JP2011093958A - Near-infrared ray absorbing adhesive composition and near infrared ray absorbing adhesive layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared absorbing adhesive composition excellent in light resistance, heat resistance and wet heat resistance; and to provide a near-infrared absorbing adhesive layer obtained from the same, and an anti-reflective near-infrared absorbing film and a filter for a display utilizing the same. <P>SOLUTION: The near-infrared absorbing adhesive composition mainly includes phthalocyanine as a near-infrared absorbing dye and further includes a triazine-based ultraviolet absorber. The near-infrared absorbing adhesive layer utilizes the near-infrared absorbing adhesive composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a near-infrared absorbing pressure-sensitive adhesive composition, a near-infrared absorbing pressure-sensitive adhesive layer obtained from the near-infrared pressure-sensitive adhesive composition of the present invention, and a near-infrared absorbing layer having the near-infrared absorbing pressure-sensitive adhesive layer. The present invention relates to a film, an antireflection near-infrared absorbing film, and a display filter.

  In recent years, thin displays such as liquid crystal displays, plasma displays, and organic EL displays have become widespread. These displays are provided with display filters having various functions.

  For example, anti-reflection function and anti-glare function to prevent reflection and reflection of outside light, electromagnetic wave shielding function to shield electromagnetic waves emitted from the display, near infrared absorption to absorb near infrared rays emitted from the display A display filter having a function or a shock absorbing function for protecting the display from an impact is disposed on the front surface of the display panel.

  In particular, it is known that a plasma display emits near infrared rays relatively strongly, and the near infrared rays adversely affect peripheral electronic devices. Therefore, the near-infrared absorption function is usually given to the plasma display filter disposed in front of the plasma display panel.

  As a method for incorporating a near-infrared absorbing function into a display filter, a so-called near-infrared absorbing film in which a resin layer (near-infrared absorbing resin layer) containing a near-infrared absorbing dye is conventionally laminated on a base film such as a plastic film. Is generally used.

  On the other hand, the display filter is designed to have various functions as described above. For example, a filter for a plasma display is usually designed to have both an electromagnetic wave shielding function, a near infrared ray absorbing function, and an antireflection function, and the electromagnetic wave shielding film, the near infrared ray absorbing film, and the antireflection film are respectively adhesive layers. It is the structure laminated by. In such a laminated structure, the near infrared absorbing film is omitted by adding a near infrared absorbing dye to the pressure-sensitive adhesive layer, thereby simplifying the structure of the filter for plasma display. Has been proposed (for example, Patent Documents 1 to 5).

  Inorganic metal and organic dyes (ie, near-infrared absorbing dyes) are known as near-infrared absorbers for imparting a near-infrared absorbing function to a display filter. Near-infrared absorbing dyes are generally used from the viewpoints of transparency, ease of addition to the resin layer and the pressure-sensitive adhesive layer, and the like. However, the near-infrared absorbing dye has a problem that it is inferior in light resistance. That is, there is a problem that near-infrared absorbing dyes deteriorate when exposed to light containing ultraviolet rays.

  In order to avoid the above problem, the base film constituting the near-infrared absorbing film may contain an ultraviolet absorber, and the layer containing the near-infrared absorbing dye may be protected from ultraviolet rays by blocking the ultraviolet rays with the base film. Known (for example, Patent Documents 6 and 7).

JP 2006-319251 A Special table 2008-540692 gazette JP 2009-13200 A JP 2009-73866 A JP 2009-84400 A JP 2006-184820 A JP 2007-334325 A

  However, in the case of a pressure-sensitive adhesive layer containing a near-infrared absorbing dye (near-infrared absorbing pressure-sensitive adhesive layer), the pressure-sensitive adhesive layer has a higher oxygen and moisture transmittance than the conventional near-infrared absorbing resin layer. There is a problem that oxygen and moisture that have entered the layer promote deterioration of the light resistance of the near infrared absorbing dye.

  Moreover, in order to ensure adhesiveness, the adhesive layer usually uses a resin having a low glass transition point. When a near-infrared absorbing dye is contained in a pressure-sensitive adhesive layer composed of a resin having a low glass transition point, the near-infrared absorbing dye moves relatively easily in the pressure-sensitive adhesive layer, thereby increasing the reactivity. There is a problem that the near infrared absorbing dye promotes deterioration of light resistance, heat resistance, and moist heat resistance.

  In addition to the problem of reduced near-infrared absorption performance (increased transmittance in the near-infrared region) when the near-infrared-absorbing dye contained in the near-infrared-absorbing adhesive layer deteriorates in light resistance, heat resistance, and moist heat resistance. Inconveniently, the luminous transmittance and color tone (chromaticity coordinates) of the near-infrared absorbing pressure-sensitive adhesive layer change. This problem may become a serious defect when the near-infrared absorbing pressure-sensitive adhesive layer is applied to a display filter such as a plasma display filter.

  The problem of deterioration of light resistance, heat resistance, and moist heat resistance in the near-infrared absorbing pressure-sensitive adhesive layer cannot be sufficiently solved even when a base film containing an ultraviolet absorber is used. That is, it is difficult for a substrate film containing an ultraviolet absorber to block 100% of ultraviolet rays continuously for a long period of time, and as a result, the near-infrared absorbing dye contained in the near-infrared absorbing pressure-sensitive adhesive layer is long-term. In particular, light resistance tends to deteriorate, and deterioration of heat resistance and moist heat resistance cannot be solved by a base film containing an ultraviolet absorber.

  In addition, the production of a base film (for example, a plastic film) containing an ultraviolet absorber has a problem that productivity is inferior to that of a base film not containing an ultraviolet absorber. It is desired to use a base film that does not contain an ultraviolet absorber as the base film constituting the film, and the light resistance in the near-infrared absorbing pressure-sensitive adhesive layer is becoming increasingly important.

  From the above viewpoint, the near-infrared absorbing pressure-sensitive adhesive layer disclosed in Patent Documents 1 to 5 described above has not sufficiently satisfied light resistance, heat resistance, and moist heat resistance.

  Then, the objective of this invention aims at providing the near-infrared absorptive adhesive composition excellent in light resistance, heat resistance, and moist heat resistance in view of the above points.

  Another object of the present invention is to provide a near-infrared absorbing pressure-sensitive adhesive layer obtained from the near-infrared absorbing pressure-sensitive adhesive composition, a near-infrared absorbing film using the near-infrared absorbing pressure-sensitive adhesive layer, and an antireflection coating. The object is to provide a near-infrared absorbing film and a display filter.

  The object of the present invention described above can be achieved by using a near-infrared absorbing adhesive composition having the following configuration 1).

  1) A near-infrared-absorbing pressure-sensitive adhesive composition containing phthalocyanine as a near-infrared absorbing dye and a triazine-based ultraviolet absorber.

  Moreover, in the near-infrared absorptive adhesive composition of this invention, it is preferable to set it as the structure in any one of the following 2) -5).

2) The near-infrared-absorbing pressure-sensitive adhesive composition as described in 1) above, which contains 60% by mass or more of phthalocyanine with respect to 100% by mass of the total amount of the near-infrared absorbing dye.
3) The near-infrared absorbing adhesive composition according to 1) or 2) above, wherein the triazine-based ultraviolet absorber is a hydroxyphenyltriazine-based ultraviolet absorber.
4) The phthalocyanine includes at least one phthalocyanine having a maximum absorption wavelength of 800 nm to 900 nm and at least one phthalocyanine having a maximum absorption wavelength of more than 900 nm and 1000 nm or less. The near-infrared absorption adhesive composition in any one of) -3).
5) The near-infrared absorbing pressure-sensitive adhesive composition according to any one of 1) to 4), wherein the phthalocyanine contains three or more phthalocyanines selected from the group consisting of the following A) to D): object.

A) Phthalocyanine having a maximum absorption wavelength of 800 nm or more and 850 nm or less B) Phthalocyanine having a maximum absorption wavelength of more than 850 nm and 900 nm or less C) Phthalocyanine having a maximum absorption wavelength of more than 900 nm and 950 nm or less D) Above 950 nm and 1000 nm or less Phthalocyanine having Maximum Absorption Wavelength Further, the above-described other object of the present invention can be achieved by forming a near-infrared absorbing pressure-sensitive adhesive layer having the following configuration 6).

  6) A near-infrared absorbing pressure-sensitive adhesive layer obtained from the near-infrared absorbing pressure-sensitive adhesive composition according to any one of 1) to 5).

  Moreover, the other objective mentioned above of this invention can be achieved by setting it as the infrared rays absorption film which has the structure of the following 7).

  7) A near-infrared absorbing film, wherein the near-infrared absorbing pressure-sensitive adhesive layer described in 6) above is laminated on a substrate film.

  In addition, the above-described other objects of the present invention can be achieved by using an antireflection near-infrared absorbing film having the following configuration 8).

  8) An antireflection film having an antireflection layer on one surface, wherein the near infrared absorbing pressure-sensitive adhesive layer according to claim 6 is laminated on a surface opposite to the surface having the antireflection layer. Anti-reflection near-infrared absorbing film.

  Further, the above-described other objects of the present invention can be achieved by providing a display filter having any one of the following 9) to 11).

  9) A display filter comprising the near-infrared absorbing pressure-sensitive adhesive layer described in 6 above.

  10) A display filter comprising the antireflection near-infrared absorbing film described in 8 above.

  11) The display filter as described in 9) or 10) above, wherein the display filter is for a plasma display.

  ADVANTAGE OF THE INVENTION According to this invention, the near-infrared absorptive adhesive composition improved in light resistance, heat resistance, and heat-and-moisture resistance can be provided.

  In addition, according to the present invention, a near-infrared absorbing pressure-sensitive adhesive layer having improved light resistance, heat resistance, and heat-and-moisture resistance, and a near-infrared absorbing film and an antireflection near-reflection film using the near-infrared absorbing pressure-sensitive adhesive layer. An infrared absorbing film and a filter for display can be provided.

  The near infrared ray absorbing pressure-sensitive adhesive composition of the present invention contains a pressure-sensitive adhesive as a main component. In other words, the near-infrared-absorbing pressure-sensitive adhesive composition of the present invention contains a near-infrared-absorbing dye (including phthalocyanine as a main component) and a triazine-based ultraviolet absorber in the pressure-sensitive adhesive.

  The near-infrared absorbing pressure-sensitive adhesive composition of the present invention (hereinafter simply referred to as “pressure-sensitive adhesive composition”) mainly contains phthalocyanine as a near-infrared absorbing dye. Here, the phrase “mainly” containing phthalocyanine as a near-infrared absorbing dye means that phthalocyanine is contained in an amount exceeding 50% by mass with respect to 100% by mass of the total amount of the near-infrared absorbing dye. The content is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and most preferably 90% by mass. % Or more. The upper limit is 100% by mass.

  Conventionally, as a near-infrared absorbing dye, phthalocyanine, diimonium, polymethine, dithiol metal complex, squarylium, cyanine, indoaniline, azo, anthraquinone, naphthoquinone, pyrylium, thiopyrylium, croconium, Tetradehydrocholine, triphenylmethane, aminium, and the like are known.

  Conventionally, as an ultraviolet absorber, benzotriazole, benzophenone, triazine, benzoxazine, salicylic acid ester, diphenylmethanone, 2-cyanopropenoic acid ester, anthranilate, cinnamic acid derivative, A camphor derivative system, a benzalmalonate derivative system, a resorcinol system, an oxalinide system, a coumarin derivative system, and the like are known.

  Among the above near-infrared absorbing dyes and ultraviolet absorbers, the present invention is such that the combination of phthalocyanine and triazine-based ultraviolet absorber is excellent in light resistance, heat resistance, and moist heat resistance in the pressure-sensitive adhesive composition, and It has been found that the effect of the combination of phthalocyanine and triazine-based UV absorber is first exhibited when phthalocyanine is mainly contained as a near-infrared absorbing dye.

  When a triazine-based ultraviolet absorber is contained in a pressure-sensitive adhesive composition mainly containing a near-infrared absorbing dye other than phthalocyanine, for example, a generally well-known diimonium dye, heat resistance and heat-and-moisture resistance are adversely affected. In addition, it has been found that the light resistance is not improved even when a UV absorber other than phthalocyanine and triazine, for example, a commonly known benzotriazole UV absorber or benzophenone UV absorber is combined.

  As described above, in the pressure-sensitive adhesive composition of the present invention, it is preferable that the content ratio of phthalocyanine as a near-infrared absorbing dye is large, but phthalocyanine and other dyes can be combined within the scope of the present invention. However, even in that case, it is preferable that a diimonium dye is not substantially used as the other dye. When a diimonium dye is contained as another dye, it is preferably 10% by weight or less, more preferably 5% by weight or less, and still more preferably not contained at all with respect to 100% by weight of the total amount of the near-infrared absorbing dye.

  As the phthalocyanine according to the present invention, a conventionally known phthalocyanine having a maximum absorption wavelength in the near infrared region of 800 nm to 1000 nm can be used. Examples of such phthalocyanines include phthalocyanines of the following general formula 1.

式中、Ｒ^１〜Ｒ^１６は、それぞれ独立に水素原子、ハロゲン原子、水酸基、アミノ基、ヒドロキシスルホニル基、アミノスルホニル基、または、窒素原子、硫黄原子、酸素原子およびハロゲン原子からなる群から選ばれる１種以上の原子を含んでもよい炭素数１〜２０の置換基を表し、かつ、隣り合う２個の置換基が連結基を介してつながっていてもよい。Ｍは２個の水素原子、２価の金属原子、３価又は４価の置換金属原子、あるいはオキシ金属を表す。

In the formula, R ^{1 to} R ¹⁶ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, or a nitrogen atom, a sulfur atom, an oxygen atom, and a halogen atom. Represents a substituent having 1 to 20 carbon atoms that may contain one or more atoms, and two adjacent substituents may be connected via a linking group. M represents two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal.

  In the above general formula 1, the following a) to u) are the substituents having 1 to 20 carbon atoms that may contain one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom, an oxygen atom and a halogen atom. The substituent of this is mentioned.

  a) Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n- A linear, branched or cyclic alkyl group such as a heptyl group, an n-octyl group, or a 2-ethylhexyl group;

  b) A halogenoalkyl group such as a chloromethyl group, a dichloromethyl group, a cyclohexyl group, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, or a nonafluorobutyl group.

  c) Alkyl groups containing heteroatoms and aromatic rings such as methoxymethyl group, phenoxymethyl group, diethylaminomethyl group, phenylthiomethyl group, benzyl group, p-chlorobenzyl group, p-methoxybenzyl group.

  d) An aryl group such as a phenyl group, a p-methoxyphenyl group, a pt-butylphenyl group, a p-chlorophenyl group, or a p-fluorophenyl group.

  e) Methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy Group, alkoxy group such as n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group and the like.

f) halogenoalkoxy groups such as a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a trifluoromethylmethoxy group, a dichloromethylmethoxy group, a cyclohexyloxy group,
g) Alkoxyalkoxy groups such as methoxyethoxy group and phenoxyethoxy group.

  h) A hydroxyalkoxy group such as a hydroxyethoxy group.

  i) Aralkyloxy groups such as benzyloxy group, p-chlorobenzyloxy group, p-methoxybenzyloxy group, phenoxy group, p-methoxyphenoxy group, pt-butylphenoxy group, p-chlorophenoxy group, o- Aryloxy groups such as aminophenoxy group and p-diethylaminophenoxy group;

  j) Acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyl Alkylcarbonyloxy groups such as an oxy group, an n-pentylcarbonyloxy group, an n-hexylcarbonyloxy group, a cyclohexylcarbonyloxy group, an n-heptylcarbonyloxy group, a 3-heptylcarbonyloxy group, and an n-octylcarbonyloxy group.

  k) Benzoyloxy group, p-chlorobenzoyloxy group, p-methoxybenzoyloxy group, p-ethoxybenzoyloxy group, p-t-butylbenzoyloxy group, p-trifluoromethylbenzoyloxy group, m-trifluoro Arylcarbonyloxy groups such as methylbenzoyloxy group, o-aminobenzoyloxy group, p-diethylaminobenzoyloxy group;

  l) Methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio Alkylthio groups such as a group, n-heptylthio group, n-octylthio group and 2-ethylhexylthio group;

  m) Aralkylthio groups such as a benzylthio group, a p-chlorobenzylthio group, and a p-methoxybenzylthio group.

  n) phenylthio group, p-methoxyphenylthio group, pt-butylphenylthio group, p-chlorophenylthio group, o-aminophenylthio group, o- (n-octylamino) phenylthio group, o- (benzylamino) ) An arylthio group such as a phenylthio group, o- (methylamino) phenylthio group, p-diethylaminophenylthio group, naphthylthio group.

  o) Methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino Group, 2-ethylhexylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butylamino group, di-sec-butylamino group, di-n-pentylamino group, di-n An alkylamino group such as a hexylamino group, a di-n-heptylamino group or a di-n-octylamino group;

  p) Arylamino groups such as phenylamino group, p-methylphenylamino group, pt-butylphenylamino group, diphenylamino group, di-p-methylphenylamino group, di-pt-butylphenylamino group .

  q) Acetylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, iso-propylcarbonylamino group, n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonyl Alkyl group such as amino group, n-pentylcarbonylamino group, n-hexylcarbonylamino group, cyclohexylcarbonylamino group, n-heptylcarbonylamino group, 3-heptylcarbonylamino group, n-octylcarbonylamino group, benzoyl Amino group, p-chlorobenzoylamino group, p-methoxybenzoylamino group, p-methoxybenzoylamino group, p-t-butylbenzoylamino group, p-chlorobenzoylamino group, p-trifluoromethyl Benzoylamino group, m- trifluoromethylbenzoyl arylcarbonylamino group such as an amino group.

  r) Hydroxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso-butyloxycarbonyl group, sec-butyloxycarbonyl group, t Alkoxycarbonyl groups such as -butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group .

  s) Alkoxyalkoxycarbonyl groups such as a methoxyethoxycarbonyl group, a phenoxyethoxycarbonyl group, and a hydroxyethoxycarbonyl group.

  Aryloxycarbonyl such as benzyloxycarbonyl group, phenoxycarbonyl group, p-methoxyphenoxycarbonyl group, pt-butylphenoxycarbonyl group, p-chlorophenoxycarbonyl group, o-aminophenoxycarbonyl group, p-diethylaminophenoxycarbonyl group Group.

  t) Aminocarbonyl group, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, n-hexylaminocarbonyl group N-heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di -Sec-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-heptylaminocarbonyl group, di-n-octylaminocarbonyl group, etc. Group.

  u) phenylaminocarbonyl group, p-methylphenylaminocarbonyl group, pt-butylphenylaminocarbonyl group, diphenylaminocarbonyl group, di-p-methylphenylaminocarbonyl group, di-pt-butylphenylaminocarbonyl An arylaminocarbonyl group such as a group;

  v) Methylaminosulfonyl group, ethylaminosulfonyl group, n-propylaminosulfonyl group, n-butylaminosulfonyl group, sec-butylaminosulfonyl group, n-pentylaminosulfonyl group, n-hexylaminosulfonyl group, n-heptyl Aminosulfonyl group, n-octylaminosulfonyl group, 2-ethylhexylaminosulfonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, di-n-propylaminosulfonyl group, di-n-butylaminosulfonyl group, di-sec-butyl Alkylaminosulfonyl groups such as an aminosulfonyl group, a di-n-pentylaminosulfonyl group, a di-n-hexylaminosulfonyl group, a di-n-heptylaminosulfonyl group, and a di-n-octylaminosulfonyl group;

  w) phenylaminosulfonyl group, p-methylphenylaminosulfonyl group, pt-butylphenylaminosulfonyl group, diphenylaminosulfonyl group, di-p-methylphenylaminosulfonyl group, di-pt-butylphenylaminosulfonyl An arylaminosulfonyl group such as a group;

  In the general formula 1, two adjacent substituents that may be connected via a linking group include a 5-membered ring or a 6-membered ring via a hetero atom represented by the following chemical formula: The substituent to form is mentioned.

  In the above general formula 1, examples of the divalent metal atom represented by M include Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II) , Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II) , Hg (II), Pb (II), Sn (II) and the like.

Examples of the trivalent substituted metal atom represented by M include Al—Cl, Al—Br, Al—F, Al—I, Ga—Cl, Ga—F, Ga—I, Ga—Br, and In—. Cl, In-Br, In- I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Al-C 6 H 5, Al-C 6 H 4 (CH 3), In- _{C 6 H 5, In-C} 6 H 4 (CH 3), Mn (OH), Mn (OC 6 H 5), Mn [OSi (CH _{3) 3],} Fe-Cl, include Ru-Cl, etc. .

Examples of tetravalent substituted metal atom represented by _{M, CrCl 2, SiCl 2,} SiBr 2, SiF 2, SiI 2, ZrCl 2, GeCl 2, GeBr 2, GeI 2, GeF 2, SnCl 2, SnBr ₂ , SnF ₂ , TiCl ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ [R represents an alkyl group, a phenyl group, a naphthyl group, and derivatives thereof], Si (OR ′) ₂ , Sn (OR ′) ₂ , Ge (OR ′) ₂ , Ti ( OR ′) ₂ , Cr (OR ′) ₂ [R ′ represents an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof], Sn (SR ″) ₂ , Ge (SR ") ₂ (R" is Group, a phenyl group, a naphthyl group, and represent a derivative thereof) and the like.

  Examples of the oxymetal represented by M include VO, MnO, TiO and the like.

  Among the metal atoms represented by M, particularly preferred metal atoms are Cu, Pd, AlCl, TiO, or VO.

The phthalocyanine preferably used in the present invention is the above-described general formula 1, wherein R ^{1 to} R ¹⁶ are a halogen atom, a C 1-20 substituent containing a halogen atom, or a C 1-20 substituent via a sulfur atom. , And at least one substituent selected from the group consisting of substituents having 1 to 20 carbon atoms via a nitrogen atom, and M is Cu, Pd, AlCl, TiO, or VO.

  As said halogen atom, a fluorine atom and a chlorine atom are preferable.

  As said C1-C20 substituent containing a halogen atom, a halogenoalkyl group, a halogenoaryl group, a halogenoalkoxy group, a halogenoaryloxy group, etc. are mentioned, As a halogen atom, a fluorine atom and a chlorine atom are preferable.

  Examples of the substituent via the sulfur atom include an aminosulfonyl group, an alkylthio group, and an arylthio group.

  Examples of the substituent via the nitrogen atom include an amino group, an alkylamino group, an arylamino group, an alkylcarbonylamino group, and an arylcarbonylamino group.

  In the present invention, it is preferable to use a combination of two or more phthalocyanines having different maximum absorption wavelengths. For example, it is preferable to combine at least one phthalocyanine having a maximum absorption wavelength of 800 nm or more and 900 nm or less with at least one phthalocyanine having a maximum absorption wavelength of more than 900 nm and 1000 nm or less.

  In the present invention, it is more preferable to use a combination of three or more phthalocyanines having different maximum absorption wavelengths. For example, the aspect which combines 3 or more types chosen from the group which consists of following A) -D) is mentioned.

A) Phthalocyanine having a maximum absorption wavelength of 800 nm or more and 850 nm or less B) Phthalocyanine having a maximum absorption wavelength of more than 850 nm and 900 nm or less C) Phthalocyanine having a maximum absorption wavelength of more than 900 nm and 950 nm or less D) Above 950 nm and 1000 nm or less Phthalocyanine having maximum absorption wavelength The maximum absorption wavelength of the above phthalocyanine was measured in a state where phthalocyanine was contained in the pressure-sensitive adhesive composition. Specifically, the maximum absorption wavelength of the phthalocyanine is determined by applying a pressure-sensitive adhesive composition containing phthalocyanine onto a PET film having a thickness of 100 μm and drying to form a pressure-sensitive adhesive layer having a thickness of 25 μm. A sample was prepared by pasting the surface of the agent layer on a glass plate (thickness 1.8 mm), and this sample was obtained by measuring with a spectrophotometer (for example, trade name “UV-3150” manufactured by Shimadzu Corporation). Is.

Examples of the phthalocyanines of A) to D) described above include the following compounds.
A) As a phthalocyanine having a maximum absorption wavelength of 800 nm or more and 850 nm or less, for example, in General Formula 1, at least four of R ^{1 to} R ¹⁶ are substituents via a nitrogen atom, and The compound which does not contain the substituent through a sulfur atom and M is copper is mentioned.
B) As a phthalocyanine having a maximum absorption wavelength of more than 850 nm and not more than 900 nm, for example, in the general formula 1, at least four of R ^{1 to} R ¹⁶ are substituents via a nitrogen atom, and The compound which does not contain the substituent through a sulfur atom and whose M is vanadium oxide is mentioned.
C) As a phthalocyanine having a maximum absorption wavelength of more than 900 nm and not more than 950 nm, for example, in General Formula 1, at least four of R ^{1 to} R ¹⁶ are substituents via a sulfur atom, and A compound in which at least three of R ^{1 to} R ¹⁶ are substituents having a chlorine atom, and M is vanadium oxide is exemplified.
D) As a phthalocyanine having a maximum absorption wavelength of more than 950 nm and 1000 nm, for example, in General Formula 1, at least four of R ^{1 to} R ¹⁶ are substituents via a sulfur atom, and chlorine A compound having no atom-containing substituent and M being vanadium oxide can be mentioned.

  The pressure-sensitive adhesive composition of the present invention is particularly suitable for a pressure-sensitive adhesive layer of a plasma display filter. In this case, the transmittance at each wavelength of 850 nm, 900 nm, and 1000 nm is adjusted to be 30% or less. It is preferably 25% or less, more preferably 20% or less. From this viewpoint, as described above, it is preferable to use a combination of two or more phthalocyanines having different maximum absorption wavelengths, and it is particularly preferable to use a combination of three or more phthalocyanines having different maximum absorption wavelengths.

  The content of phthalocyanine in the pressure-sensitive adhesive composition according to the present invention is appropriately set according to the properties required for the product or member to which the pressure-sensitive adhesive composition is applied. For example, when applied to the pressure-sensitive adhesive layer of a plasma display filter, the content ratio of phthalocyanine is suitably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive, and 0.3 to 10 parts by weight. The range of parts is preferred, the range of 0.5 to 8 parts by weight is more preferred, and the range of 1 to 5 parts by weight is most preferred.

  The pressure-sensitive adhesive composition of the present invention contains a triazine-based ultraviolet absorber. As the triazine-based ultraviolet absorber, those conventionally known can be used.

  As the triazine-based UV absorber according to the present invention, a hydroxyphenyl triazine-based UV absorber is preferably used. The hydroxyphenyl triazine-based ultraviolet absorber can absorb ultraviolet rays stably by allowing the hydroxyl group at the ortho position of hydroxyphenyl to interact with nitrogen of the triazine ring.

  The hydroxyphenyltriazine-based ultraviolet absorber can be represented by the following general formula 2, for example.

式中、Ｒ^２１、Ｒ^２２、Ｒ^２３は、それぞれ独立的に、水素原子、ハロゲン原子、アルキル基、あるいはアルコキシ基を表し、Ｒ^２４、Ｒ^２５は、それぞれ独立的に、アルキル基あるいはアリール基を表す。

In the formula, R ²¹ , R ²² and R ²³ each independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ²⁴ and R ²⁵ each independently represents an alkyl group or an aryl group. Represents.

  Among the above general formulas 2, compounds of the following general formula 3 are particularly preferable.

式中、Ｒ^２１、Ｒ^２２、Ｒ^２３は、一般式２と同義である。Ｒ^２６、Ｒ^２７、Ｒ^２８は、それぞれ独立的に、水素原子、ハロゲン原子、アルキル基、アリール基、あるいはアルコキシ基を表す。

In formula, R <^21> , R <^22> , R < ²³ > is synonymous with General formula 2. R ²⁶ , R ²⁷ and R ²⁸ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an alkoxy group.

Specific examples of the hydroxyphenyltriazine-based ultraviolet absorbers represented by the above general formulas 2 and 3 will be given below, but the present invention is not limited thereto.
2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-pentoxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine,
2,4-diphenyl-6- (2-hydroxy-4- (2-butoxyethoxy) phenyl) -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-pentoxyphenyl) -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine,
2,4-di-p-trail-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine,
2,4-di-p-tolyl-6- (2-hydroxy-4- (2-hexyloxyethoxy) phenyl) -1,3,5-triazine,
2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,
2- [4-[(2-Hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- Triazine,
2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3,5-triazine,
2- (2-hydroxy-4-[(1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine,
Etc.

  The above triazine-based ultraviolet absorbers are commercially available from Ciba Japan Co., Ltd. under the trade names TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479.

  In the pressure-sensitive adhesive composition of the present invention, the content of the triazine-based ultraviolet absorber is suitably in the range of 0.5 to 20 parts by weight, more preferably in the range of 1 to 15 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive. The range of 2-10 mass parts is especially preferable.

  The pressure-sensitive adhesive composition according to the present invention contains a pressure-sensitive adhesive as a main component. The content of the pressure-sensitive adhesive in the pressure-sensitive adhesive composition of the present invention is suitably in the range of 60 to 99% by weight and in the range of 70 to 96% by weight with respect to 100% by weight of the total solid content of the pressure-sensitive adhesive composition. The range of 80 to 95% by mass is particularly preferable.

  As such an adhesive, a conventionally known adhesive can be used. For example, acrylic pressure-sensitive adhesive, rubber pressure-sensitive adhesive, polyester-based pressure-sensitive adhesive, urethane-based pressure-sensitive adhesive, silicone-based pressure-sensitive adhesive, and the like. Among these, acrylic pressure-sensitive adhesive is transparent, light-resistant, heat-resistant, and It is preferably used in terms of resistance to moist heat.

  The glass transition point of the resin constituting the pressure-sensitive adhesive is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, and particularly preferably −20 ° C. or lower from the viewpoint of ensuring the adhesiveness. The lower limit is about −80 ° C. However, in the pressure-sensitive adhesive composed of a resin having a low glass transition point as described above, the near-infrared absorbing dye contained therein moves relatively easily, thereby increasing the reactivity, and as a result, absorbing near-infrared light. The deterioration of the light resistance, heat resistance and wet heat resistance of the dye was promoted.

  Even if the pressure-sensitive adhesive composition of the present invention uses a pressure-sensitive adhesive composed of a resin having a glass transition point of 0 ° C. or lower, more preferably −10 ° C. or lower, particularly −20 ° C. or lower, the near-infrared absorbing dye The deterioration of the light resistance, heat resistance and wet heat resistance can be suppressed.

  The pressure-sensitive adhesive composition of the present invention preferably contains a crosslinking agent. Examples of such a cross-linking agent include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, and methylol polymers. In the present invention, polyisocyanate compounds are preferably used.

  Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Isocyanates and the like, and biurets, isocyanurates, and adducts that are a reaction product with a low molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. be able to.

  The said crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the crosslinking agent is suitably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive, and preferably in the range of 0.1 to 10 parts by mass.

  The pressure-sensitive adhesive composition of the present invention preferably contains a dye having a maximum absorption wavelength at 570 to 610 nm, so-called neon light cut dye. The plasma display emits so-called neon orange light centered around 600 nm, and there is a problem that orange is mixed with red, and a vivid red cannot be obtained. Can be solved.

  Examples of the neon light-cutting dye include, for example, tetraazaporphyrin, cyanine, squarylium, indole compound, azomethine, xanthene, oxonol, azo, quinone, azurenium, pyrylium, croconium, Examples include pyromethene and porphyrin. These dyes can be used alone or in combination of two or more. In the present invention, tetraazaporphyrin, cyanine, and squarylium dyes are preferably used.

  In the case of a filter for plasma display to which a near-infrared absorbing pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the present invention is applied, the transmittance at the maximum absorption wavelength at 570 to 610 nm is 40% or less, preferably 30% or less. More preferably, the content is adjusted so as to be 20% or less, and the content of the neon light cut pigment is appropriately selected so as to achieve the above-described transmittance. Specifically, the neon light cut colorant is suitably in the range of 0.001 to 1 part by weight, preferably in the range of 0.01 to 0.5 part by weight, with respect to 100 parts by weight of the adhesive.

  The pressure-sensitive adhesive composition of the present invention can contain a dye having absorption in the visible region for color tone adjustment. Examples of the color tone adjusting dye include anthraquinone, cyanine, squarylium, coumarin, styryl, rhodamine, azomethine, xanthene, oxonol, azo, quinone, perinone, azurenium, pyrylium, croconium. System, pyromethene, porphyrin and the like.

  In addition, the pressure-sensitive adhesive composition of the present invention further includes a leveling agent, an antistatic agent, a heat stabilizer, a light stabilizer, an antioxidant, a dispersant, a flame retardant, and a lubricant as long as the effects of the present invention are not impaired. Or you may contain the plasticizer etc.

  The pressure-sensitive adhesive composition of the present invention is an organic solvent for dissolving near-infrared absorbing dyes, triazine-based ultraviolet absorbers, etc. in order to dissolve near-infrared-absorbing dyes, triazine-based ultraviolet absorbers, etc. It is preferable to contain a solvent. Examples of such organic solvents include aromatics such as toluene and xylene, amides such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetone, methanol, ethanol, i Examples include alcohols such as propyl alcohol, hydrocarbons such as hexane, tetrahydrofuran, and the like. These organic solvents may be used alone, or may be appropriately mixed and used as necessary.

  The pressure-sensitive adhesive composition of the present invention is coated on a substrate and dried or cured to obtain the near-infrared absorbing pressure-sensitive adhesive layer of the present invention. Hereinafter, the near-infrared absorbing pressure-sensitive adhesive layer of the present invention is simply referred to as “pressure-sensitive adhesive layer of the present invention”.

  The coating method of the pressure-sensitive adhesive composition for obtaining the pressure-sensitive adhesive layer of the present invention is not particularly limited, and conventionally known coating methods can be used. For example, dip coating method, spray coating method, spinner coating method, bead coating method, wire bar coating method, blade coating method, roller coating method, curtain coating method, slot die coater method, gravure coater method, slit reverse coater method, micro A coating method such as a gravure method or a comma coater method can be used.

  Examples of the substrate on which the pressure-sensitive adhesive composition of the present invention is applied include a plastic film and a glass plate. The plastic film may be a release film, or may be a near-infrared absorbing film, an antireflection near-infrared absorbing film, or a substrate film constituting a display filter, which will be described later.

  The near-infrared absorbing film of the present invention is obtained by applying the pressure-sensitive adhesive composition of the present invention on the base film and laminating the pressure-sensitive adhesive layer of the present invention. Here, the base film is preferably a base film having a function other than the near-infrared absorbing function, such as an antireflection function, an antiglare function, a hard coat function, an electromagnetic wave shielding function, a color tone adjusting function, or the like. ,In particular. A base film having an antireflection function is preferred. What laminated | stacked the adhesive layer of this invention on the base film which has said antireflection function is synonymous with the antireflection near-infrared absorption film mentioned later.

  As the substrate film, a plastic film is preferable. Examples of the resin constituting the plastic film include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as triacetyl cellulose, polyolefin resins such as polyethylene, polypropylene, and polybutylene, acrylic resins, polycarbonate resins, arton resins, Examples thereof include an epoxy resin, a polyimide resin, a polyetherimide resin, a polyamide resin, a polysulfone resin, a polyphenylene sulfide resin, and a polyether sulfone resin. Among these, a polyester resin, a polyolefin resin, and a cellulose resin are preferable, and a polyester resin is particularly preferably used. These plastic films are preliminarily provided with an easy-adhesion layer for improving the adhesion to the layers laminated on the plastic film (the pressure-sensitive adhesive layer of the present invention, the hard coat layer and the antireflection layer described later). A plastic film is preferred.

  As thickness of a base film, the range of 50-300 micrometers is suitable, and the range of 90-250 micrometers is preferable.

  The release film is for protecting the pressure-sensitive adhesive layer of the present invention, and is peeled off before the pressure-sensitive adhesive layer of the present invention is used. Such a release film is subjected to release treatment for improving the peelability from the pressure-sensitive adhesive layer, for example, silicone treatment, long chain alkyl treatment, fluorine treatment, etc., on the surface of a plastic film such as polyethylene, polypropylene, polyethylene terephthalate. It has been done. About 30-100 micrometers is suitable for the thickness of a release film.

  The thickness of the pressure-sensitive adhesive layer of the present invention is suitably in the range of 3 to 100 μm, preferably in the range of 5 to 75 μm, and most preferably in the range of 10 to 50 μm.

  The pressure-sensitive adhesive layer of the present invention is preferably used for an antireflection near-infrared absorbing film or a display filter.

  The antireflective near-infrared absorbing film having the pressure-sensitive adhesive layer of the present invention (hereinafter referred to as “antireflective near-infrared absorbing film of the present invention”) is the surface of the antireflective film on which the antireflective layer is not provided. The agent layer is laminated.

  The antireflection film used for the antireflection near-infrared absorbing film of the present invention is one in which an antireflection layer is provided on one side of a base film such as a plastic film. Conventionally known layers can be used as the antireflection layer. Examples of the antireflection layer include a single layer configuration of a low refractive index layer and a stacked configuration of a high refractive index layer and a low refractive index layer. The refractive index of the low refractive index layer is generally in the range of 1.25 to 1.44, and preferably in the range of 1.30 to 1.43. The refractive index of the high refractive index layer is generally in the range of 1.45 to 1.80, and preferably in the range of 1.50 to 1.70.

  In addition, the antireflection film used in the antireflection near-infrared absorbing film of the present invention preferably has a hard coat layer provided between the base film and the antireflection layer, and the hard coat layer is preferably an antireflection layer. A high refractive index hard coat layer also serving as a high refractive index layer is more preferable. As the antireflection film using the high refractive index hard coat layer, a film in which a high refractive index hard coat layer and a low refractive index layer are laminated in this order on a substrate is preferably used.

  The pressure-sensitive adhesive layer of the present invention is preferably used for a display filter, particularly a plasma display filter. The above-described antireflection near-infrared absorbing film of the present invention can also be used as a constituent member of a filter for plasma display.

  When the pressure-sensitive adhesive layer of the present invention is applied to an antireflection near-infrared absorbing film or a filter for plasma display, the thickness of the pressure-sensitive adhesive layer of the present invention is suitably in the range of 3 to 100 μm, preferably in the range of 5 to 75 μm, In particular, the range of 10 to 50 μm is most preferable.

  The filter for plasma display to which the pressure-sensitive adhesive layer of the present invention is applied will be described in detail.

  Two types of plasma display filters are known. One type is a so-called front-mounted type that is arranged with a space from the display panel, and the other type is a so-called direct-attached type that is directly attached to the display panel.

  In general, the pre-installed type that has been generally known has a glass plate as an essential component, and various functional films such as an antireflection film, an electromagnetic wave shielding film, a near-infrared absorbing film, and the like are attached to the glass plate with an adhesive layer. It is a combined configuration.

  The direct attachment type generally known from the past is one in which an adhesive layer for direct attachment is laminated on one side of a laminated film in which the various functional films described above are attached together with an adhesive layer. In the direct attachment type, a glass plate is usually not used.

  In addition, a function integrated film in which two or more functions such as an antireflection function, an electromagnetic wave shielding function, and a near infrared absorption function are integrated is also known. It is known to use types.

  Examples of the function integrated film include those in which an antireflection layer and a near infrared absorption layer are provided on one plastic film, those in which an electromagnetic wave shielding layer and an antireflection layer are provided on one plastic film, and electromagnetic wave shielding. The layer and the near-infrared absorbing layer are provided on one plastic film, or the antireflection layer, the electromagnetic wave shielding layer, and the near-infrared absorbing layer are provided on one plastic film. The antireflection near-infrared absorbing film of the present invention described above is also one of the function integrated films.

  The pressure-sensitive adhesive layer of the present invention is preferably applied to the above-mentioned front-type and direct-attach type plasma display filters. That is, in the case of the front type, the pressure-sensitive adhesive layer of the present invention can be used as a pressure-sensitive adhesive layer for bonding various functional films or functional integrated films to a glass plate. The pressure-sensitive adhesive layer of the present invention can be used as a pressure-sensitive adhesive layer for bonding the function-integrated film or as a pressure-sensitive adhesive layer for direct attachment.

  By applying the pressure-sensitive adhesive layer of the present invention to a display filter such as a plasma display filter, a near-infrared absorbing film or a near-infrared absorbing resin layer for imparting a near-infrared absorbing function to the display filter is omitted. As a result, the number of constituent members can be reduced, and the simplification and cost reduction of the display filter can be realized.

  Although the structural example of the filter for plasma displays using the adhesive layer of this invention is illustrated below, this invention is not limited to these illustrations.

  In the following configuration example, the component described on the left side is the display panel side, and the “other pressure-sensitive adhesive layer” is a general pressure-sensitive adhesive layer that does not contain a near-infrared absorbing dye.

<Example of front-end configuration>
a) Electromagnetic wave shielding film / adhesive layer of the present invention / glass plate / other adhesive layer / antireflection film b) Electromagnetic shielding film / other adhesive layer / glass plate / adhesive layer / antireflection film of the present invention c) Glass plate / adhesive layer of the present invention / electromagnetic wave shielding antireflection function integrated film d) electromagnetic wave shielding film / adhesive layer of the present invention / glass plate

<Direct paste type>
e) Direct adhesive layer / electromagnetic wave shielding film / antireflection near-infrared absorbing film of the present invention (adhesive layer / antireflection film of the present invention)
f) The pressure-sensitive adhesive layer of the present invention (also serves as a pressure-sensitive adhesive layer for direct attachment) / Electromagnetic wave shielding film / Other pressure-sensitive adhesive layer / Antireflection film g) The pressure-sensitive adhesive layer of the present invention (also serves as a pressure-sensitive adhesive layer for direct attachment) / Electromagnetic wave shielding / antireflection function integrated film Specific structures of the electromagnetic wave shielding / antireflection function integrated film in the above configuration examples include, for example, a) electromagnetic wave shielding layer / substrate film / antireflection layer (including hard coat layer), b) ) Base film / electromagnetic wave shielding layer / antireflection layer (including hard coat layer).

  As the electromagnetic wave shielding layer used in the filter for plasma display according to the present invention, a so-called conductive mesh obtained by processing a conductive metal layer into a mesh pattern ensures the transmittance of the filter for plasma display, It is preferably used from the viewpoint of processing cost and electromagnetic wave shielding performance.

  When the pressure-sensitive adhesive layer of the present invention is applied to a display filter such as a plasma display filter, it is particularly effective for a display filter having the following constitution. That is, when the display filter including the pressure-sensitive adhesive layer of the present invention is attached to the display panel, the base material (located at a position farther than the pressure-sensitive adhesive layer with respect to the display panel) placed on the viewing side from the pressure-sensitive adhesive layer ( The pressure-sensitive adhesive layer of the present invention is particularly effective in a filter for a display that is not provided with an ultraviolet shielding function on a plastic film or a glass plate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

  In addition, the PET film, the glass plate, and the release PET film used in the following examples and comparative examples are not provided with an ultraviolet shielding function.

The evaluation method of each sample produced in the following examples and comparative examples is shown below.
(1) Transmission characteristics Using a spectrophotometer (manufactured by Shimadzu Corporation, trade name “UV-3150”), the spectrum of a 50 × 50 mm square specimen cut out from each sample was measured in the range of 350 to 1100 nm. The visual average transmittance Tv and chromaticity coordinates (x, y) of 380 to 780 nm in a D65 light source were calculated. Further, the transmittance in the near infrared region (850 nm, 900 nm, 1000 nm) was set to Tn1, Tn2, and Tn3, respectively. Each numerical value used the indoor air permeability as a comparative control.

  In the following evaluation of light resistance, heat resistance, and moist heat resistance, the difference between measured values before and after the test is an absolute value. All the characteristics indicate that the difference between before and after the test is closer to 0, the better.

  As one criterion for evaluation, when the difference in luminous average transmittance (ΔTv) is 1.0% or more, there is a possibility of practical problems, and the difference in chromaticity coordinates (Δx, Δy) is 0.004 or more. Then, there is a possibility of practical problems, and when any one of the transmittance differences (ΔTn1, ΔTn2, ΔTn3) in the near-infrared region (850 nm, 900 nm, 1000 nm) becomes 3.0% or more, it becomes a practical problem. there is a possibility.

(2) Evaluation of light resistance A test piece whose transmission characteristics were measured by the method of (1) above was set in a light resistance tester (trade name “Xenon Fade Meter” manufactured by Suga Test Instruments Co., Ltd.), and the test was performed for 50 hours. Irradiation was performed (approximately 550 W / m ^{2 in} terms of integrated light amount). Subsequently, the transmission characteristic of the test piece taken out from the light resistance tester was measured by the method (1). The difference in luminous average transmittance before and after the test (ΔTv), the difference in chromaticity coordinates (Δx, Δy), and the transmittance difference (ΔTn1, ΔTn2, ΔTn3) in the near infrared region (850 nm, 900 nm, 1000 nm) were determined. It was used as an index.

(3) Evaluation of heat resistance The test piece whose permeation | transmission characteristic was measured by the method of said (1) in the constant temperature thermostat set to the temperature of 80 degreeC was left to stand for 1000 hours. Subsequently, the permeation | transmission characteristic of the test piece taken out from the constant temperature thermostat was measured by the method of said (1). The difference in luminous average transmittance before and after the test (ΔTv), the difference in chromaticity coordinates (Δx, Δy), and the transmittance difference (ΔTn1, ΔTn2, ΔTn3) in the near infrared region (850 nm, 900 nm, 1000 nm) were determined. It was used as an index.

(4) Evaluation of moisture and heat resistance A test piece whose transmission characteristics were measured by the method of (1) above was left in a constant temperature and humidity tester set at a temperature of 60 ° C. and a relative humidity of 90% for 1000 hours. Subsequently, the permeation | transmission characteristic of the test piece taken out from the constant temperature and humidity tester was measured by the method of said (1). The difference in luminous average transmittance (ΔTv) before and after the test, the difference in chromaticity coordinates (Δx, Δy), and the transmittance difference (ΔTn1, ΔTn2, ΔTn3) in the near infrared region (850 nm, 900 nm, 1000 nm) were determined. It was used as an index.

Example 1
<Preparation of pressure-sensitive adhesive composition>
Phthalocyanine having a maximum absorption wavelength of 800 nm or more and 850 nm or less as a near-infrared absorbing dye (manufactured by Nippon Shokubai Co., Ltd., trade name “EEX COLOR IR-14”), 0.56 parts by mass, 850 nm to 900 nm or less Phthalocyanine having a wavelength (0.43 parts by mass, manufactured by Nippon Shokubai Co., Ltd., trade name “EEX Color IR-12”), phthalocyanine having a maximum absorption wavelength of more than 900 nm and not more than 950 nm (manufactured by Nippon Shokubai Co., Ltd.) 1. Product name “e-ex color IR-20”) 0.2 parts by mass, phthalocyanine having a maximum absorption wavelength of more than 950 nm and 1000 nm or less (product name “e-ex color IR-915” manufactured by Nippon Shokubai Co., Ltd.) Tetraazaporphyri as a neon light-cutting dye having 84 parts by mass and a maximum absorption wavelength at 570 to 610 nm 0.28 parts by mass (trade name “PD-320”, manufactured by Mitsui Chemicals, Inc.) and hydroxyphenyl triazine-based ultraviolet absorber (trade name “TINUVIN479”, manufactured by Ciba Japan Co., Ltd.) as an ultraviolet absorber Part by mass in 155.2 parts by mass of ethyl acetate and 155.2 parts by mass of toluene, and acrylic adhesive (manufactured by Toyo Ink Manufacturing Co., Ltd., trade name “BPS6271”; adhesive content is 29% by mass And mixed with 689.6 parts by mass of ethyl acetate and toluene, and further mixed with 10.3 parts by mass of an isocyanate crosslinking agent (trade name “BXX6105” manufactured by Toyo Ink Manufacturing Co., Ltd.) An agent composition was prepared.

<Preparation of a sample with an adhesive layer>
The pressure-sensitive adhesive composition was coated on a release PET film (thickness 38 μm) with a slot die coater so that the dry thickness was 25 μm, and dried to form a pressure-sensitive adhesive layer. Then, a PET film (thickness 100 μm) was bonded to the pressure-sensitive adhesive layer surface. In this state, after leaving at room temperature for 7 days, the release film on the pressure-sensitive adhesive layer surface was peeled off, and the pressure-sensitive adhesive layer surface was bonded to a glass plate (thickness 1.8 mm), and PET film / pressure-sensitive adhesive layer / glass plate Were prepared in this order.

Example 2
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the ultraviolet absorber was changed to the trade name “TINUVIN405” manufactured by Ciba Japan Co., Ltd., which is a hydroxyphenyltriazine-based ultraviolet absorber. A sample in which the pressure-sensitive adhesive layer was laminated was produced in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was changed.

Example 3
Near infrared absorbing dye, phthalocyanine having a maximum absorption wavelength of 800 nm or more and 850 nm or less (made by Nippon Shokubai Co., Ltd., trade name “EEX Color IR-14”), 0.56 parts by mass, 850 nm to 900 nm or less Phthalocyanine having an absorption wavelength (manufactured by Nippon Shokubai Co., Ltd., trade name “EEX Color IR-12”) 0.46 parts by mass, phthalocyanine having a maximum absorption wavelength of more than 950 nm and 1000 nm or less (manufactured by Nippon Shokubai Co., Ltd.) Product name “EEX Color IR-915”) 1.84 parts by mass, dithiol metal complex dye (manufactured by API Corporation, product name “APE-004”) A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1. A sample in which an adhesive layer was laminated was prepared in the same manner as in Example 1 except that the adhesive composition was changed.

Comparative Example 1
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that no ultraviolet absorber was contained. A sample in which the pressure-sensitive adhesive layer was laminated was produced in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was changed.

Comparative Example 2
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the ultraviolet absorber was changed to a benzotriazole-based ultraviolet absorber (trade name “TINUVIN109” manufactured by Ciba Japan Co., Ltd.). A sample in which the pressure-sensitive adhesive layer was laminated was produced in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was changed.

Comparative Example 3
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the ultraviolet absorber was changed to a benzotriazole-based ultraviolet absorber (SEPRORB 704, manufactured by Sipro Kasei Co., Ltd.). A sample in which the pressure-sensitive adhesive layer was laminated was produced in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was changed.

Comparative Example 4
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the ultraviolet absorber was changed to a benzophenone-based ultraviolet absorber (trade name “CHIMASSORB81” manufactured by Ciba Japan Co., Ltd.). A sample in which an adhesive layer was laminated was prepared in the same manner as in Example 1 except that the adhesive composition was changed.

Comparative Example 5
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the near-infrared absorbing dye was changed to 2 parts by mass of a diimonium dye (manufactured by Nippon Kayaku Co., Ltd., trade name “IRG-069”). A sample in which the pressure-sensitive adhesive layer was laminated was produced in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was changed.

Comparative Example 6
A phthalocyanine (Nippon Shokubai Co., Ltd.) having 1.5 parts by mass of a near-infrared absorbing dye as a diimonium dye (made by Nippon Kayaku Co., Ltd., trade name “IRG-069”) and having a maximum absorption wavelength of 800 nm or more and 850 nm or less. Phthalocyanine having a maximum absorption wavelength of more than 850 nm and not more than 900 nm (made by Nippon Shokubai Co., Ltd., trade name “e-ex color IR-12”) 0 A pressure-sensitive adhesive composition was produced in the same manner as in Example 1 except that the content was changed to .46 parts by mass. A sample in which the pressure-sensitive adhesive layer was laminated was produced in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was changed.

Comparative Example 7
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1 except that the near-infrared absorbing dye was changed to 4 parts by mass of a dithiol metal complex dye (manufactured by API Corporation, trade name “APE-004”). did. A sample in which the pressure-sensitive adhesive layer was laminated was produced in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was changed.

Comparative Example 8
Near infrared absorbing dye, phthalocyanine having a maximum absorption wavelength of 800 nm or more and 850 nm or less (made by Nippon Shokubai Co., Ltd., trade name “EEX Color IR-14”), 0.56 parts by mass, 950 nm to 1000 nm or less 1.84 parts by weight of phthalocyanine having an absorption wavelength (trade name “EEX Color IR-915”, manufactured by Nippon Shokubai Co., Ltd.), dithiol metal complex dye (manufactured by API Corporation, trade name “APE-004”) ]) Except changing to 3.6 mass parts, it carried out similarly to Example 1, and produced the adhesive composition. A sample in which the pressure-sensitive adhesive layer was laminated was produced in the same manner as in Example 1 except that this pressure-sensitive adhesive composition was changed.

[Evaluation]
About the sample produced as mentioned above, the permeation | transmission characteristic, light resistance, heat resistance, and heat-and-moisture resistance were evaluated. Table 1 shows the contents of the sample and the permeability (initial value) before the test, and Table 2 shows the results of light resistance, heat resistance, and moist heat resistance.

  From the above results, it can be seen that the examples of the present invention are excellent in any of light resistance, heat resistance, and moist heat resistance.

  In contrast, Comparative Example 1 using phthalocyanine but containing no UV absorber, Comparative Example 2 and Comparative Example 3 combining phthalocyanine and a benzotriazole UV absorber, and combining phthalocyanine and a benzophenone UV absorber In all of Comparative Examples 4, the light resistance was greatly deteriorated.

  Further, Comparative Example 5 in which 100% by mass of a diimonium dye and a hydroxyphenyltriazine ultraviolet absorber are combined, and Comparative Example in which 60% by mass of a diimonium dye and 40% by mass of phthalocyanine are contained, and which contains a hydroxyphenyltriazine ultraviolet absorber. As for No. 6, light resistance, heat resistance, and heat-and-moisture resistance deteriorated, and especially heat resistance and heat-and-moisture resistance deteriorated greatly.

  Further, Comparative Example 7 in which 100% by mass of a dithiol metal complex dye and a hydroxyphenyltriazine ultraviolet absorber were combined, and 60% by mass of a dithiol metal complex dye and 40% by mass of phthalocyanine, and a hydroxyphenyltriazine ultraviolet absorber In Comparative Example 8 containing, the light resistance, heat resistance, and moist heat resistance were greatly deteriorated.

Example 4
The antireflection near-infrared absorbing film of the present invention was produced in the following manner.
<Preparation of pressure-sensitive adhesive composition>
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1.

<Preparation of antireflection film>
The following antireflection layer was laminated on one surface of a PET film (thickness: 100 μm). The antireflection layer is obtained by sequentially laminating a high refractive index hard coat layer and a low refractive index layer on a PET film.

<Lamination of high refractive index hard coat layer>
An antistatic high refractive index hard coat paint (XJC-0357; refractive index 1.66) manufactured by Pernox Co., Ltd. was coated on a PET film with a micro gravure coater, dried at 90 ° C., and then irradiated with ultraviolet light 400 mJ / It was cured by irradiating cm ^2, and an antistatic high refractive index hard coat layer having a thickness of about 1.7 μm was provided.

<Lamination of low refractive index layer>
Low refractive index having a solid content concentration of 3% by mass by adding methyl isobutyl ketone and propylene glycol monobutyl ether in a ratio of 1: 1 to a commercially available low refractive index paint (TU2180 manufactured by JSR Corporation: refractive index 1.37). A coating solution for forming a rate layer was prepared. This coating solution for forming a low refractive index layer is coated on the high refractive index hard coat layer laminated on the PET film with a micro gravure coater, dried at 90 ° C., and then irradiated with ultraviolet rays of 400 mJ / cm ² . And cured to form a low refractive index layer having a thickness of about 100 nm.

<Preparation of antireflection near-infrared absorbing film of the present invention>
The pressure-sensitive adhesive composition prepared above was applied to the back surface of the antireflection film prepared above (the surface opposite to the surface on which the antireflection layer was laminated) with a slot die coater so that the dry thickness was 25 μm, and dried. Thus, an adhesive layer was formed. Next, a release PET film (thickness 38 μm) was bonded to the pressure-sensitive adhesive layer surface to produce an antireflection near-infrared absorbing film of the present invention.

[Evaluation]
The antireflection near-infrared absorbing film produced as described above was evaluated for light resistance, heat resistance, and moist heat resistance. As a result, excellent results were obtained as in Example 1.

Example 5
A plasma display filter was produced in the following manner.
<Preparation of electromagnetic shielding film>
On one side of a PET film (thickness 100 μm), a nickel layer (thickness 0.02 μm) by sputtering, a copper layer (thickness 2.5 μm) by vacuum deposition, and a copper nitride layer (thickness 0.03 μm) by sputtering are formed. Then, a photoresist layer is applied and formed on the surface of the copper nitride layer side, and the photoresist layer is exposed and developed through a mask of a lattice mesh pattern, and then subjected to an etching treatment to form a mesh pattern (electromagnetic wave shielding) Layer; conductive mesh) to form an electromagnetic wave shielding film.

<Direct adhesive layer>
As a direct adhesive layer for directly attaching a plasma display filter to a panel, a release PET film (thickness 38 μm) was prepared on both sides of an acrylic adhesive layer having a thickness of 25 μm. .

<Preparation of plasma display filter>
The release PET film on the surface of the pressure-sensitive adhesive layer of the antireflection near-infrared absorbing film of the present invention produced in the same manner as in Example 4 was peeled off, and the anti-reflection near-infrared absorbing film of the present invention and the above-mentioned film were peeled through this pressure-sensitive adhesive layer. The electromagnetic wave shielding layer surfaces of the electromagnetic wave shielding films were bonded so that the surfaces face each other. Next, one release PET film of the pressure-sensitive adhesive layer for direct attachment was peeled and laminated on the surface opposite to the electromagnetic wave shielding layer surface of the electromagnetic wave shielding film.

  The filter for plasma display produced as described above is a release PET film / adhesive layer for direct attachment / electromagnetic wave shielding film / antireflection near-infrared absorbing film of the present invention (adhesive layer / antireflection film of the present invention). Are stacked in order from the display panel side.

[Evaluation]
About the filter for plasma displays produced as mentioned above, when light resistance, heat resistance, and heat-and-moisture resistance were evaluated, the result excellent similarly to Example 1 was obtained.

Example 6
A plasma display filter was produced in the following manner.
<Preparation of electromagnetic shielding film>
An electromagnetic wave shielding film was produced in the same manner as in Example 5.

<Preparation of integrated film for electromagnetic wave shielding / antireflection function>
On the electromagnetic wave shielding layer of the electromagnetic wave shielding film produced above, the following hard coat layer and antireflection layer (low refractive index layer) were sequentially laminated to produce an electromagnetic wave shielding antireflection function integrated film.

<Lamination of hard coat layer>
A commercially available hard coat agent (Opstar (registered trademark) Z7534 manufactured by JSR; solid content concentration 60% by weight) is diluted with methyl isobutyl ketone so that the solid content concentration is 35% by weight, and a coating for forming a hard coat layer is prepared. did. This hard coat layer-forming coating material is coated on the electromagnetic wave shielding layer of the electromagnetic wave shielding film produced above with a micro gravure coater, dried at 90 ° C., and then cured by irradiation with ultraviolet rays of 500 mJ / cm ² to obtain a thickness. A hard coat layer having a thickness of about 9 μm was laminated.

<Lamination of low refractive index layer>
Low refractive index having a solid content concentration of 3% by mass by adding methyl isobutyl ketone and propylene glycol monobutyl ether in a ratio of 1: 1 to a commercially available low refractive index paint (TU2180 manufactured by JSR Corporation: refractive index 1.37). A coating solution for forming a rate layer was prepared. This coating solution for forming a low refractive index layer is coated on the hard coat layer laminated on the electromagnetic wave shielding layer of the electromagnetic wave shielding film as described above by a micro gravure coater, dried at 90 ° C., and ultraviolet rays 400 mJ / cm ^2. Was cured by irradiation to form a low refractive index layer having a thickness of about 100 nm.

<Preparation of plasma display filter>
A pressure-sensitive adhesive composition was prepared in the same manner as in Example 1. This pressure-sensitive adhesive composition was coated and dried on the surface opposite to the electromagnetic wave shielding layer of the electromagnetic wave shielding / antireflection function integrated film obtained above with a slot die coater so that the dry thickness was 25 μm. The pressure-sensitive adhesive layer of the invention was laminated, and a release PET film (thickness 38 μm) was further laminated on the surface of the pressure-sensitive adhesive layer of the present invention to produce a plasma display filter.

[Evaluation]
About the filter for plasma displays produced as mentioned above, when light resistance, heat resistance, and heat-and-moisture resistance were evaluated, the result excellent similarly to Example 1 was obtained.

Claims (11)

  A near-infrared-absorbing pressure-sensitive adhesive composition comprising phthalocyanine as a near-infrared absorbing dye and containing a triazine-based ultraviolet absorber.   The near-infrared-absorbing pressure-sensitive adhesive composition according to claim 1, comprising 60% by mass or more of phthalocyanine with respect to 100% by mass of the total amount of the near-infrared absorbing dye.   The near-infrared absorbing adhesive composition according to claim 1 or 2, wherein the triazine-based ultraviolet absorber is a hydroxyphenyl triazine-based ultraviolet absorber.   The phthalocyanine includes at least one phthalocyanine having a maximum absorption wavelength of 800 nm or more and 900 nm or less and at least one phthalocyanine having a maximum absorption wavelength of more than 900 nm and 1000 nm or less. 4. The near-infrared absorbing adhesive composition according to any one of 3 above. The near-infrared absorbing adhesive composition according to any one of claims 1 to 4, wherein the phthalocyanine contains three or more phthalocyanines selected from the group consisting of A) to D) below.
A) Phthalocyanine having a maximum absorption wavelength of 800 nm or more and 850 nm or less B) Phthalocyanine having a maximum absorption wavelength of more than 850 nm and 900 nm or less C) Phthalocyanine having a maximum absorption wavelength of more than 900 nm and 950 nm or less D) Above 950 nm and 1000 nm or less Phthalocyanine with maximum absorption wavelength   A near-infrared absorbing pressure-sensitive adhesive layer obtained from the near-infrared absorbing pressure-sensitive adhesive composition according to claim 1.   The near-infrared absorptive adhesive layer according to claim 6 is laminated on a substrate film.   An antireflection film having an antireflection layer on one surface, wherein the near infrared absorbing pressure-sensitive adhesive layer according to claim 6 is laminated on a surface opposite to the surface having the antireflection layer. Anti-reflection near-infrared absorbing film.   A display filter comprising the near-infrared absorbing pressure-sensitive adhesive layer according to claim 6.   A display filter comprising the antireflection near-infrared absorbing film according to claim 8.   The display filter according to claim 9 or 10, wherein the display filter is for a plasma display.