18m/ minute (speed is 0.9 than G/F), and also making kiss-coating length is 10mm, is 0.7N/mm at the tension force of the MD direction of the coating part of base film ²

After the coating coating fluid, be incorporated in the drying oven, making them in 20 seconds is that 40 ℃ and wind speed are the 5m/ dry section of second (the 1st drying process) by temperature, then, making them in 20 seconds is that 150 ℃ and wind speed are the 20m/ dry section of second (the 2nd drying process) by temperature, and then making them in 10 seconds is that 90 ℃ and wind speed are the 20m/ cooling zone of second (refrigerating work procedure) by temperature, makes its drying.Thus, make the near-infrared absorbing film of width (TD direction) continuously, and coil into drum for the length of 1.275m.The evaluation result of this near-infrared absorbing film is as shown in table 14.

Experiment 8-2

Except becoming 1.0N/mm at the tension force of the MD direction of the coating part of base film ²Outside, make long near-infrared absorbing film in the same manner continuously with experiment 8-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 14.

Experiment 8-3

Except becoming 1.2N/mm at the tension force of the MD direction of the coating part of base film ²Outside, make long near-infrared absorbing film in the same manner continuously with experiment 8-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 14.

Experiment 8-4

Except becoming 0.5N/mm at the tension force of the MD direction of the coating part of base film ²Outside, make long near-infrared absorbing film in the same manner continuously with experiment 8-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 14.

Experiment 8-5

Except the material with scraper becomes Sweden's formula steel, make long near-infrared absorbing film in the same manner continuously with experiment 8-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 14.

Experiment 8-6

Form with in the coating fluid near infrared ray absorption layer, equivalent increases cyclopentanone and toluene so that solid component concentration becomes 15 quality %, and speed is become 1.6 than the G/F change, in addition, make long near-infrared absorbing film in the same manner continuously with experiment 8-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 14.

Experiment 8-7

Except the contact angle change with scraper becomes 75 degree, speed is become 0.8 than the G/F change, make long near-infrared absorbing film in the same manner continuously with experiment 8-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 14.

Experiment 8-8

Except becoming 1.4N/mm at the tension force of the MD direction of the coating part of base film ²Outside, make long near-infrared absorbing film in the same manner continuously with experiment 8-1, and coil into drum.The evaluation result of this near-infrared absorbing film is as shown in table 14.

Experiment 8-9

Except becoming 0.3N/mm at the tension force of the MD direction of the coating part of base film ²Outside, try and test 8-1 and make long near-infrared absorbing film in the same manner continuously.But, the phenomenon of crawling has appearred in base film when the coating coating fluid, long near-infrared absorbing film can't be coiled into drum well.Thus, this film is not estimated.

Table 14

As shown in Table 14, with regard at experiment 8-1 to testing with regard to the near-infrared absorbing film that obtains among the 8-7, the transmitance of near infrared region is low, the transmitance height in the visible region.And then aberration Δ E (TD) is less in the maximal value of the TD of film direction, and tone has been subjected to inhibition in the variation of the TD of film direction.In addition, the outward appearance of near infrared ray absorption layer is also very good.

Relative therewith, with regard to the near-infrared absorbing film that obtains among the experiment 8-8, at the central portion of TD direction, banded striped occurs many on the MD direction, and the tonal variation of TD direction is also bigger.

Experiment 9

In this experimental example, except said determination, evaluation method, following mensuration, evaluation method have also been adopted.

[acid number of resin]

Make under 100 ℃, the condition of 133Pa dry 2 hours resin: 0.2g is dissolved in the chloroform of 20ml, is that the KOH ethanolic solution of 0.1mol% carries out titration with concentration, obtains per 10 ⁶The equivalent of g (1t) (equivalent/t).Wherein, used phenolphthalein as the indicator of judging usefulness.

[spectral characteristic]

Use self-recording spectrophotometer (Hitachi's system, U-2001 type), measured the light penetration of scope from wavelength 1100nm to wavelength 200nm.

[b ^*]

Use color colour difference meter (Japanese electric look industry system, ZE2000 system), measure with illuminant-C.

[environmental stability]

In 60 ℃ of temperature, relative humidity is to place sample 500 hours in 95% the atmosphere, subsequently, measures above-mentioned spectral characteristic and b ^*, calculate the maximal value of the variable quantity V (%) of transmitance with following formula (14), calculate Δ b with following formula (15) ^*

V＝100×|T _0(WL)-T _1(WL)|/T _0(WL) ……(14)

Δb ^*＝b ^* ₁-b ^* ₀ ……(15)

[coating spot]

Cut out the sample of 15cm * 15cm size from near-infrared absorbing film, and then be cut into 9 samples and the big or small 5cm * 5cm of being altogether.Use color colour difference meter (Japanese electric look industry system, ZE2000 type), these 9 samples are measured L ^*(use illuminant-C) obtains their maximal value and minimum value poor.

Experiment 9-1-1

1. the 1st adhesiveness modified layer is used the synthetic of resin

In the stainless steel autoclave that possesses stirring machine, thermometer and partial reflux formula condenser, put into dimethyl terephthalate (DMT) 163 mass parts, dimethyl isophthalate 163 mass parts, 1,4-butylene glycol 169 mass parts, ethylene glycol 324 mass parts and tetra-n-butyl titanate 0.5 mass parts, be warming up to 220 ℃ from 160 ℃, with carrying out ester exchange reaction in 4 hours.

Then, add fumaric acid 14 mass parts and decanedioic acid 203 mass parts, be warming up to 220 ℃ from 200 ℃ with 1 hour time, carry out esterification.Then, be warming up to 255 ℃, reaction system is slowly reduced pressure, under the pressure of 29Pa, reacted 1.5 hours then, obtain copolymer polyester resin (A-1).The copolymer polyester resin that obtains (A-1) is faint yellow transparence, and composition and the weight-average molecular weight measured with nuclear magnetic resonance spectroscopy (NMR) are shown in table 15.

Then, carry out the grafting of above-mentioned copolymer polyester resin (A-1).In the reactor that possesses stirring machine, thermometer, reflux and quantitative Dropping feeder, put into copolymer polyester resin (A-1) 75 mass parts, methyl ethyl ketone 56 mass parts and isopropyl alcohol 19 mass parts, at 65 ℃ of heating and stirrings down, dissolving resin.After complete dissolving resin, maleic anhydride 15 mass parts are added in the above-mentioned polyester liquid.

Then, styrene 10 mass parts and azo two (methyl pentane nitrile) 1.5 mass parts are dissolved in methyl ethyl ketone 12 mass parts, will drip in the above-mentioned polyester liquid, and then continue to stir 2 hours by the speed of the above-mentioned solution that obtains with 0.1ml/ minute.Get the sample of analyzing usefulness from reaction solution, make it to contain methyl alcohol 5 mass parts then.Then, in reaction solution, add water 300 mass parts and triethylamine 15 mass parts, stirred 1 hour.

Subsequently, make the internal temperature of reactor rise to 100 ℃, remove methyl ethyl ketone, isopropyl alcohol, excessive triethylamine, obtain faint yellow transparent aqueous dispersion graft resin (B-1a, the 1st adhesiveness modified resin) by distillation.The acid number of this aqueous dispersion graft resin (B-1a) of measuring with said method is 1400 equivalents/t.

2. the modulation of the coating fluid used of the 1st adhesiveness modified layer

Mixed water disperses aqueous dispersions 40 mass parts, water 24 mass parts and isopropyl alcohol 36 mass parts of 25 quality % of graft resin (B-1a), and then add propionic acid and negative ion is surfactant and makes it be respectively 1 quality % with respect to coating fluid, add colloidal silica particulate (daily output chemical industry system, ス ノ one テ Star Network ス OL; Mean grain size 40nm) aqueous dispersions and make with respect to the resin solid state component and count 5 quality % with silica volume is as coating fluid (C-1).

3. the formation of the making of base film and the 1st adhesiveness modified layer

Under the decompression of 133Pa and under 135 ℃, be the drying that 0.62dl/g and the PET resin particle that does not contain particle in fact carried out 6 hours to limiting viscosity.Subsequently, this particle is offered biaxial extruder, melt extrude the flakiness shape under about 280 ℃, remain in surface temperature on 20 ℃ the rotation chill roll and to apply method by static and its quenching is adhered to solidify, obtaining thickness is the not stretching PET thin slice of 1400 μ m.

Use the roller group and the infrared heater that have heated, this PET thin slice that do not stretch is heated to 100 ℃, go up 3.5 times of stretchings by the roller group that has difference at length direction (direction of travel) subsequently, obtain unilateral stretching PET film.

Then, adopt the reverse rollers method, on the two sides of PET film, be coated with above-mentioned coating fluid (C-1), and to make dried coating weight be 0.6g/m ², subsequently, drying is 20 seconds under 80 ℃.After the drying, continue under 120 ℃, on Width, to stretch 4.0 times with stenter, and then under the state of the length of the Width of fixed film, the 1st adhesiveness modified layer was heated 0.5 second under 260 ℃ by infrared heater, and then 3% the tension and relaxation of implementing Width under 200 ℃, 23 seconds condition handles, and obtained being laminated with the base film (D-1) of the 1st adhesiveness modified layer.

4. the formation of near infrared ray absorption layer

The near infrared ray absorption layer of the composition shown in the modulometer 16 forms uses coating fluid N3-1.Utilize gravure roll this coating fluid of coating on a face of the base film (D-1) of stacked the 1st adhesiveness modified layer, and to make dried coating weight be 7.0g/m ²,, obtain near-infrared absorbing film No.1 130 ℃ of following heated-air dryings 1 minute.In the near infrared ray absorption layer of this near-infrared absorbing film No.1, Ji Yinmoni diimmonium salt based compound is 3.4 quality % with respect to the content of resin.

The evaluation result of above-mentioned near-infrared absorbing film No.1 is shown among table 18 and Fig. 5.Wherein, Fig. 5 is that expression is measured the transmittance curve that obtains by the spectral characteristic of near-infrared absorbing film No.1.

Experiment 9-1-2

As the 1st adhesiveness modified layer resin, use following aqueous dispersion graft resin (B-1b) to replace aqueous dispersion graft resin (B-1a), in addition, 9-1-1 has obtained near-infrared absorbing film No.2 in the same manner with experiment.The evaluation result of this near-infrared absorbing film No.2 is also remembered in table 18.

With the aqueous dispersion graft resin (B-1a) of experiment 9-1-1 in the same manner, disperse graft resin (B-1b) from copolymer polyester resin (A-1) 75 mass parts, maleic anhydride 10 mass parts, styrene 7 mass parts, ethyl acrylate 8 mass parts synthetic waters.The acid number of the aqueous dispersion graft resin of measuring with said method (B-1b) that obtains is 950 equivalents/t.

Experiment 9-1-3

Copolymer polyester resin (A-2) with the synthetic in the same manner weight-average molecular weight that has the described composition of measuring by NMR of table 15 and measure by GPC of the copolymer polyester resin (A-1) of experiment 9-1-1.And then, except using this copolymer polyester resin (A-2), with the aqueous dispersion graft resin (B-1a) of experiment 9-1-1 in the same manner synthetic water disperse graft resin (B-2).The acid number of the aqueous dispersion graft resin of measuring with said method (B-2) that obtains is 1370 equivalents/t.

As the 1st adhesiveness modified layer resin, use above-mentioned aqueous dispersion graft resin (B-2) to replace aqueous dispersion graft resin (B-1a), in addition, 9-1-1 has obtained near-infrared absorbing film No.3 in the same manner with experiment.The evaluation result of this near-infrared absorbing film No.3 is also remembered in table 18.

Experiment 9-1-4

Except the resin that will be used near infrared ray absorption layer changed to following copolymer polyester resin, 9-1-1 had made near-infrared absorbing film No.4 in the same manner with experiment.The evaluation result of this near-infrared absorbing film No.4 is also remembered in table 18.

5. near infrared ray absorption layer forms synthesizing with resin

In the autoclave that possesses thermometer, stirring machine, put into dimethyl terephthalate (DMT) 136 mass parts, dimethyl isophthalate 58 mass parts, ethylene glycol 96 mass parts, tristane dimethanol 137 mass parts, antimony trioxide 0.09 mass parts, be warming up to 220 ℃ from 170 ℃, with carrying out ester exchange reaction in 180 minutes.Then, make the temperature of reaction system be warming up to 245 ℃, the pressure control of system below the above 10mmHg of 1mmHg, is continued to react 180 minutes, obtain copolymer polyester resin.The limiting viscosity of the copolymer polyester resin that obtains is 0.40dl/g, and Tg is 90 ℃.In addition, with regard to the copolymerization ratio of components of analyzing by NMR, with respect to 100 moles of % of sour composition, 71 moles of % of terephthalic acid (TPA), 29 moles of % of m-phthalic acid are with respect to 100 moles of % of pure composition, ethylene glycol is 28 moles of %, and the tristane dimethanol is 72 moles of %.

Experiment 9-1-5

Except the resin that near infrared ray absorption layer is formed usefulness becomes the following acrylic acid series polymeric compounds, 9-1-1 has made near-infrared absorbing film No.5 in the same manner with experiment.The evaluation result of this near-infrared absorbing film No.5 is also remembered in table 18.

6. near infrared ray absorption layer is used the synthetic of resin

In reaction vessel, add n-BMA 60 mass parts, ethyl acetate 120 mass parts, methyl alcohol 120 mass parts, azoisobutyronitrile 0.51 mass parts as monomer, under nitrogen atmosphere, when 60 ℃ are stirred down, carry out 8 hours reaction.After reaction, reaction solution put into polymkeric substance is precipitated again and reclaim.The weight-average molecular weight of the acrylic acid series polymeric compounds that obtains is 100000.

Experiment 9-1-6

Adopt and the identical method of copolymer polyester resin (A-1), synthetic to have a table 15 described by the composition of NMR measurement and the copolymer polyester resin (A-3) of weight-average molecular weight.Wherein, the acid number of the copolymer polyester resin of measuring with said method (A-3) is 50 equivalents/t.As the 1st adhesiveness modified layer, use copolymer polyester resin (A-3) to replace aqueous dispersion graft resin (B-1a), in addition, 9-1-1 obtains near-infrared absorbing film No.6 in the same manner with experiment.The evaluation result of this near-infrared absorbing film No.6 is also remembered in table 18.

Experiment 9-1-7

Using following co-polypropylene acid is that resin (A-4) replaces aqueous dispersion graft resin (B-1a), and in addition, 9-1-1 obtains near-infrared absorbing film No.7 in the same manner with experiment.But, form with in the coating fluid, add butyl cellosolve so that co-polypropylene acid is resin (A-4) can dissolve in the 1st adhesiveness modified layer.Wherein, the co-polypropylene acid of measuring with said method is that the acid number of resin (A-4) is 2 equivalents/t.The evaluation result of this near-infrared absorbing film No.7 is also remembered in table 18.

(co-polypropylene acid is the synthetic of resin (A-4))

In reaction vessel, adding is as methyl methacrylate 42 mass parts, ethyl acrylate 17.4 mass parts, acrylic acid 2-hydroxyl ethyl ester 0.6 mass parts of monomer, ethyl acetate 120 mass parts, methyl alcohol 120 mass parts as solvent, azoisobutyronitrile 0.51 mass parts as catalyzer, under nitrogen atmosphere, when 60 ℃ are stirred down, carry out 8 hours reaction.After reaction, reaction solution is put in the hexane, polymkeric substance is precipitated again, obtaining co-polypropylene acid is resin (A-4).The co-polypropylene acid that obtains is that the weight-average molecular weight of resin (A-4) is 100000.

Experiment 9-1-8

Except the near infrared absorbing coloring matter that will contain in the near infrared ray absorption layer only change become dithiol metal complex based compound (Mitsui Chemicals system, SIR-128) outside, with the experiment 9-1-1 obtained near-infrared absorbing film No.8 in the same manner.The evaluation result of this near-infrared absorbing film No.8 is also remembered in table 18.

Experiment 9-1-9

Except the near infrared ray absorption layer of using the composition shown in the table 17 forms with the coating fluid, 9-1-4 has obtained near-infrared absorbing film No.9 in the same manner with experiment.The evaluation result of this near-infrared absorbing film No.9 is also remembered in table 18.

Table 15

In table 15, the composition of each compound is represented the composition of the composition that is derived from these compounds in the resin, is derived from the one-tenth component of aromatic dicarboxylic acid in the composition that is derived from sour composition 100% in " aromatic component " expression resin.

Table 16

Table 17

Table 18

Wherein, in table 18, project (a) to (e) is meant following evaluation content.

(a): light penetration from wavelength 820nm to wavelength 1100nm

(b): light penetration from wavelength 450nm to wavelength 650nm

(c): the maximal value of the variable quantity V (%) of the light penetration at above-mentioned wavelength region may place

(d)：Δb ^*

(e): Ji Yinmoni diimmonium salt based compound is with respect to the content (quality %) of resin.

Shown in table 18, near-infrared absorbing film No.1 to No.5 is in environmental stability is estimated, and the variation of spectral characteristic and the variation of tone have been subjected to inhibition, and the absorption of near infrared range is bigger, and the transmitance of visible region is also bigger.Relative therewith, near-infrared absorbing film No.6 and No.7 are in environmental stability is estimated, and the variation of spectral characteristic and tone is bigger.

In addition, near-infrared absorbing film No.8 does not contain the reference example of Ji Yinmoni diimmonium salt based compound as near infrared absorbing coloring matter, although the environmental stability evaluation result is good, and the absorption difference of near infrared range.Near-infrared absorbing film No.9 is the reference example that surpasses the scope that is fit to as the content of the Ji Yinmoni diimmonium salt based compound of near infrared absorbing coloring matter, if No.1 to No.5 compares with near-infrared absorbing film, the spectral characteristic during environmental stability is estimated and the variation of tone are bigger.

Experiment 9-2

Experiment 9-2-1

Use the high frequency magnetic control sputtering device, form 380 on the near infrared ray absorption layer surface of the near-infrared absorbing film No.1 that in experiment 9-1-1, makes

Stannic oxide layer, then use the DC magnetic control sputtering device, form 200

Silver layer, and then adopt said method to form 410

Stannic oxide layer, be provided with the electromagnetic wave blocking layer thus.The surface resistance of near-infrared absorbing film No.1 behind the formation electromagnetic wave blocking layer is about 4 Ω/.

Experiment 9-2-2

On the surface of the 1st adhesiveness modified layer of the side that near infrared ray absorption layer is not set of the near-infrared absorbing film No.1 that in experiment 9-1-1, makes, hard conating is set.When this hard conating is set, adopt and to be coated with method firmly and to be coated with on above-mentioned the 1st adhesiveness modified layer surface that to add benzophenone 4 mass parts to epoxy acrylic be the ultraviolet-curing resin composition that forms in resin 100 mass parts, under 80 ℃, carry out 5 minutes predrying, pass through 500mJ/cm then ²Ultraviolet ray irradiation make its curing.The thickness of the hard conating after the curing is 5 μ m.

Experiment 9-2-3

On the near infrared ray absorption layer surface of the near-infrared absorbing film No.1 that in experiment 9-1-1, makes, by acrylic acid series ultraviolet hardening bonding agent coating thickness is the Copper Foil of 9 μ m, use photoresist to make above-mentioned Copper Foil form pattern, implement etch processes and formed the electromagnetic wave blocking layer.The Copper Foil live width of this moment is about 15 μ m, and spacing is 115 μ m, and numerical aperture is 75%.

Experiment 9-2-4

On the surface of the 1st adhesiveness modified layer of the side that near infrared ray absorption layer is not set of the near-infrared absorbing film No.1 that in experiment 9-1-1, makes, adopt the coating of photogravure coating process to contain the coating fluid of composition as described below, and with high-pressure sodium lamp with 300mJ/cm ²Shine, forming thickness is the solidfied material layer of 3.5 μ m, and wherein said coating fluid contains five acrylic acid dipentaerythritol ester (photopolymerization monomer), 100 mass parts, diethoxy benzophenone (photoreaction initiator) 2 mass parts, silicone-based surfactant 1 mass parts, methyl ethyl ketone 50 mass parts, ethyl acetate 50 mass parts and isopropyl alcohol 50 mass parts.And then, adopt vacuum vapour deposition with the electron beam heating, and the thin layer of formation MgF on the surface of this layer (thickness: 0.1 μ m), as anti-reflection layer.42 molded breadth plasma displays (Fujitsu's system, front face side PDS4211J-H) is provided with this film, and with anti-reflection layer as the identification side, the result does not see the remarkable reflection of exterior light.

Experiment 9-3

Unload 42 molded breadth plasma display (Fujitsu's systems, PDS4211J-H) front panel, replace and near-infrared absorbing film No.1 is set, faulty operation do not occur near the infrared remote controller of result being arranged at the plasma display front as the near-infrared absorbing light filter.

Experiment 9-4

Form with in the coating fluid of N1-3 in the near infrared ray absorption layer shown in the table 16, add silicone-based surfactant (ダ ウ コ one ニ Application グ system, ペ イ Application Star De 57; HLB=6.7) in addition 0.034 mass parts, has made long near-infrared absorbing film in the same manner with experiment 9-1-1.With regard to the spectral characteristic of the near-infrared absorbing film that obtains, wavelength 820nm is 13% to the maximum transmission of wavelength 1100nm, wavelength 450nm to the minimum transmitance of wavelength 650nm be 65%.And then, in long near-infrared absorbing film in the scope of 10m continuously, visualization the outward appearance of applicator surface, but do not see shortcoming such as coming off of coating layer.

Experiment 9-5

Experiment 9-5-1

In experiment 9-1-1, after the coating near infrared ray absorption layer forms with coating fluid N1-3, carry out 2 stage dryings at once, promptly under 40 ℃, carry out 1 minute drying, and then under 130 ℃, carry out 1 minute drying.In addition, made long near-infrared absorbing film in the same manner with experiment 9-1-1.With regard to the spectral characteristic of the near-infrared absorbing film that obtains, wavelength 820nm is 13% to the maximum transmission of wavelength 1100nm, wavelength 450nm to the minimum transmitance of wavelength 650nm be 65%.In addition, the length direction that cuts out film from the near-infrared absorbing film of the length of having made is the sample of 15cm for 15cm, Width.Then, the surface of the sample that visualization has cut out, but do not see the coating spot.And then, the sample that has cut out is cut into 5cm * 5cm, gather totally 9 samples.The L of 9 samples that obtain ^*The maximal value of value and the difference of minimum value are 0.6.

Experiment 9-5-2

In experiment 9-5-1, be coated with near infrared ray absorption layer formation with after spending 5 seconds after the coating fluid N1-3, make its 1 stage drying of 1 minute of drying under 130 ℃, in addition, made long near-infrared absorbing film in the same manner with experiment 9-5-1.With regard to the spectral characteristic of the near-infrared absorbing film that obtains, wavelength 820nm is 13% to the maximum transmission of wavelength 1100nm, wavelength 450nm to the minimum transmitance of wavelength 650nm be 65%.In addition, cut out film in the same manner with experiment 9-16.Then, the surface of the sample that visualization has cut out, the result has seen the coating spot.And then 9-5-1 cuts out 9 samples in the same manner with experiment.The L of 9 samples that obtain ^*The maximal value of value and the difference of minimum value are 2.0.

Experiment 9-6

At the described near infrared ray absorption layer formation coating fluid N1-3 that is used for testing 9-1-1 of table 16, be contained near pigment (the consonance fermentation industry system that absorption is arranged the neon light emission wavelength, SD-184) 0.067 mass parts, in addition, obtained long near-infrared absorbing film in the same manner with experiment 9-1-1.The near-infrared absorbing film that obtains optionally has precipitous absorption peak at wavelength 585nm place, and the transmitance at this wavelength place is 30%, in addition, and with coming to the same thing of experiment 9-1-1.

Experiment 9-7

(1) contains the modulation of the masterbatch of ultraviolet light absorber

Mixing dry cyclic imide acid esters is ultraviolet light absorber (サ イ テ Star Network system, CYASORB UV3638; 2,2 '-(1, the 4-phenylene) two (4H-3,1-benzoxazine-4-ketone)) 10 mass parts and do not contain polyethylene terephthalate (PET) resin (Japan's weaving system of particle, ME553) 90 mass parts, use mixing extruder to carry out melting mixing, be extruded as the strand shape from metal mouth nozzle.The extrusion temperature of this moment is 285 ℃, and finding time is 7 minutes.Then, cool off above-mentioned strand, cut the section of making masterbatch then with tank.

(2) be laminated with the making of the base film of the 1st adhesiveness modified layer

Under 135 ℃, be that (Japan's weaving system, ME553) 90 mass parts, the above-mentioned masterbatch that contains ultraviolet light absorber 10 mass parts are carried out 6 hours drying under reduced pressure (1Torr:1.33 * 10 for the particle of 0.62dl/g and the PET resin that does not contain particle to limiting viscosity ²Pa), offer extruder then.Making fusing department from extruder, kneading part, polymer pipe, gear-type pump, be 280 ℃ to the resin temperature of filtrator, is 275 ℃ in polymer pipe subsequently, and the metal mouth by flat-die is extruded into laminar.Used the filter materials (nominal filtering accuracy: can remove 95% the above particle of 10 μ m) of stainless steel sintered body to carry out in the above-mentioned filtrator.In addition, making the resin temperature in the flat-die is 275 ℃.Use static to apply casting, making above-mentioned being melted be extruded into laminar resin, to be twisted in surface temperature be that cooling curing makes non-stretched film simultaneously on 30 ℃ the curtain coating drum (roller diameter: 400mm Φ, Ra:0.1 μ m is following).The spray volume of this moment is 48kg/hr, the wide 300mm of the non-stretched film that obtains, thick 1400 μ m.Below, 9-1-1 has made the base film of the length that stacked the 1st adhesiveness modified layer forms on the two sides in the same manner with experiment.

(3) formation of near infrared ray absorption layer

On by an above-mentioned face that the adhesiveness modified layer is laminated in the base film that forms on the two sides that obtains, 9-1-1 is uniformly set near infrared ray absorption layer with experiment, makes long near-infrared absorbing film.

4. light fastness test

About the near-infrared absorbing film that in above-mentioned, obtains, carried out sunproof accelerated test.In the black panel temperature is that 63 ℃, humidity are 50%, illumination is 50W/m ², irradiation time is under 24 hours the condition, (ス ガ testing machine corporate system XL-75) has been carried out exposure experiment, measures the transmitance at very big absorbing wavelength place of the near infrared range of the sample before and after this test to utilize ultraviolet self-discoloration meter.Transmitance before the test is made as T, the transmitance after the test is made as T ₁, obtaining near-infrared absorbing ability survival rate R (%) by following formula (16) by this measured value, the result is more than 90%.

R(％)＝(T/T ₁)×100 ……(16)

Industrial utilizability

Near-infrared absorbing filter of the present invention, identical with in the past near-infrared absorbing filter, Not only can absorb the otiose near infrared ray from display emission, prevent the mistake behaviour of precision instrument Do, also owing to the specifically existence of surfactant, the formative of near infrared ray absorption layer (outward appearance) Become very good, so the quality of completed near-infrared absorbing filter is also outstanding.

In addition, not only can absorb the light of the orange wavelength that makes the excitation reduction to carry out complementary color, also tool Antireflection and ultraviolet-absorbing are arranged, so optical characteristics is outstanding, and durability is outstanding, especially Can suppress the deterioration by the UV-induced near infrared absorbing coloring matter that contains in the outer light.

And then, because by getting involved the adhesiveness that is consisted of by the adhesiveness modified resin with specific acid number Modified layer has formed near infrared ray absorption layer, so even at hot and humid lower long-time placement, spectrum The variation of characteristic or tone is littler. In addition because with resin as the main composition raw material, so processing Property is outstanding, light weight and can also suppress cost lower.

In addition, with regard to near-infrared absorbing film of the present invention, tone is less in the variation of the length direction of long film, so can reduce the poor of tone that the chassis by manufactured plasma display causes, simultaneously, tone is also less in the variation of the Width of film, so be used for plasma display with under the situation of light filter, can in whole display frame, suppress the variation of tone, the outward appearance of near infrared ray absorption layer is good, optical defect is few, so be suitable as the optics light filter that requirements such as plasma display have the display device etc. of absorption near infrared ray function.

And then, with regard to near-infrared absorbing film of the present invention, under the condition of many films of not fitting, realized multiple stratification, so easy filming, good near-infrared absorbing ability or antireflection ability can be guaranteed, and then the light permeability of outstanding visible region can be guaranteed.Then,, can improve operation to the attaching that is attached thing (plasma display) by filming, economical also outstanding.

By manufacture method of the present invention, can make near-infrared absorbing film well with very outstanding outward appearance.

Claims (24)

1. near-infrared absorbing film, it is the near-infrared absorbing film that transparent base film is provided with the near infrared ray absorption layer that is made of following composition, contain the near infrared absorbing coloring matter and the resin that have very big absorption at wavelength 800nm～1200nm place in the described composition, wherein, the HLB that contains 0.01～2.0 quality % in described composition is 2～12 surfactant.

2. near-infrared absorbing film as claimed in claim 1, wherein,

Described surfactant is that silicone-based surfactant or fluorine are surfactant.

3. near-infrared absorbing film as claimed in claim 1, wherein,

Also contain the complementary color pigment that has very big absorption at wavelength 550～620nm place in the described near infrared ray absorption layer.

4. near-infrared absorbing film as claimed in claim 1, wherein,

Contain aromatic series Ji Yinmoni (diimmonium) salt based compound in the described near infrared absorbing coloring matter.

5. near-infrared absorbing film as claimed in claim 1, wherein,

Described transparent base film is made of the laminate film more than at least 3 layers, and the layer that contains ultraviolet light absorber is set at the part beyond the top layer.

6. near-infrared absorbing film as claimed in claim 1, wherein,

Described near infrared ray absorption layer is the adhesiveness modified layer of the above adhesiveness modified resin of 200 equivalents/t as major component by getting involved with acid number, is formed on the transparent base film.

7. near-infrared absorbing film as claimed in claim 6, wherein,

Described adhesiveness modified resin be on polyester based resin grafting to have the polyester that the acid anhydrides of at least 1 two key forms be graft copolymer.

8. near-infrared absorbing film as claimed in claim 1, wherein,

The transmitance of the light of the wavelength region may of 450～650nm is more than 55%, and the transmitance of the light of the wavelength region may of 820～1100nm is below 20%.

9. near-infrared absorbing film as claimed in claim 3, wherein,

The transmitance of the light of the wavelength region may of 550～600nm is 10～60%, and the transmitance of the light of the wavelength region may of 820～1100nm is below 20%.

10. near-infrared absorbing film as claimed in claim 1, wherein,

Be arranged on described transparent base film on the opposite face of near infrared ray absorption layer on, be provided with anti-reflection layer.

11. near-infrared absorbing film volume, be that the described near-infrared absorbing film of claim 1 is rolled into the near-infrared absorbing film volume that forms more than the long 100m, more than the wide 0.5m, wherein, the maximal value that is rolled into the aberration Δ E on the length direction this near-infrared absorbing film, that obtain by following determination method (A) of web-like is below 2.0

(A) when measuring the tone of described film, on the length direction of this film, one end in the constant zone that the film rerum natura is stable is as the 1st end, with the other end as the 2nd end, at this moment, carry out primary mensuration at the inboard 2m of the 1st end with interior, in addition, carry out last mensuration with interior, once measure every about 10m from primary locating simultaneously at the inboard 2m of the 2nd end, calculate the aberration Δ E on the length direction that defines with following formula that respectively locates

Aberration Δ E=[(L on the length direction _a-L _m) ²+ (a _a-a _m) ²+ (b _a-b _m) ²] ^1/2

Here, L _m, a _m, b _mBe meant tone L, a, the b that respectively locate, L _a, a _a, b _aBe meant all tone L, a that locate, the mean value of b.

12. near-infrared absorbing film volume, it is that the described near-infrared absorbing film of claim 1 is rolled into the near-infrared absorbing film volume that forms more than the long 100m, more than the wide 0.5m, wherein, the maximal value that is rolled into the aberration Δ E on the Width this near-infrared absorbing film, that obtain by following determination method (B) of web-like is below 1.0;

(B) when measuring the tone of described film, on the Width of this film, one end in the constant zone that the film rerum natura is stable is as the 1st end, with the other end as the 2nd end, at this moment, carry out primary mensuration at the inboard 0.1m of the 1st end with interior, in addition, carry out last mensuration at the inboard 0.1m of the 2nd end with interior, simultaneously between primary the locating to the end of locating, measure roughly uniformly-spaced to carry out 3 places, calculate that this 5 place locates with the aberration Δ E on the Width of following formula definition

Aberration Δ E=[(L on the Width _a-L _m) ²+ (a _a-a _m) ²+ (b _a-b _m) ²] ^1/2

Here, L _m, a _m, b _mBe meant tone L, a, the b that respectively locate, L _a, a _a, b _aBe meant all tone L, a that locate, the mean value of b.

13. the manufacture method of a near-infrared absorbing film, make its drying and the formation near infrared ray absorption layer after wherein on transparent base film, being coated with the coating fluid that contains near infrared absorbing coloring matter, resin, surfactant and organic solvent, using HLB as described surfactant is 2～12 surfactant, contains this surfactant of 0.01～2.0 quality % simultaneously with respect to the solid state component of described coating fluid.

14. the manufacture method of near-infrared absorbing film as claimed in claim 13, wherein,

In the drying process after the described coating fluid of coating, the drying process that utilizes hot blast is divided into 2 multistages more than the stage, in the drying process in the 1st stage, carrying out the drying below 120 seconds more than 10 seconds under 20～80 ℃, in the highest drying process of baking temperature after the 2nd stage, carrying out the drying below 60 minutes more than 5 seconds under 80～180 ℃.

15. the manufacture method of near-infrared absorbing film as claimed in claim 13, wherein,

As the coating process of described coating fluid, adopt reverse photogravure method.

16. the manufacture method of near-infrared absorbing film as claimed in claim 15, wherein,

In described reverse photogravure method, the diameter of photogravure is made as below the 80mm.

17. the manufacture method of a near-infrared absorbing film volume, the coating fluid that wherein will contain near infrared absorbing coloring matter, resin, surfactant and organic solvent is coated on the transparent base film continuously and carries out drying, form near infrared ray absorption layer, be rolled into the near-infrared absorbing film that obtains more than the long 100m afterwards, more than the wide 0.5m and make the near-infrared absorbing film volume, wherein

Using HLB as described surfactant is 2～12 surfactant, contains this surfactant of 0.01～2 quality % simultaneously with respect to the solid state component of described coating fluid,

At the described coating fluid of coating and after carrying out drying, light penetration by online mensuration tone and/or specific wavelength, regulate the coating condition and/or the drying condition of coating fluid according to its measurement result, the maximal value of the aberration Δ E on the length direction that will obtain by following determination method (A) is controlled at below 2.0 thus;

(A) when measuring the tone of described film, on the length direction of this film, one end in the constant zone that the film rerum natura is stable is as the 1st end, with the other end as the 2nd end, at this moment, carry out primary mensuration at the inboard 2m of the 1st end with interior, in addition, carry out last mensuration with interior, once measure every about 10m from primary locating simultaneously at the inboard 2m of the 2nd end, calculate the aberration Δ E on the length direction that defines with following formula that respectively locates

Aberration Δ E=[(L on the length direction _a-L _m) ²+ (a _a-a _m) ²+ (b _a-b _m) ²] ^1/2

Here, L _m, a _m, b _mBe meant tone L, a, the b that respectively locate, L _a, a _a, b _aBe meant all tone L, a that locate, the mean value of b.

18. the manufacture method of near-infrared absorbing film volume as claimed in claim 17, wherein,

The photogravure applying device that use has gravure roll carries out the coating of described coating fluid, and the rotational speed G of described gravure roll is made as 0.8～1.5 with respect to the speed of the speed of travel F of film than G/F, and the unit of described G and F is m/ minute.

19. the manufacture method of near-infrared absorbing film volume as claimed in claim 18, wherein,

Use following device as described photogravure applying device, promptly, the gravure roll that has by reverse rotation is gathered together coating fluid and is utilized the mechanism of the coating fluid that it is unnecessary that scraper is flattened from the feed flow dish, and the part that contacts with gravure roll at least in the scraper is ceramic or nickel system.

20. the manufacture method of a near-infrared absorbing film volume, the coating fluid that wherein will contain near infrared absorbing coloring matter, resin, surfactant and organic solvent is coated on the transparent base film continuously and carries out drying, form near infrared ray absorption layer, this near-infrared absorbing film that will obtain afterwards is rolled into more than the long 100m, wide 0.5m is above and make the near-infrared absorbing film volume, wherein

Using HLB as described surfactant is 2～12 surfactant, contains this surfactant of 0.01～2 quality % simultaneously with respect to the solid state component of described coating fluid,

Be coated with described coating fluid by the kiss-coating mode, the tension force by the film length direction in the coating part that makes transparent base film is 0.5N/mm ²More than, 1.2N/mm ²Below, the maximal value of the aberration Δ E on the Width that will obtain by following determination method (B) is controlled at below 1.0;

(B) when measuring the tone of described film, on the Width of this film, one end in the constant zone that the film rerum natura is stable is as the 1st end, with the other end as the 2nd end, at this moment, carry out primary mensuration at the inboard 0.1m of the 1st end with interior, in addition, carry out last mensuration at the inboard 0.1m of the 2nd end with interior, simultaneously between primary the locating to the end of locating, measure roughly uniformly-spaced to carry out 3 places, calculate that this 5 place locates with the aberration Δ E on the Width of following formula definition

Aberration Δ E=[(L on the Width _a-L _m) ²+ (a _a-a _m) ²+ (b _a-b _m) ²] ^1/2

Here, L _m, a _m, b _mBe meant tone L, a, the b that respectively locate, L _a, a _a, b _aBe meant all tone L, a that locate, the mean value of b.

21. the manufacture method of near-infrared absorbing film volume as claimed in claim 20, wherein,

The photogravure applying device that use has gravure roll carries out the coating of described coating fluid, and the rotational speed G of described gravure roll is made as 0.8～1.5 with respect to the speed of the speed of travel F of film than G/F, and the unit of described G and F is m/ minute.

22. the manufacture method of near-infrared absorbing film volume as claimed in claim 21, wherein,

Use following device as described photogravure applying device, promptly, the gravure roll that has by reverse rotation is gathered together coating fluid and is utilized the mechanism of the coating fluid that it is unnecessary that scraper is flattened from the feed flow dish, and the part that contacts with gravure roll at least in the scraper is ceramic or nickel system.

23. the manufacture method of near-infrared absorbing film volume as claimed in claim 21, wherein,

In the drying process after the described coating fluid of coating, the drying process that utilizes hot blast is divided into 2 multistages more than the stage, in the drying process in the 1st stage, carrying out the drying below 120 seconds more than 10 seconds under 20～80 ℃, in the highest drying process of baking temperature after the 2nd stage, carrying out the drying below 60 minutes more than 5 seconds under 80～180 ℃; And then, after multistage heated-air drying operation, carry out refrigerating work procedure, utilize the wind that temperature is less than or equal to the glass temperature of the resin that constitutes near infrared ray absorption layer to cool off in the described refrigerating work procedure.

24. near-infrared absorbing light filter, it is the near-infrared absorbing light filter that is set at the plasma display front, wherein, this near-infrared absorbing light filter is to use the described near-infrared absorbing film of claim 10 to form, and the anti-reflection layer of being arranged to described near-infrared absorbing film during use is positioned at face side, near infrared ray absorption layer is positioned at described display side.

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