JP2016033666A - Film laminate and polarizing plate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polarizer protective film with a protective film having such properties that upon peeling the protective film, no glue remains on a surface of the polarizer protective film and that when used in a liquid crystal display device including an optical transparent resin present between a liquid crystal panel and a front plate, the polarizer protective film gives excellent appearance quality and visibility without inducing air bubbles on an interface with the optical transparent resin, and to provide a polarizing plate.SOLUTION: A film laminate comprises a polarizer protective film 10 having a surface-treated layer 12, and a protective film 20 having an adhesive layer 22 and laminated at the adhesive layer 22 side on the surface of the surface treated layer 12. Only the surface-treated layer 12 in the surface-treated layer 12 and the adhesive layer 22 contains an organic siloxane. In the measurement of a relative intensity value of negative ions on the surface of the surface-treated layer 12 by TOF-SIMS, relative intensity values X, Y obtained before the protective film 20 is laminated and immediately after the protective film is peeled, respectively, satisfy Y/X<4 for all of specific negative ions. A polarizer using the film laminate is also disclosed.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a film laminate in which a protective film is laminated on the surface of a polarizer protective film for laminating and protecting the polarizer layer, and a polarizing plate using the same.

  In general, a liquid crystal display device includes a backlight, a liquid crystal panel including a liquid crystal cell, a back side polarizing plate disposed on the backlight side of the liquid crystal cell, and a front side polarizing plate disposed on the viewing side of the liquid crystal cell. Consists of. The polarizing plate usually has a structure in which a polarizer protective film, for example, a transparent resin film typified by triacetyl cellulose (TAC) is bonded to one or both sides of a polarizer (polarizing film) via an adhesive layer or the like. It has become. The polarizer protective film disposed on the viewing side of the front-side polarizing plate is often provided with a surface treatment layer for imparting a predetermined function to the polarizer protective film such as a hard coat layer or an antiglare layer.

  In recent years, liquid crystal display devices have been required to further improve visibility against the background of 3D (three-dimensional) compatible applications. As a liquid crystal display configuration for improving visibility, a front panel such as a glass plate is placed on the viewing side of the liquid crystal panel with a certain space, and an optically transparent resin (optical transparent resin) is placed in this space. The structure to fill is conventionally known (for example, Patent Documents 1 and 2). In such a liquid crystal display device in which an optical transparent resin is interposed between the liquid crystal panel and the front plate, an air layer is formed between the liquid crystal panel and the front plate (not filled with the optical transparent resin). Thus, irregular reflection of external light and backlight light incident on the liquid crystal panel can be reduced, so that higher contrast and color reproducibility can be realized. It is also advantageous from the viewpoint of impact resistance.

JP 2008-282000 A JP 2009-186957 A

  When the optical transparent resin is filled between the liquid crystal panel and the front plate, the resin composition before curing is applied to the front surface of the liquid crystal panel, that is, the polarizer protective film surface on the front side (viewing side), A method of laminating a front plate thereon and then curing the resin composition is generally used. At this time, when the wettability of the resin composition to the surface of the polarizer protective film is low (the surface of the polarizer protective film is easy to play the resin composition), the step of laminating the front plate and the step of curing the resin composition, Since the part where the resin composition is repelled becomes air bubbles and the appearance quality is impaired, and in some cases, the refraction, scattering, and reflection of light by the air bubbles causes the problem that the visibility of the liquid crystal display device is lowered. Is required not to play the resin composition.

  On the other hand, a protective film (also referred to as a peeling film or a surface protective film) that can be peeled off may be bonded to the surface of the polarizer protective film in order to protect the surface during production. This protective film is peeled and removed, for example, when the resin composition before curing is applied to the surface of the polarizer protective film.

  However, when the protective film is peeled off, a part of the adhesive of the film may remain on the surface of the polarizer protective film (so-called adhesive residue). The surface on which the adhesive residue is generated easily repels the resin composition and generates bubbles.

  Therefore, when the protective film is peeled off, no adhesive residue is generated on the surface of the polarizer protective film, and the present invention is applied to a liquid crystal display device in which an optical transparent resin is interposed between the liquid crystal panel and the front plate. A polarizer protective film with a protective film (film laminate) and a polarizing plate using the same can be obtained without causing bubbles at the interface with the optical transparent resin. With the goal.

The present invention relates to a film laminate including a polarizer protective film and a protective film laminated on one surface thereof, and relates to time-of-flight secondary ion mass spectrometry (TOF-). The relative intensity value of negative ions when the surface is measured by SIMS), where X is the relative intensity value before lamination of the protective film, and Y is the relative intensity value immediately after the protective film is peeled, _{^{-, CH 3 SiO -, SiO}} 2 -, CH 3 SiO 2 -, C 3 H 9 SiO -, C 3 H 9 Si 2 O 3 -, C 5 H 15 Si 2 O 2 -, C 5 H 15 Si 3 For all negative ions of O ₄ ⁻ and C ₇ H ₂₁ Si ₃ O ₃ ⁻ , the following formula (1):
Y / X <4 (1)
It is characterized by satisfying.

The film laminate of the present invention is preferably the following formula (2):
Y / X <2.5 (2)
Meet.

  In one preferable embodiment, the polarizer protective film includes a base film and a surface treatment layer laminated on one surface thereof, and the protective film is laminated on the surface of the surface treatment layer. Examples of the surface treatment layer include a hard coat layer, an antiglare layer, a light diffusion layer, and an antireflection layer.

  Moreover, this invention provides a polarizing plate provided with the film laminated body which concerns on the said invention, and the polarizer layer laminated | stacked on the surface on the opposite side to the side by which the protective film in a polarizer protective film is laminated | stacked.

  According to the film laminate and the polarizing plate of the present invention, adhesive residue that causes repelling of the resin composition that forms the optical transparent resin even when the protective film is peeled off, and generation of bubbles at the interface with the optical transparent resin associated therewith Can be effectively suppressed. As a result, the appearance quality and visibility of the liquid crystal display device can be improved.

It is a schematic sectional drawing which shows an example of the film laminated body of this invention. It is a schematic sectional drawing which shows an example of the polarizing plate of this invention.

Hereinafter, embodiments of the present invention will be described in detail.
<Film laminate>
FIG. 1 is a schematic cross-sectional view showing an example of the film laminate of the present invention. With reference to FIG. 1, the film laminated body which concerns on this invention is a polarizer protective film with a protective film provided with the protective film 20 laminated | stacked on the polarizer protective film 10 and the one surface. The polarizer protective film 10 is a film for laminating and protecting the polarizer layer, and is a member constituting a polarizing plate. The polarizer protective film 10 includes at least a base film 11 that is a transparent resin film, and includes a base film 11 and a surface treatment layer 12 laminated on one surface thereof in a preferred embodiment. The surface treatment layer 12 is a layer that imparts a predetermined function such as an optical function to the polarizer protective film 10 (and thus the polarizing plate), such as a hard coat layer, an antiglare layer, a light diffusion layer, an antireflection layer, and the like. Can be. The surface treatment layer 12 can be laminated on the base film 11 via other layers such as an adhesive layer, a pressure-sensitive adhesive layer, a primer layer, and other surface treatment layers.

  The protective film 20 is a film having releasability that is bonded to protect the surface of the polarizer protective film 10 (in particular, the surface of the surface treatment layer 12 in the case of having the surface treatment layer 12) for a certain period of time. The support film 21 and the pressure-sensitive adhesive layer 22 that can be peeled off from the polarizer protective film 10 are laminated on one surface thereof. The certain period is, for example, from the production of the polarizer protective film to the production of the liquid crystal display device (the step of applying the optical transparent resin-forming resin composition to the surface of the polarizer protective film).

The film laminate of the present invention is the surface of the polarizer protective film 10 to which the protective film 20 is bonded (the surface of the surface treatment layer 12 when the surface treatment layer 12 is provided, and a plurality of surface treatment layers are laminated). In particular, it has characteristics in the surface characteristics of the surface treatment layer of the outermost layer), specifically, time-of-flight secondary ion mass spectrometry (Time-of-Flight Secondary Ion Mass Spectrometry): When the relative intensity value of negative ions when the surface is measured by TOF-SIMS), the relative intensity value before lamination of the protective film is X, and the relative intensity value immediately after the protective film is peeled is Y For all negative ions belonging to group A shown below, the following formula (1):
Y / X <4 (1)
And preferably the following formula (2):
Y / X <2.5 (2)
Meet. X and Y satisfy X> 0 and Y> 0, respectively.

[Group A]
Si ^- [ion count (hereinafter the same): 28]
CH ₃ SiO ^- [59]
SiO ₂ ^- [60]
CH ₃ SiO ₂ ^- [75]
C ₃ H ₉ SiO ^- [89]
_{C 3 H 9 Si 2 O 3} - [149]
_{C 5 H 15 Si 2 O 2} - [163]
_{C 5 H 15 Si 3 O 4} - [223]
_{C 7 H 21 Si 3 O 3} - [237]
Below, the negative ion which comprises the said group A which can be detected by TOF-SIMS is named generically, and it is also called "organosiloxane type fragment ion."

  The above formulas (1) and (2) indicate that the relative intensity value Y of any organosiloxane fragment ion on the surface of the polarizer protective film immediately after the protective film is peeled from the film laminate is a polarizer before lamination of the protective film. It means that the relative strength value X on the surface of the protective film is less than 4 times, preferably less than 2.5 times. According to the film laminate having such surface characteristics, the adhesive residue that causes the resin composition to form the optical transparent resin even when the protective film is peeled off, and the bubbles at the interface with the optical transparent resin associated therewith are removed. Since generation | occurrence | production can be suppressed effectively, it becomes possible to improve the external appearance quality and visibility of a liquid crystal display device. According to the study by the present inventors, in contrast to the relative intensity value of the negative ions belonging to the group A, the relative intensity value of the positive ions and the occurrence of adhesive residue (bubble generation) may not be correlated. It has become clear.

  The optically transparent resin referred to here is, for example, a transparent resin obtained by curing the resin composition described in Patent Documents 1 and 2, or an optical resin composition described in JP2009-294360A. It can be a transparent resin obtained by curing. More specifically, the resin composition includes at least one polymer selected from the group consisting of acrylic resins, terpene hydrogenated resins, xylene resins, butadiene polymers, and isoprene polymers, and at least one kind. And those containing (meth) acrylate monomers and a photopolymerization initiator.

  Examples of the acrylic resin include polyurethane (meth) acrylate, polyisoprene (meth) acrylate, esterified product of polyisoprene (meth) acrylate, and the like.

  Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxy. Butyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopenteni Examples include roxyethyl (meth) acrylate.

  Whether the film laminate satisfies the above formula (1) (preferably (2)) is determined as follows. First, about the polarizer protective film before laminating | stacking a protective film, the TOF-SIMS analysis of the surface where a protective film is bonded is performed, and the relative intensity value X of each peak of the said organosiloxane type fragment ion is measured. The “relative intensity value” is the ratio of the peak intensity value of the target negative ion to the total peak intensity value of all negative ions detected by TOF-SIMS analysis (the relative intensity value Y is the same).

  Next, after a protective film is laminated to produce a film laminate, the protective film is peeled off, and immediately after that, a TOF-SIMS analysis is performed on the surface of the polarizer protective film on which the protective film is bonded, and the organic The relative intensity value Y of each peak of the siloxane fragment ion is measured. And it is confirmed whether all nine types of organosiloxane type fragment ions satisfy | fill said Formula (1) (preferably (2)).

Hereafter, the element which comprises a film laminated body is demonstrated in detail.
[Polarizer protective film]
The base film 11 constituting the polarizer protective film 10 is made of a cellulose resin (triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, etc.); (meth) acrylic resin (methyl methacrylate resin) Olefin resins (chain olefin resins such as polypropylene resins, cyclic olefin resins, etc.); polyester resins (polybutylene terephthalate resins, polyethylene terephthalate resins, etc.); styrene resins; polycarbonate resins; Polyamide resin; Polyacetal resin; Polysulfone resin; Polyethersulfone resin; Polyarylate resin; Polyamidoimide resin; Polyimide resin; Polyvinyl chloride resin It can be a Lum.

  The base film 11 can contain an additive as long as the transparency and adhesiveness with the polarizer layer are not impaired. The thickness of the base film 11 is usually 10 to 500 μm, preferably 10 to 300 μm, more preferably 20 to 300 μm from the viewpoint of thinning the polarizing plate.

  The polarizer protective film 10 preferably includes a surface treatment layer 12 laminated on the base film 11. As described above, the surface treatment layer 12 is a layer that imparts a predetermined function such as an optical function to the polarizer protective film 10, and is, for example, a hard coat layer, an antiglare layer, a light diffusion layer, an antireflection layer, or the like. be able to.

  The hard coat layer is a layer that imparts scratch resistance to the surface of the polarizer protective film 10 and can be made of a cured product of an active energy ray curable resin such as an ultraviolet curable resin or an electron beam curable resin. Active energy ray-curable resins include polyfunctional acrylates such as polyhydric alcohol acrylic acid or methacrylic acid ester; synthesized from diisocyanate and polyhydric alcohol and acrylic acid or methacrylic acid hydroxy ester, etc. A polyfunctional urethane acrylate is mentioned. In addition to these, polyether resins having an acrylate functional group, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like can also be used.

  The hard coat layer is formed by coating a coating liquid containing a resin containing an active energy ray-curable resin on the base film 11 and then irradiating the active energy ray to cure the coating layer. Can do. When an ultraviolet curable resin or the like is used as the active energy ray curable resin, the coating liquid usually contains a photopolymerization initiator (radical polymerization initiator). The photopolymerization initiator is appropriately selected depending on the resin to be used. For example, acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, triazine photopolymer A polymerization initiator, an oxadiazole-based photopolymerization initiator, or the like can be used. The coating liquid may contain other additives such as a solvent such as an organic solvent, a leveling agent, a dispersant, and an antifouling agent.

  The coating method of the coating liquid is a conventionally known method such as a gravure coating method, a micro gravure coating method, a roll coating method, a rod coating method, a knife coating method, an air knife coating method, a kiss coating method, or a die coating method. It's okay.

  The active energy ray to be irradiated can be appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays, etc., depending on the type of the active energy ray curable resin. Lines are preferable, and ultraviolet rays are particularly preferable because they are easy to handle and high energy can be easily obtained.

  The antiglare layer is an optical functional layer provided with a predetermined uneven shape on the surface for preventing reflection of external light. The antiglare layer is, for example, (a) a method in which a coating liquid containing translucent fine particles and a translucent resin is applied onto the substrate film 11 and then the coating layer is cured as necessary ( (B) coating liquid containing translucent resin (which may further contain translucent fine particles) is applied on the base film 11; Thereafter, the coating layer can be cured as necessary while pressing a mold having a predetermined surface irregularity shape on the coating layer, and can be formed by a method of imparting surface irregularities to the coating layer.

  The translucent resin constituting the antiglare layer is not particularly limited as long as it has translucency. For example, in addition to the cured product of the active energy ray curable resin as described above, Cured product; thermoplastic resin; metal alkoxide polymer and the like. Especially, the hardened | cured material of active energy ray curable resin is suitable. When an ultraviolet curable resin or the like is used as the active energy ray curable resin, the coating liquid contains a photopolymerization initiator (radical polymerization initiator) as described above, and is applied by irradiating active energy rays. Harden the construction layer.

  Examples of the thermosetting resin include a thermosetting urethane resin composed of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin.

  Examples of thermoplastic resins include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose; vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like. Acetal resins such as polyvinyl formal and polyvinyl butyral; (meth) acrylic resins such as acrylic resins and copolymers thereof, methacrylic resins and copolymers; polystyrene resins; polyamide resins; polyester resins; Examples include polycarbonate resins.

  As the metal alkoxide-based polymer, a silicon oxide-based matrix using a silicon alkoxide-based material as a raw material can be used. Specifically, the metal alkoxide polymer can be an inorganic or organic-inorganic composite matrix obtained by dehydration condensation of a hydrolyzate of alkoxysilane such as tetramethoxysilane or tetraethoxysilane.

  When a cured product of a thermosetting resin or a metal alkoxide polymer is used as the translucent resin, heating may be required after coating the coating liquid.

  Translucent fine particles include, for example, organic fine particles such as (meth) acrylic resin, melamine resin, polyethylene, polystyrene, organic silicone resin, acrylic-styrene copolymer, and calcium carbonate, silica, aluminum oxide, barium carbonate And inorganic fine particles such as barium sulfate, titanium oxide, and glass. One kind or two or more kinds of fine particles can be used as the translucent fine particles. In order to obtain desired antiglare properties and other optical characteristics, the kind, particle diameter, refractive index, content, and the like of the light-transmitting fine particles are appropriately adjusted.

  The light diffusion layer is an optical functional layer for diffusing the backlight light that has passed through the liquid crystal cell for the purpose of expanding the viewing angle of the liquid crystal display device. For example, the light diffusion layer is coated on the base film 11 with a coating liquid containing translucent fine particles (light diffusing agent) and a translucent resin, and then the coating layer is cured as necessary. It can be formed by a method. As the light-transmitting fine particles and the light-transmitting resin, the same materials as those described for the antiglare layer can be used. In order to obtain a desired light diffusibility, the type of base film, the type of translucent resin, the type of translucent fine particles, the particle diameter, the refractive index, the content, the thickness of the light diffusing layer, and the like are appropriately adjusted. .

  The antireflection layer is an optical functional layer for reducing or preventing reflection of external light, and may include, for example, a low refractive index layer. Moreover, the multilayer structure further provided with the high refractive index layer and / or the middle refractive index layer between the base film 11 and the low refractive index layer may be sufficient. The hard coat layer described above may be provided between the antireflection layer and the base film 11.

The low refractive index layer is coated with a coating solution containing a light-transmitting resin such as a cured product of the above-described active energy ray-curable resin or a metal alkoxide polymer, and inorganic fine particles, and then the coating layer is used as necessary. And can be formed by a method of curing. Examples of the inorganic fine particles include LiF (refractive index 1.4), MgF (refractive index 1.4), 3NaF · AlF (refractive index 1.4), AlF (refractive index 1.4), Na ₃ AlF ₆ ( Examples thereof include low refractive fine particles such as a refractive index of 1.33) and hollow silica fine particles.

  The high refractive index layer is formed by applying a coating liquid containing a light-transmitting resin such as a cured product of the above-described active energy ray-curable resin or a metal alkoxide polymer, and inorganic fine particles and / or organic fine particles. It can form by the method of hardening a construction layer as needed. Examples of the inorganic fine particles include zinc oxide, titanium oxide, cerium oxide, aluminum oxide, silane oxide, tantalum oxide, yttrium oxide, ytterbium oxide, zirconium oxide, antimony oxide, and indium tin oxide (ITO). By forming such a high refractive index layer, antistatic performance can be imparted.

[Protect film]
The protect film 20 can include a support film 21 and an adhesive layer 22 that is laminated on one surface of the protect film 20 and can be peeled off from the polarizer protective film 10. The support film 21 may be a transparent resin film similar to the above-described base film, but among them, a polyester resin film such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, polybutylene terephthalate is preferably used. The polyester resin film may be stretched.

  In the film laminate of the present invention, as long as the above formula (1) is satisfied, the relative intensity value of the organosiloxane fragment ions on the surface of the polarizer protective film can be increased or decreased before and after the protective film is attached and peeled off. When the relative strength value after sticking / peeling of the protective film increases (Y / X> 1) is when the organosiloxane component contained in the adhesive layer 22 is transferred to the polarizer protective film, etc. The case where the relative intensity value decreases (Y / X <1) is a case where the organosiloxane component on the surface of the polarizer protective film moves to the adhesive layer 22.

  Examples of the pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer 22 include those having an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyether, or the like as a base polymer. Among these, an acrylic pressure-sensitive adhesive having an acrylic polymer as a base polymer is preferably used.

  The acrylic base polymer constituting the acrylic pressure-sensitive adhesive includes an acrylic acid alkyl ester having an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a butyl group, or a 2-ethylhexyl group, An acrylic copolymer with a functional group-containing (meth) acrylic monomer such as a hydroxyl group or a carboxyl group such as (meth) acrylic acid or 2-hydroxyethyl (meth) acrylate is preferably used.

  The pressure-sensitive adhesive layer 22 is formed on the support film 21 with a pressure-sensitive adhesive composition containing a base polymer, a crosslinking agent (such as a polyisocyanate compound), and various additives (such as a solvent) other than an organic siloxane component added as necessary. It can be formed by coating and drying. The thickness of the pressure-sensitive adhesive layer 22 is usually about 1 to 40 μm, preferably about 3 to 25 μm.

  A film laminate is obtained by sticking the protect film 20 to the surface of the polarizer protective film 10 on the pressure-sensitive adhesive layer 22 side.

  In addition, when laminating the film laminate on the polarizer layer to produce a polarizing plate, the base film 11 is subjected to saponification treatment, corona discharge treatment, plasma treatment, for the purpose of improving adhesiveness with the polarizer layer. Surface activation treatment such as ultraviolet irradiation treatment and electron beam irradiation treatment can be performed, but this surface activation treatment is usually performed after the protective film 20 is attached.

<Polarizing plate>
FIG. 2 is a schematic sectional view showing an example of the polarizing plate of the present invention. Referring to FIG. 2, the polarizing plate of the present invention includes a film laminate according to the present invention and a surface opposite to the side on which the protective film 20 of the polarizer protective film 10 is laminated (of the base film 11. And a polarizer layer 30 laminated on the outer surface. An optical compensation film such as a conventionally known polarizer protective film and / or retardation film (retardation plate) may be laminated on the other surface of the polarizer layer 30.

  As the polarizer layer 30, a uniaxially stretched polyvinyl alcohol resin film obtained by adsorbing and orienting a dichroic dye or a dichroic dye such as iodine is preferably used. The polyvinyl alcohol resin can be obtained by saponification of a polyvinyl acetate resin. The polyvinyl acetate resin may be a copolymer of vinyl acetate which is a homopolymer of vinyl acetate, or a copolymer of vinyl acetate and another monomer copolymerizable therewith. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. The thickness of the polarizer layer 30 is usually in the range of 5 to 40 μm.

  Bonding of the film laminated on the polarizer layer 30 such as the polarizer protective film 10 and the polarizer layer 30 can be performed using an adhesive. As an adhesive, an adhesive composed of an active energy ray or a thermosetting resin composition such as a curable resin composition containing an epoxy resin, or an aqueous adhesive containing a polyvinyl alcohol resin or a urethane resin as an adhesive component Etc. can be preferably used.

  According to the polarizing plate of the present invention, it is possible to effectively suppress the adhesive residue on the outermost surface after the protective film is peeled off. Therefore, when applied to a liquid crystal display device in which an optical transparent resin is interposed between the liquid crystal panel and the front plate In this case, it is possible to obtain excellent appearance quality and visibility without generating bubbles at the interface between the optical transparent resin and the polarizing plate.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

<Example 1>
On a substrate film made of triacetylcellulose (TAC), pentaerythritol tetraacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), isophorone diisocyanate (IPDI), organic fine particles made of styrenic resin, photopolymerization initiator ( After coating a coating solution containing 1-hydroxy-cyclohexyl-phenyl-ketone) and an antifouling agent (organosiloxane antifouling agent), the coating layer is dried and cured by irradiation with ultraviolet rays. A 5.9 μm antiglare layer was formed. Subsequently, the saponification process was performed and the polarizer protective film A was obtained. The antiglare layer surface of the polarizer protective film A was subjected to TOF-SIMS analysis under the following conditions, and the relative intensity X of the organosiloxane fragment ions was measured.

  Next, a protective film a having an adhesive layer on a support film made of polyethylene terephthalate (PET) is attached to the antiglare layer surface of the polarizer protective film A on the adhesive layer side, and the temperature is 25 ° C. The film laminate was obtained by standing for 168 hours under the condition of 50% relative humidity. The adhesive layer of the protective film a is an acrylic copolymer mainly composed of 2-ethylhexyl acrylate (2EHA), 2-hydroxyethyl acrylate (2HEA) and 2-ethylhexyl methacrylate (2EHM), and a crosslinking agent. It consists of an adhesive composition containing tolylene diisocyanate (TDI) and coronate L.

  Next, the obtained film laminate was bonded and fixed to a 10 cm × 15 cm acrylic substrate on the base film side using an adhesive, and then the protective film a was peeled off, and the polarizer protective film A immediately after peeling. The surface of the antiglare layer was subjected to TOF-SIMS analysis under the following conditions, and the relative intensity Y of the organosiloxane fragment ions was measured.

<Comparative Example 1>
A film laminate was prepared in the same manner as in Example 1 except that the protect film b was used instead of the protect film a, and the relative strength Y was measured. The pressure-sensitive adhesive layer of the protective film b is made of the same pressure-sensitive adhesive composition as the pressure-sensitive adhesive layer of the protective film a except that it contains an organosiloxane component.

<Comparative Example 2>
On a base film made of triacetyl cellulose (TAC), pentaerythritol tetraacrylate (PETA), isophorone diisocyanate (IPDI), organic fine particles made of styrene resin, photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone ) And an antifouling agent (organosiloxane antifouling agent) are applied, and then the coating layer is dried and cured by ultraviolet irradiation to form an antiglare layer having a thickness of 5.7 μm. did. Next, a saponification treatment was performed to obtain a polarizer protective film B. The anti-glare layer surface of the polarizer protective film B was subjected to TOF-SIMS analysis under the following conditions, and the relative intensity X of the organosiloxane fragment ions was measured. Next, using the protective film b, a film laminate was produced in the same manner as in Comparative Example 1, and the relative strength Y was measured.

Table 1 shows the calculation results of the relative intensity ratio Y / X of the organosiloxane fragment ions. In the table, each fragment 1-9, Si ^- [ion count (hereinafter the same): 28], CH ₃ SiO ^- [59], SiO ₂ ^- [60], CH ₃ SiO ₂ ^- [75], C ₃ H ₉ SiO ^- _{[89], C 3 H 9 Si 2 O} 3 - _{[149], C 5 H 15 Si 2 O} 2 - _{[163], C 5 H 15 Si 3 O} 4 - [223], C ₇ H ₂₁ Si ₃ O ₃ ⁻ [237] is represented.

The TOF-SIMS analysis was performed under the following measurement conditions.
(1) Apparatus: “TRIFT II” manufactured by Physical Electronics,
(2) Irradiated primary ions: ⁶⁹ Ga ⁺ ,
(3) Measurement range (area): about 150 μm □.

  Moreover, about each of the obtained film laminated body, the grade of the bubble generation | occurrence | production in the interface of an anti-glare layer surface and an optical transparent resin when forming an optical transparent resin on the anti-glare layer surface was evaluated. The evaluation test method is as follows.

Mainly composed of styrene-butadiene rubber and xylene resin, 1.8% by weight of 2-hydroxyethyl acrylate, 6.9% by weight of benzyl methacrylate and 2.5% by weight of isobornyl acrylate as photopolymerizable monomers, photopolymerization initiator As a resin composition containing 0.5% by weight of 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4,6-trimethylbenzoic acid as a solvent, and isophorone diisocyanate as a cross-linking agent All were coated on the surface of the antiglare layer using a bar coater (number 30), and allowed to stand for 60 minutes in a cool and dark place, and then a glass plate was laminated on the surface of the coating layer. Then, using an ultraviolet irradiation device, the coating layer was cured by irradiating ultraviolet rays from the glass plate side so that the integrated light amount was 5000 mJ / cm ² , thereby forming an optical transparent resin on the surface of the antiglare layer. The antiglare layer / optical transparent resin interface of the obtained sample was visually observed, and the degree of bubble generation was evaluated according to the following criteria. The results are shown in Table 1.

A: No or almost no air bubbles can be confirmed,
B: Some bubbles can be confirmed, but there is no problem.
C: Many bubbles can be confirmed.

  DESCRIPTION OF SYMBOLS 10 Polarizer protective film, 11 Base film, 12 Surface treatment layer, 20 Protect film, 21 Support film, 22 Adhesive layer, 30 Polarizer layer.

Claims (5)

A film laminate comprising a polarizer protective film and a protective film laminated on one surface thereof,
The polarizer protective film comprises a base film and a surface treatment layer laminated on one surface thereof,
The protective film comprises a support film and an adhesive layer laminated on one surface thereof,
The protective film is laminated on the surface of the surface treatment layer on the pressure-sensitive adhesive layer side,
Of the surface treatment layer and the pressure-sensitive adhesive layer, only the surface treatment layer contains an organosiloxane,
The relative intensity value of negative ions when measuring the surface of the surface treatment layer by time-of-flight secondary ion mass spectrometry, where X is the relative intensity value before lamination of the protective film, and the protective film is peeled off When the relative intensity value immediately after the annealing is Y, Si ⁻ , CH ₃ SiO ⁻ , SiO ₂ ⁻ , CH ₃ SiO ₂ ⁻ , C ₃ H ₉ SiO ⁻ , C ₃ H ₉ Si ₂ O ₃ ⁻ , C ₅ H For all negative ions of ₁₅ Si ₂ O ₂ ⁻ , C ₅ H ₁₅ Si ₃ O ₄ ⁻ , and C ₇ H ₂₁ Si ₃ O ₃ ⁻ , the following formula (1):
Y / X <4 (1)
Film laminate satisfying the requirements. Following formula (2):
Y / X <2.5 (2)
The film laminated body of Claim 1 which satisfy | fills.   The film laminate according to claim 1, wherein X> 0 and Y> 0.   The film laminate according to any one of claims 1 to 3, wherein the surface treatment layer is a hard coat layer, an antiglare layer, a light diffusion layer, or an antireflection layer.   A polarizing plate comprising: the film laminate according to any one of claims 1 to 4; and a polarizer layer laminated on a surface of the polarizer protective film opposite to a side on which the protective film is laminated. .

Images