JP2009013200A - Near-infrared absorbing pressure-sensitive adhesive and near-infrared absorbing pressure-sensitive adhesive sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared absorbing pressure-sensitive adhesive forming a near-infrared absorbing pressure-sensitive adhesive layer which can absorb near-infrared radiation over a wide range and substantially avoids deterioration of its near-infrared absorption capacity even when exposed at high temperature or at high temperature and high humidity over a long period of time. <P>SOLUTION: The near-infrared absorbing pressure-sensitive adhesive comprises a polyester resin (D) having a glass transition temperature in a range of -80 to 0°C and having a hydroxy group and/or a carboxy group in a side chain, a diimonium salt compound (e1), another near-infrared absorbing agent (e2) different from the diimonium salt compound (e1) in absorption maximum wavelength, and a reactive compound (F) reacting with the hydroxy group and/or the carboxy group in the resin (D). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyester-based pressure-sensitive adhesive having a near-infrared absorbing function, and more particularly to a near-infrared-absorbing pressure-sensitive adhesive. More specifically, a display that absorbs near-infrared rays generated from a plasma display (hereinafter also referred to as PDP), an image output device such as a CRT, a liquid crystal, etc., thereby blocking near-infrared entry and preventing malfunction of peripheral electronic devices. It is related with the near-infrared absorptive pressure-sensitive-type adhesive suitable for use of the front panel arrange | positioned in front.

  In recent years, various types of displays have been developed and commercialized as large displays. A plasma display is one of them, and is particularly attracting attention as a large display for hanging on the wall from the viewpoint of enlargement, thickness reduction, and weight reduction of 40 inch size or more. This plasma display emits light rays other than the wavelength bands of the three primary colors (red, green, and blue) of the color image from the visible light region to the infrared wavelength region due to structural factors of each pixel portion constituting the light source or the discharge unit. For example, strong near-infrared emission occurs at wavelengths of 820 nm, 880 nm, 980 nm, and the like. Since these near infrared rays match the operating wavelengths of peripheral electronic devices such as televisions, remote controllers for video and coolers, portable communication, and near infrared communication devices such as personal computers, malfunctions occur.

  Therefore, it has been proposed to use an optical filter that absorbs near infrared rays. As such a near-infrared absorption filter, a phosphate glass filter containing divalent copper ions, a thin layer of metal (for example, silver) on the surface of glass or the like, vapor deposition method, sputtering method, ion plating method, etc. Examples thereof include a filter molded by a method and a filter in which a dye absorbing a wavelength in the near infrared region is added to a resin.

  However, among the near-infrared absorbing filters as described above, the phosphate-containing glass filter has a problem that it is complicated to manufacture and easily absorbs moisture. In addition, when a thin layer of metal is provided on the surface of glass or the like, although it is less compared to the near infrared region, light in the visible light region is also reflected. There are also problems such as high manufacturing costs. Furthermore, since these methods use glass in common, there are problems that the obtained filter is heavy and easily broken, and that processing is difficult.

In contrast, a filter in which a dye that absorbs a wavelength in the near-infrared region is added to a resin is advantageous in that it is lighter and easier to manufacture than a filter using glass.
For example, a dye that absorbs wavelengths in the near-infrared region is melted and kneaded into a thermoplastic resin under heating to form a film. This film can be used as a near-infrared absorbing filter, or a dye that absorbs wavelengths in the near-infrared region can be incorporated into the resin. There is a method in which a near-infrared absorbing laminate formed by applying a coating agent to be added to a base material such as a plastic film and forming a near-infrared absorbing layer is used as a near-infrared absorbing filter (see Patent Documents 1 to 5). ).

By the way, the PDP front panel is generally configured by laminating layers having various functions such as an electromagnetic wave absorption layer and an antireflection layer in addition to a layer having a near infrared absorption function. And when laminating | stacking each layer, it was common to use a pressure sensitive adhesive layer.
Therefore, from the viewpoint of reducing the size of the PDP front panel and reducing the number of processes, the invention of providing a near-infrared absorbing function to a pressure-sensitive adhesive layer used for lamination or a non-pressure-sensitive adhesive layer is disclosed in Patent Document 6. To 9 mag.

  Citation 6: Japanese Patent Application Laid-Open No. 7-178861 discloses that an ethylene-vinyl acetate (EVA) -based adhesive polymer containing a near-infrared absorbing dye and an ultraviolet absorber and glass or a resin plate are bonded together under heating to form a near-infrared ray. An invention for obtaining an absorbent plate is described.

Citation 7: Japanese Patent Laid-Open No. 10-156991 discloses a near-infrared absorbing pressure-sensitive adhesive layer using a pressure-sensitive adhesive containing various near-infrared absorbers such as diimonium compounds and dithiol metal complex compounds, and transparent An antireflection film having a near infrared absorption characteristic in which a resin film and an antireflection layer are sequentially laminated is described.
Unlike the adhesive polymer described in the cited document 6, the pressure-sensitive adhesive disclosed in the cited document 7 generally does not need to be heated at the time of sticking. Therefore, although it has excellent near-infrared absorption characteristics like diimonium-based compounds, it is more pressure-sensitive than non-pressure-sensitive adhesives from the viewpoint that it is easy to use even near-infrared absorbers whose absorption characteristics are susceptible to thermal degradation. An adhesive is preferred.

By the way, the surface of the light emitting substrate of the plasma display is about 50 ° C. to 80 ° C., and the near-infrared absorption filter laminated on the front plate is exposed to such a temperature for a long time.
Therefore, pigments that can have a near infrared absorption function used in near infrared absorption filters have long-term heat resistance (also referred to as thermal stability) as a near infrared absorption filter as well as heat resistance during the production of near infrared absorption filters. Required.
In the case of a pressure-sensitive adhesive that does not require heating at the time of sticking, the glass transition point (Tg) of the main component constituting the pressure-sensitive adhesive needs to be sufficiently low, unlike an adhesive other than the pressure-sensitive adhesive. Specifically, Tg needs to be low enough to be pasted at about 20 ° C.
Pressure sensitive adhesives that are forced to use a main component having a low Tg, because of their low Tg, can suppress and prevent thermal decomposition of the near-infrared absorber in the near-infrared absorbing filter over a long period of time. This is much more difficult than in the case of adhesives other than coating agents and pressure sensitive adhesives that can use the components.

Citation 8: Japanese Patent Application Laid-Open No. 2001-207142 discloses a near-infrared absorbing sensation containing an adhesive resin, a near-infrared absorber having a maximum absorption wavelength at 700 to 1100 nm, a polyfunctional (meth) acrylate monomer, and a photopolymerization initiator. A pressure-sensitive adhesive composition is described. Specifically, in order to avoid thermal damage during production, monomers are polymerized using ultraviolet rays, and near infrared absorption performance as an infrared absorption filter is stabilized for a long time under high temperature and high quality. An invention is described in which a cross-linked structure is to be introduced into a pressure-sensitive adhesive layer using a functional (meth) acrylate monomer.
However, in order to obtain an infrared absorption filter using the pressure-sensitive adhesive composition disclosed in Cited Document 8, the pressure-sensitive adhesive composition is coated on another functional layer, dried, and then subjected to ultraviolet light or the like. It is necessary to irradiate energy rays, and the manufacturing process becomes complicated.

Citation 9: Japanese Patent Application Laid-Open No. 2005-272588 discloses an acrylic pressure-sensitive adhesive containing a specific dye having excellent heat resistance. However, there is a problem that the dye used is subject to versatility.
JP 2001-174626 A JP 2001-175185 A JP 2003-43244 A Japanese Patent No. 3451228 Japanese Patent No. 3321705 JP-A-7-178861 Japanese Patent Laid-Open No. 10-156991 JP 2001-207142 A JP 2005-272588 A

  The present invention absorbs near infrared rays emitted from a plasma display to prevent malfunction of peripheral electronic devices, has high visible light transmittance, and is suitable for downsizing a PDP front panel. Pressure adhesives, specifically, near-infrared absorbing pressure-sensitive adhesives that can form a near-infrared-absorbing pressure-sensitive adhesive layer that is placed on the front face of a display and does not easily reduce near-infrared absorbing ability even when exposed to high temperatures for a long period of time The purpose is to do.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the first invention is a polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain, a diimonium salt compound (e1), and a diimonium salt having a glass transition temperature in the range of −80 to 0 ° C. Near-infrared ray comprising a reactive compound (F) capable of reacting with a hydroxyl group and / or a carboxyl group in the resin (D) with another near-infrared absorbing agent (e2) having an absorption maximum wavelength different from that of the compound (e1) The present invention relates to an absorbent pressure-sensitive adhesive.

  In the second invention, the other near-infrared absorbing agent (e2) comprises an aminium compound, an anthraquinone compound, a polymethine compound, a cyanine compound, a phthalocyanine compound, a benzopyridium compound, and a thiometal complex compound. The near-infrared-absorbing pressure-sensitive adhesive according to the invention, which is at least one selected from the group.

  In the third invention, a diimonium salt compound (e1) and another near-infrared absorbing agent (e2) are added in total to 100 parts by weight of a polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain. It is related with the near-infrared absorptive pressure sensitive adhesive in any one of the said invention characterized by including 0.01-20 weight part and reactive compound (F) 0.001-20 weight part.

In the fourth invention, the polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain is:
A dibasic acid component (A) having no hydroxyl group;
A diol (B) having no carboxyl group;
A trihydric or higher polyhydric alcohol (c1), a trihydric or higher polyhydric carboxylic acid (c2), a compound having two cyclic ether groups in the molecule (c3), two hydroxyl groups and one carboxyl group in one molecule At least one side-chain functional group-introducing component selected from the group consisting of dioxycarboxylic acid (c4) having the above and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule ( The near-infrared-absorbing pressure-sensitive adhesive according to any one of the above inventions, which is a polyester resin (D1) obtained by reacting C).

  In the fifth invention, the side chain functional group in the polyester resin (D1) having a hydroxyl group and / or carboxyl group in the side chain and a polyester resin (D1) having a hydroxyl group and / or a carboxyl group in the side chain. And a polyester resin (D2) obtained by ring-opening addition of the cyclic ester compound (G), wherein the ring-opening portion of the cyclic ester compound (G) has a side chain and a hydroxyl group at the terminal of the ring-opening portion. It is related with the near-infrared absorptive pressure-sensitive adhesive as described in the said invention characterized by the above-mentioned.

  The sixth invention is any one of the above inventions, wherein the reactive compound (F) has two or more functional groups capable of reacting with the side chain functional group in the polyester resin (D) in one molecule. The near-infrared absorptive pressure-sensitive adhesive described in 1.

  In a seventh aspect of the invention, a near-infrared-absorbing pressure-sensitive adhesive layer formed from the near-infrared-absorbing pressure-sensitive adhesive according to any one of the above inventions is laminated on at least one surface of the sheet-like substrate. The present invention relates to a near-infrared absorbing pressure-sensitive adhesive sheet.

  By using the near-infrared-absorbing pressure-sensitive adhesive resin composition of the present invention, the near-infrared absorptivity is less likely to be lowered even if it is placed in front of the display and exposed to high temperatures for a long period of time. An infrared-absorbing pressure-sensitive adhesive layer can be formed.

  The polyester resin (D) used in the present invention has a glass transition temperature of −80 to 0 ° C. and has a hydroxyl group and / or a carboxyl group in the side chain. The hydroxyl group and / or carboxyl group of the side chain reacts with the reactive compound (F) described later to form a pressure-sensitive adhesive layer. It is important that the polyester resin (D) for the pressure-sensitive adhesive has a functional group such as a hydroxyl group or a carboxyl group not only at the end of the main chain but also at the side chain.

The pressure sensitive adhesive is used to form a pressure sensitive adhesive sheet.
The basic laminate structure of the pressure-sensitive adhesive sheet is a sheet-like substrate / pressure-sensitive adhesive layer / single-sided pressure-sensitive adhesive sheet such as a release sheet, or a release sheet / pressure-sensitive adhesive layer / sheet-like substrate / pressure-sensitive type. It is a double-sided pressure-sensitive adhesive sheet such as an adhesive layer / release sheet. At the time of use, the release sheet is peeled off, and the pressure-sensitive adhesive layer is attached to the adherend. The pressure-sensitive adhesive is not only a pressure-sensitive adhesive layer that has a tack at the moment when the pressure-sensitive adhesive layer touches the adherend but also an adhesive other than the pressure-sensitive adhesive (hereinafter simply referred to as a pressure-sensitive adhesive). Unlike adhesives), it is necessary to have a cohesive force for maintaining the sticking state while having a tack and appropriate hardness without being completely solidified even during sticking. The cohesive force greatly depends on the molecular weight.

Since the polyester resin is formed by polycondensation, it is practically impossible to form a resin having a molecular weight exceeding hundreds of thousands. In the case of a polyester resin, if the condensation and decomposition reach an equilibrium state, the molecular weight will no longer increase, and if the reaction conditions are changed and further condensation is attempted, it will compete with deterioration. It is.
A polyester resin produced by polycondensation of a diol component and a dibasic acid component generally has a hydroxyl group or a carboxyl group at the end of the main chain. By reacting the hydroxyl group or carboxyl group at the end of the main chain of a polyester resin having a relatively low molecular weight with a relatively large amount of curing agent, it is possible to form an adhesive layer that is completely solidified, but with a relatively high molecular weight. A pressure-sensitive adhesive layer that needs to have tack and moderate hardness during bonding can be formed by simply reacting the hydroxyl group or carboxyl group at the end of the main chain of a polyester resin with a relatively small amount of curing agent. I couldn't. This is because crosslinking (curing) is sparse and sufficient cohesive force cannot be expressed. In the present invention, an appropriate cross-linked (cured) state can be formed by using a polyester resin (D) having a functional group such as a hydroxyl group or a carboxyl group not only at the end of the main chain but also at the side chain. .

The polyester resin (D) having a hydroxyl group or a carboxyl group in the side chain can be obtained by various methods.
For example, when a dibasic acid component (A) having no hydroxyl group is reacted with a diol (B) having no carboxyl group to obtain a polyester resin, a trihydric or higher polyhydric alcohol (c1), trivalent The above polyvalent carboxylic acid (c2), compound (c3) having two cyclic ether groups in the molecule, dioxycarboxylic acid (c4) having two hydroxyl groups and one or more carboxyl groups in one molecule, and one By using at least one side chain functional group-introducing component (C) selected from the group consisting of oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in the molecule, polyester resin (D) A hydroxyl group or a carboxyl group can be introduced into the side chain.

Examples of the dibasic acid component (A) having no hydroxyl group used in the present invention include known dicarboxylic acids and acid anhydrides thereof, and dicarboxylic acids and acid anhydrides and monoalcohols such as methanol and ethanol. Examples include esterified products.
For example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, etc. Aliphatic dicarboxylic acids;

  For example, o-phthalic acid, isophthalic acid, terephthalic acid, 2,5-dimethylterephthalic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane Aromatic dicarboxylic acids such as -4,4'-dicarboxylic acid and phenylindanedicarboxylic acid;

For example, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid,
Alicyclic dicarboxylic anhydrides such as hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride;

  For example, succinic anhydride, methyl succinic anhydride, 2,2-dimethyl succinic anhydride, butyl succinic anhydride, isobutyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, phenyl succinic anhydride Glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethyl glutaric anhydride, 2,4-diethyl glutaric anhydride, butyl glutaric anhydride, hexyl glutaric anhydride, maleic anhydride, 2-methyl maleic anhydride 2,3-dimethylmaleic anhydride, butylmaleic anhydride, pentylmaleic anhydride, hexylmaleic anhydride, octylmaleic anhydride, decylmaleic anhydride, dodecylmaleic anhydride, 2,3-dichloromaleic anhydride, phenyl Maleic anhydride, 2,3-diphenyl maleic anhydride, none Itaconic acid, citraconic anhydride, phthalic anhydride, 4-methylphthalic anhydride, dimer acid, 1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride Acid, methylbutenyl-1,2,3,6-tetrahydrophthalic anhydride, chlorendic anhydride, head acid anhydride, biphenyldicarboxylic anhydride, hymic anhydride, endomethylene-1,2,3,6-tetrahydrophthalic anhydride Methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 1-cyclopentene-1,2-dicarboxylic anhydride, B hexene dicarboxylic acid anhydride, trimellitic anhydride, 1,8-naphthalene dicarboxylic acid anhydride, acid anhydrides such as octahydro-1,3-dioxo-4,5-isobenzofurandione carboxylic acid anhydrides.

  High molecular weight dicarboxylic acids obtained by ring-opening addition of high molecular weight polyols such as polyester polyols, polyether polyols, polyurethane polyols and polycarbonate polyols with the above acid anhydrides are also included in the dicarboxylic acids.

  These dicarboxylic acids, their acid anhydrides, or esterified compounds thereof may be used alone or in combination of two or more.

  The dibasic acid component (A) having no hydroxyl group preferably includes a dibasic acid component (a1) having an aromatic ring and / or an alicyclic structure, and the dibasic component is contained in the polyester resin (D). The structure derived from the acid component (a1) is preferably contained in an amount of 5 to 50 mol%, and containing 10 to 35 mol% provides a polyester resin (D) excellent in adhesiveness, heat resistance, moist heat resistance and transparency. Therefore, it is most preferable. When the structure derived from the dibasic acid component (a1) is less than 5 mol% or more than 50 mol%, the adhesion property balance of the polyester resin to be obtained (especially compatibility between tack and cohesive force) should be ensured. In addition, since the heat resistance and heat-and-moisture resistance are reduced, it is difficult to obtain the target resin.

  Examples of the diol (B) having no carboxyl group include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, 2-methyl-1,3-propanediol, and 2-methyl-2-ethyl-1. , 3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-methyl-1,3-propanediol, 2 -Butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, , 3,5-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 3,3 -Dimethylol heptane, polyoxyethylene glycol (addition mole number 10 or less), polyoxypropylene glycol (addition mole number 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, 3-butyl-3-ethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, Aliphatic or alicyclic diols such as cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol;

  For example, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4,4 '-(2-norbornylidene) diphenol, 4,4'-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4'-isopropylidenephenol, 1,2-indanediol, , 3-naphthalenediol, 1,5-naphthalenediol, 1,7-naphthalenediol, 9,9′-bis (4-hydroxyphenyl) fluorene, 9,9′-bis (3-methyl-4-hydroxyphenyl) Fluorene, bisphenols such as bisphenol A and bisphenol F, ethylene oxide, propylene By adding an alkylene oxide such as Kisaido and aromatic diols such as bisphenols comprising.

  These diols (B) may be used alone or in combination of two or more. A polyester diol obtained by reacting a dibasic acid component with a diol component having a relatively low molecular weight can also be used as the diol (B).

The side chain functional group introduction component (C) used in the present invention will be described.
As the side chain functional group-introducing component (C), a trihydric or higher polyhydric alcohol (c1), a trivalent or higher polyvalent carboxylic acid (c2), a compound having two cyclic ether groups in the molecule (c3) Dioxycarboxylic acid (c4) having two hydroxyl groups and one or more carboxyl groups in one molecule and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule are preferably used. be able to.

  Examples of the trihydric or higher polyhydric alcohol (c1) used in the present invention include glycerin, trimethylolethane, trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane. 1,1,1-trimethylolhexane, 1,1,1-trimethylolheptane, 1,1,1-trimethyloloctane, 1,1,1-trimethylolnonane, 1,1,1-trimethyloldecane 1,1,1-trimethylol undecane, 1,1,1-trimethylol dodecane, 1,1,1-trimethylol tridecane, 1,1,1-trimethylol tetradecane, 1,1,1-trimethylol Pentadecane, 1,1,1-trimethylol hexadecane, 1,1,1-trimethylol heptadecane, 1,1,1-trimethyl Ruokutadekan, trimethylol linear alkanes 1,1,1-trimethylol nano-decane, etc.,

1,1,1-trimethylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonane, 1,1,1-trimethylol-tert- Tridecane, 1,1,1-trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1 -Trimethylol branched alkanes such as trimethylol-2-ethyl-hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylolisoheptadecane,

  Trimethylol butene, trimethylol heptene, trimethylol pentene, trimethylol hexene, trimethylol heptene, trimethylol octene, trimethylol decene, trimethylol dodecene, trimethylol tridecene, trimethylol pentadecene, trimethylol hexadecene, tri Trihydric alcohols such as metrolheptadecene, trimethyloloctadecene, 3-methylpentane-1,3,5-triol, 1,2,6-hexanetriol;

  Pentaerythritol, dipentaerythritol, tripentaerythritol, diglycerin, triglycerin, polyglycerol, ditrimethylolethane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, inositol, tetrakishydroxymethylphosphonium chloride, sorbitan, Examples include tetravalent or higher alcohols such as sorbitol, mannitol, saccharose, and cellulose.

  These trivalent or higher valent alcohols (c1) can be used alone or in combination at any desired ratio. The trihydric or higher polyhydric alcohol (c1) reacts with the dibasic acid component (A) having no hydroxyl group as the hydroxyl component in the same manner as the diol (B) having no carboxyl group, so that only the main chain end is reacted. Instead, a hydroxyl group is introduced into the side chain.

Examples of the trivalent or higher polyvalent carboxylic acid (c2) used in the present invention include trimellitic acid, pyromellitic acid, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, and 1,2. , 3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, ethylene glycol bistrimellitate carboxylic acid, 9,9-bis (3,4-dicarboxyphenyl) fluorene diacid, 2,2 ′ , 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, 3,3 ′, 4,4′-bi Ester such as monoalcohol trifunctional or more polycarboxylic acids and anhydrides thereof such as methanol or ethanol, such as E sulfonic tetracarboxylic acid.
These trivalent or higher polyvalent carboxylic acids (c2) can be used singly or in combination in any quantity ratio. The trivalent or higher polyvalent carboxylic acid (c2) reacts with the diol (B) not having a carboxyl group as a carboxyl group component in the same manner as the dibasic acid component (A) having no hydroxyl group, A carboxyl group is introduced not only at the terminal but also in the side chain.

  Examples of the compound (c3) having two cyclic ether groups in the molecule used in the present invention include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. , Propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Diglycidyl ester of glycerin diglycidyl ether, diglycidyl amine, butadiene dioxide, dimer acid Aliphatic diglycidyl compound of;

  2,6-diglycidylphenyl ether, phthalic acid diglycidyl ester, trimellitic acid diglycidyl ester, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, 2,2-bis (4-hydroxyphenyl) ) Propanediglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, 1,1-bis (4-hydroxyphenyl) ethanediglycidyl ether, 3,3 ′, 5,5′-tetramethyl-4,4 '-Dihydroxybiphenyl diglycidyl ether, 2,2-bis (4- (β-hydroxypropoxy) phenyl) propane diglycidyl ether, resorcinol diglycidyl ether, bisphenoxyethanol fluorangeglycidyl Ether, aromatic diglycidyl compounds such as bis aryl diglycidyl ether;

  Cyclohexanedimethanol diglycidyl ether, dicyclopentadiene dioxide, 3,4-glycidylcyclohexylmethyl-3,4-glycidylcyclohexanecarboxylate, 3,4-glycidyl-6-methylcyclohexylmethyl-3,4-glycidyl-6 Methylcyclohexanecarboxylate, vinylcyclohexene dioxide, dicyclodienol epoxide glycidyl ether, tetrahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) ) Alicyclic diglycidyl compounds such as propanediglycidyl ether;

  In addition, bisphenol A high molecular weight glycidyl resin, bisphenol F high molecular weight glycidyl resin, or high molecular weight diglycidyl resin such as phenoxy resin obtained by reacting the diglycidyl compound may be used.

  Examples of the compound having an oxetanyl group used in the present invention include carbonate bisoxetane, adipate bisoxetane, xylylene bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylate bisoxetane, and bis (3-ethyl-3-oxetanylmethyl). Examples include ether, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di {1-ethyl- (3-oxetanyl)} methyl ether, and the like.

  The compound (c3) having two cyclic ether groups in the molecule can be used either alone or in combination at an arbitrary quantitative ratio. When the dibasic acid component (A) and the diol (B) undergo a polycondensation reaction, the cyclic ether group of the compound (c3) having two cyclic ether groups in the molecule undergoes a ring-opening addition reaction to form a side chain. Secondary hydroxyl groups are introduced. Since the secondary hydroxyl group of the side chain has a low activity of the esterification reaction, a three-dimensional reaction is unlikely to occur during the esterification reaction. As a result, the resulting polyester resin (D) is difficult to partially agglomerate, is excellent in uniformity, exhibits good fluidity, and when blended with a reactive compound (F) described later, it feels rich in cohesion after curing. A pressure-sensitive adhesive having a relatively long pot life that can form a pressure-sensitive adhesive layer can be obtained.

  Examples of the dioxycarboxylic acid (c4) having two hydroxyl groups and one or more carboxyl groups in one molecule used in the present invention include dihydroxyfumaric acid, dihydroxymaleic acid, and 2,2-bis (hydroxymethyl). ) Ethanoic acid (also known as dimethylolacetic acid), 2,3-dihydroxypropanoic acid (also known as glyceric acid), 2,2-bis (hydroxymethyl) propanoic acid (also known as 2,2-dimethylolpropionic acid), 3, 3-bis (hydroxymethyl) propanoic acid (also known as 3,3-dimethylolpropionic acid), 2,3-dihydroxy-2-methylpropanoic acid, 2,2-bis (hydroxymethyl) butanoic acid (also known as dimethylolbutyric acid) ), 2,2-dihydroxybutanoic acid, 2,3-dihydroxybutanoic acid, 2,4-dihydroxybutanoic acid (also known as -Deoxytetronic acid), 3,4-dihydroxybutanoic acid, 2,4-dihydroxy-3,3-dimethylbutanoic acid, 2,3-dihydroxy-2-methylbutanoic acid, 2,3-dihydroxy-2-ethylbutanoic acid, 2,3-dihydroxy-2-isopropylbutanoic acid, 2,3-dihydroxy-2-butylbutanoic acid, (R) -2,4-dihydroxy-3,3-dimethylbutanoic acid (also known as bantoic acid), 2,3 -Dihydroxybutanedioic acid (also known as tartaric acid), 2,2-bis (hydroxymethyl) pentanoic acid (also known as dimethylolvaleric acid), 3,5-dihydroxy-3-methylpentanoic acid (also known as mevalonic acid), 2, 2-bis (hydroxymethyl) hexanoic acid (also known as dimethylol caproic acid), 2,2-bis (hydroxymethyl) heptanoic acid (also known as, Methylol enanthate), 3,5-dihydroxyheptanoic acid, 2,2-bis (hydroxymethyl) octanoic acid (also known as dimethylolcaprylic acid), 2,2-bis (hydroxymethyl) nonanoic acid (also known as dimethylolberal) Gonic acid), 2,2-bis (hydroxymethyl) decanoic acid (also known as dimethylol capric acid), 2,2-bis (hydroxymethyl) dodecanoic acid (also known as dimethylol lauric acid), 2,2-bis ( Hydroxymethyl) tetradecanoic acid (also known as dimethylol myristic acid), 2,2-bis (hydroxymethyl) pentadecanoic acid, 2,2-bis (hydroxymethyl) hexadecanoic acid (also known as dimethylol palmitic acid), 2,2- Bis (hydroxymethyl) heptadecanoic acid (also known as dimethylol margaric acid), 2,2-bis ( Hydroxymethyl) octadecanoic acid (also known as dimethylol stearic acid), dimethylol oleic acid, dimethylol linoleic acid, dimethylol linolenic acid, dimethylol aracodonic acid, dimethylol docosahexaenoic acid, dimethylol eicosapentaenoic acid, etc. Dioxycarboxylic acids;

  For example, 2,3-dihydroxybenzoic acid (also known as o-pyrocatechuic acid), 2,4-dihydroxybenzoic acid (also known as β-resorcinic acid), 2,5-dihydroxybenzoic acid (also known as gentisic acid), 2, 6-dihydroxybenzoic acid (also known as γ-resorcinic acid), 3,4-dihydroxybenzoic acid (also known as protocatechuic acid), 3,5-dihydroxybenzoic acid (also known as α-resorcinic acid), 2,6-dihydroxy- 4-methylbenzoic acid, 2,4-dihydroxy-6-dimethylbenzoic acid (also known as o-orceric acid), 3,5-dihydroxy-4-methylbenzoic acid, 2,4-dihydroxy-3,6-dimethylbenzoic acid Acid, 2,3-dihydroxy-4-methoxybenzoic acid, 3,4-dihydroxy-5-methoxybenzoic acid, 2,4-dihydroxymethylbenzoic acid, 3, -Dihydroxymethylbenzoic acid, 4-bromo-3,5-dihydroxybenzoic acid, 5-bromo-2,4-dihydroxybenzoic acid, 3-chloro-2,6-dihydroxybenzoic acid, 5-chloro-2,4- Dihydroxybenzoic acid, hydroxy (4-hydroxy-3-methoxyphenyl) acetic acid (also known as vanylmandelic acid), D, L-3,4-dihydroxymandelic acid, 2,5-dihydroxyphenylacetic acid (also known as homogentisic acid), 3 , 4-Dihydroxyphenylacetic acid (also known as homoprotocatechuic acid), 3,4- (methylenedioxy) phenylacetic acid, 3- (3,4-dihydroxyphenyl) propanoic acid (also known as hydrocaffeic acid), 3- (2, 4-dihydroxyphenyl) acrylic acid (also known as umbelic acid), 3- (3,4-dihydroxyphenyl) a Lauric acid (also known as caffeic acid), 4,4′-bis (p-hydroxyphenyl) pentanoic acid, 3- (3,4-methylenedioxyphenyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, 2,4-dihydroxycinnamic acid, 2,5-dihydroxy cinnamic acid, cinnamyl-3,4-dihydroxy-α-cyanocinnamic acid, 2-bromo-4,5-methylenedioxycinnamic acid, 3,4-methylenedioxy Cinnamic acid, 4,5-methylenedioxy-2-nitrocinnamic acid, 2,6-dihydroxyisonicotinic acid, DL-3,4-dihydroxymandelic acid, 1,4-dihydroxy-2-naphthalenecarboxylic acid, 3, 5-dihydroxy-2-naphthalenecarboxylic acid, 3,7-dihydroxy-2-naphthalenecarboxylic acid, 4,8-dihydroxyquinoline-2-carboxylic acid , Xanthurenic acid) 3- (3,4-dihydroxyphenyl) propionic acid, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,6-dihydroxypyridine-4-carboxylic acid (also known as citrazic acid), 2,4 -Dihydroxythiazole-5-acetic acid, 2- (1-thienyl) ethyl-3,4-dihydroxybenzylidenecyanoacetic acid, 6-estradiol dipropionate, 2,5-dihydroxy-1,4-benzenediacetic acid, (2R , 3R) -2,3-dihydroxy-3- (phenylcarbamoyl) propionic acid and the like, and aromatic ring- or heterocycle-containing dioxycarboxylic acids. In addition, when it has an aromatic ring, what does not directly bond two hydroxyl groups to an aromatic ring is preferable.

  The publicly known dioxycarboxylic acid (c4) used in the present invention can be used alone or in combination at any arbitrary ratio.

Since the dioxycarboxylic acid (c4) has two hydroxyl groups, it is polycondensed with the dibasic acid component (A) as an OH component in the same manner as the diol (B) having no carboxyl group, and used in the present invention. A polyester resin (D) is produced. And the carboxyl group derived from dioxycarboxylic acid (c4) becomes a carboxyl group of the side chain of the polyester resin (D).
It is preferable that the two hydroxyl groups in the dioxycarboxylic acid (c4) are both primary in that they are rich in activity during the esterification reaction. On the other hand, when the dioxycarboxylic acid (c4) functions as a COOH component during the esterification reaction, it easily reacts three-dimensionally during the reaction, easily causes gelation, or the polyester resin (D) does not gel. Even if it is obtained, it tends to agglomerate partially. Therefore, in the esterification reaction, the carboxyl group in the dioxycarboxylic acid (c4) is secondary or so that the dioxycarboxylic acid (c4) functions exclusively as an OH component and not as a COOH component. It is preferable that it is tertiary. Since the activity of the esterification reaction is low, the dioxycarboxylic acid (c4) can have one or more secondary or tertiary carboxyl groups in one molecule.

  Examples of the oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule used in the present invention include dihydroxyfumaric acid, dihydroxymaleic acid, 2-hydroxy-2-methylsuccinic acid (also known as , Citramalic acid), 2-hydroxypropane diacid (also known as tartronic acid), 2,2-dihydroxypropane diacid, 2-hydroxypentanedioic acid (also known as 2-hydroxyglutaric acid), 2,3,4-tri Hydroxypentanedioic acid, 2-hydroxybutanedioic acid (also known as malic acid), 2,2-dihydroxybutanedioic acid, 2,3-dihydroxybutanedioic acid (also known as tartaric acid), 3- [2,3-dihydroxy- 3- (pentyloxycarbonyl) propanoyloxy] -2-hydroxybutanedioic acid, 2,3-dihydroxyheptane (Also known as 2,3-dihydroxypimelic acid), 2,4-dihydroxyhexanedioic acid (also known as 2,4-dihydroxyadipic acid), 2,5-dihydroxyoctanedioic acid (also known as 2,5-dihydroxysuberine) Acid), 2,6-dihydroxynonanedioic acid (also known as 2,6-dihydroxyrepargylic acid), 2,7-dihydroxydecanedioic acid (also known as 2,7-dihydroxysebacic acid), 2-hydroxycyclohexane-1 Aliphatic or alicyclic oxydicarboxylic acids such as 1,4-dicarboxylic acid and 3-hydroxycyclohexane-1,4-dicarboxylic acid;

  For example, 4-hydroxyphthalic acid, 3,6-dihydroxyphthalic acid, 4,5-dihydroxyphthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 4-hydroxypyridine-2,6-dicarboxylic acid, 3- Hydroxy-4-oxo-4H-pyran-2,6-dicarboxylic acid (also known as meconic acid), 1-hydroxy-2,3-naphthalenedicarboxylic acid, 2-hydroxy-1,8-naphthalenedicarboxylic acid, 3-hydroxy -2,5-pyridinedicarboxylic acid, (1α, 2β, 4aα, 4bβ, 10β) -2,4a, 7-trihydroxy-1-methyl-8-methylenediva-3-ene-1,10-dicarboxylic acid 1, Aromatic or hetero ring-containing oxydicarboxylic acids such as 4a-lactone (also known as gibberellic acid) are exemplified.

  The well-known oxydicarboxylic acid (c5) used for this invention can be used individually or in combination of 2 or more types, respectively.

Since the oxydicarboxylic acid (c5) has two carboxyl groups, it is polycondensed with the diol (B) as a COOH component in the same manner as the dibasic acid component (A) having no hydroxyl group, and used in the present invention. A polyester resin (D) is produced. And the hydroxyl group derived from oxydicarboxylic acid (c5) turns into a hydroxyl group of the side chain of a polyester resin (D).
It is preferable that the two carboxyl groups in the oxydicarboxylic acid (c5) are both primary in terms of rich activity during the esterification reaction. On the other hand, when the oxydicarboxylic acid (c5) functions as an OH component during the esterification reaction, it easily undergoes a three-dimensional reaction during the reaction, and gelation is likely to occur, or the polyester resin (D) is obtained without gelation. Even if it is done, it is easy to partly aggregate. Therefore, in the esterification reaction, the hydroxyl group in the oxydicarboxylic acid (C) is secondary or tertiary so that the oxydicarboxylic acid (c5) functions exclusively as a COOH component and not as an OH component. Preferably there is. Since the activity of the esterification reaction is low, the oxydicarboxylic acid (c5) can have one or more secondary or tertiary hydroxyl groups in one molecule.
In the case of the oxydicarboxylic acid (c5) having an aromatic ring, OH directly bonded to the aromatic ring is preferable in that the activity of the esterification reaction is low, but the reaction activity with the reactive compound (F) is also low. Therefore, the hydroxyl group of the oxydicarboxylic acid (c5) is preferably a secondary or tertiary hydroxyl group that is not directly connected to the aromatic ring.

  The polyester resin (D1) used in the present invention preferably contains 0.1 to 10 mol% of the structure derived from the side chain functional group introduction component (C). That is, the amount of hydroxyl group and / or carboxyl group introduced into the side chain depends on the structure derived from the side chain functional group introduction component (C). The hydroxyl group and / or carboxyl group introduced into the side chain crosslinks with the reactive compound (F) described later to form a pressure-sensitive adhesive layer, and contributes to the improvement of cohesive strength, adhesiveness, heat resistance, and moist heat resistance. . However, if there are too many hydroxyl groups and / or carboxyl groups introduced by the side chain functional group-introducing component (C), the pot life will be shortened, while if too little, the cohesive force and adhesion of the pressure-sensitive adhesive layer formed will be reduced. , Heat resistance and moist heat resistance are reduced. Therefore, from the balance between the pot life as the pressure-sensitive adhesive and the performance of the pressure-sensitive adhesive layer, the structure derived from the side chain functional group introduction component (C) is 0.1 to 0.1 in the polyester resin (D1). It is preferably 10 mol%.

  A polyester resin having a hydroxyl group or a carboxyl group in the side chain by a reaction between the dibasic acid component (A) having no hydroxyl group, the diol (B) having no carboxyl group, and the side chain functional group introduction component (C) ( When forming D1), the reaction proceeds even without catalyst, but a catalyst can be used as appropriate in order to allow the reaction to proceed more smoothly. Catalysts used include ammonia, amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, tin, lead, titanium, iron, zinc, zirconium. , Organometallic compounds containing cobalt, metal halides, and the like.

  Examples of amines include triethylamine, pyridine, aniline, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine, dimethyloxazoline, imidazole, N-methylimidazole, N, N- Examples thereof include dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethylisopropanolamine, N-methyldiethanolamine and the like.

  Examples of the quaternary ammonium salts include tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium fluoride trihydrate, tetramethylammonium hexafluorophosphate, tetramethylammonium hydrogen phthalate, tetramethylammonium hydroxide pentahydrate. , Tetramethylammonium hydroxide, tetramethylammonium iodide, tetramethylammonium nitrate, tetramethylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetramethylammonium tribromide, phenyltrimethylammonium bromide, tetraethylammonium bromide, tetraethylammonium chloride Tetraethylammonium fluoride trihydrate, tetraethylammonium hydroxide, tetraethylammonium iodide, tetraethylammonium perchlorate, tetraethylammonium tetrafluoroborate, tetraethylammonium-p-toluenesulfonate, tetrapropylammonium bromide, tetrapropylammonium chloride, tetra Propylammonium iodide, tetrapropylammonium hydroxide, tetrapropylammonium perchlorate, tetra-n-propylammonium hydrogensulfate, tetra-n-propylammonium pearlate (VII), tetrabutylammonium bromide, tetrabutylammonium trichloride bromide, Trabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetrabutylammonium nitrate, tetrabutylammonium tetrahydroborate, tetrabutylammonium tetrafluoroborate, Tetrabutylammonium cyanotrihydroborate, tetrabutylammonium difluorotriphenylstannate, tetrabutylammonium fluoride trihydrate, tetrabutylammonium tetrathiophenate (IV), tetrabutylammonium fluoride hydrate, tetra-n-butyl Ammonium dihydrogen trifluoride, Tetra-n-butylammonium trifluoromethanesulfonate, tributylammonium bis (2,3-dimercapto-2-butenedinylolylate-S, S ′) nicolate, tetra-n-heptylammonium bromide, tetra-n-heptylammonium chloride, Tetra-n-heptylammonium iodide, tetra-n-hexylammonium benzoate, tetra-n-hexylammonium bromide, tetra-n-hexylammonium chloride, tetra-n-hexylammonium iodide, tetra-n-hexylammonium perchlorate , Tetraoctyl ammonium bromide, tetraoctadecyl ammonium bromide and the like.

Quaternary phosphonium salts include, for example, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium tetrafluoroborate, Tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium benzotriazolate, tetrabutylphosphonium bis (1,2-benzenedithiolate) nicolate (III), tetrabutylphosphonium bis (4-methyl-1) , 2-Benzenedithiolate) Nicolate (III), Tetrabutylphospho Umubisu (4,5-mercapto-1,3-dithiol-2 thionating -S ^4, S ⁵⁾ Nikoreto (III) and the like.

Examples of the alkali metal or alkaline earth metal hydroxide include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide;
Alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide;
Can be mentioned.

  Examples of the organic tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, Examples thereof include tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Examples of organic zirconium compounds include zirconium acetate, zirconium benzoate, zirconium naphthenate, and the like.

  Examples of the organic titanium compounds include dibutyltitanium dichloride, tetrabutyltitanate, tetrabutoxytitanate, tetraethyltitanate, tetraisopropyltitanate, butoxytitanium trichloride, and the like.

  Examples of the organic lead compounds include lead acetate, lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.

  Examples of organic iron compounds include iron 2-ethylhexanoate and iron acetylacetonate.

  Examples of the organic cobalt compounds include cobalt acetate, cobalt benzoate, and cobalt 2-ethylhexanoate.

  Examples of the organic zinc compounds include zinc acetate, zinc oxalate, zinc naphthenate, and zinc 2-ethylhexanoate.

  Examples of metal halides include stannous chloride, stannous bromide, stannous iodide, and the like.

  Furthermore, Lewis acids such as boron trifluoride, manganese acetate, germanium oxide, antimony trioxide, aluminum trichloride, zinc chloride, and titanium chloride are exemplified, but not limited thereto. A catalyst may use only 1 type or may use 2 or more types together. The catalyst is used in an amount of 10 parts by weight or less with respect to 100 parts by weight of all reaction components. The range of 0.0001 to 1 part by weight is more preferable. When the amount exceeding 10 parts by weight is used, there arises a disadvantage that the product is colored or a catalyst that has not been deactivated remains and acts as a negative catalyst, causing a decomposition reaction.

The polyester resin (D1) used in the present invention can be produced according to a conventionally known polyester reaction method. For example, it can be obtained by the following method.
(1) One-step reaction: the dibasic acid component (A), the diol (B), and the side chain functional group introduction component (C) are 160 to 260 ° C, preferably 180 to 250 ° C, more preferably 200 to 250. Direct esterification reaction at 0 ° C. After cooling, an organic solvent can be appropriately added to prepare a pressure-sensitive adhesive.
(2) Two-stage reaction: a dibasic acid component (A), a diol (B), and a side chain functional group-introducing component (C) are subjected to dehydration reaction or transesterification at 160 to 260 ° C., preferably 180 to 250 ° C. The reaction is performed, and then the excess diol component is removed by heating to 180 to 280 ° C., preferably 200 to 260 ° C. under a reduced pressure of 5 Torr or less to obtain a polyester resin. After cooling, an organic solvent can be appropriately added to prepare a pressure-sensitive adhesive.
The component (C) for introducing a side chain functional group may be charged into the reaction vessel from the beginning together with the dibasic acid component (A) and the diol (B), or the dibasic acid component (A) and The reaction may be conducted after the dehydration reaction or transesterification reaction of the diol (B).
Incidentally, when the polymerization temperature is less than the above lower limit, the reaction does not proceed sufficiently. On the other hand, if the polymerization temperature exceeds the upper limit, side reactions such as decomposition may occur or coloring may be easily caused. The reaction time can usually be about 1 to 60 hours.

In the present invention, the cyclic ester compound (G) is further subjected to ring-opening addition to the hydroxyl group or carboxyl group of the side chain introduced using the side chain functional group introduction component (C), and the cyclic ester compound (G) A pressure-sensitive adhesive can also be obtained by using a polyester resin (D2) having a ring-opening portion as a side chain and a hydroxyl group at the end of the ring-opening portion. When the ring-opening addition of the cyclic ester compound (G), the side chain functional group of the polyester resin (D1) is preferably a hydroxyl group in terms of reactivity. That is, it is preferable to further utilize the side chain hydroxyl group introduced by (c1), (c3) or (c5) in the side chain functional group introduction component (C).
For example, the polyester resin (D1) obtained by the above method (1) or (2) and the cyclic ester compound (G) are mixed together and then reacted together, or the polyester resin (D1). The polyester-based resin (D2) can be obtained by reacting while adding the cyclic ester compound (G) or by adding the polyester resin (D1) to the cyclic ester compound (G). Alternatively, the cyclic ester compound (G) may be added and reacted during the reaction of the polyester resin (D1). The polyester resin (D1) is preferably used in a solution state. For example, the ring-opening addition reaction is preferably performed at 20 to 220 ° C, more preferably 60 to 180 ° C. By opening the cyclic ester compound (G), an ester bond can be introduced into the side chain of the polyester resin (D1). Further, the cyclic ester compound (G) can be further subjected to ring-opening addition to the added hydroxyl group at the end of the ring-opening portion, and the side chain can be lengthened to have a high molecular weight. By introducing an ester bond into the side chain, an improvement in adhesive properties (particularly tack) is expected. The obtained polyester-based resin (D2) can be adjusted for non-volatile content by appropriately adding an organic solvent after cooling.

    As the cyclic ester compound (G) used in the present invention, a cyclic ester (g1) of hydroxycarboxylic acid can be preferably used.

The cyclic ester (g1) of hydroxycarboxylic acid used in the present invention is not particularly limited, and intramolecular or intermolecular condensates of aliphatic, alicyclic, aromatic and heterocyclic hydroxycarboxylic acids can be used. .
Examples of the aliphatic hydroxycarboxylic acid include glycolic acid, lactic acid, hydroacrylic acid, α-oxybutyric acid, α-hydroxyisobutyric acid, hydroxyvaleric acid, α-hydroxycaproic acid, δ-hydroxycaproic acid, glyceric acid, and tartron. Acid, malic acid, citric acid, caprylic acid, lauric acid, ricinoleic acid, α-hydroxytriacontanoic acid, α-hydroxytetratriacontanoic acid, α-hydroxyhexatriacontanoic acid, α-hydroxyoctatriacontanoic acid, α -Hydroxytetraacontanic acid, hydroxypiparic acid, hydroxypropionic acid, 6-hydroxypentanoic acid, α-hydroxyheptanoic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, 10-hydroxydecanoic acid, 12-hydroxydodecane acid, -Hydroxymistilic acid, 16-hydroxyhexadecanoic acid, 15-hydroxypentadecanoic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid, α-hydroxyhexaicosanoic acid, α- Examples include hydroxyoctaeicosanoic acid, α-hydroxytriacontanoic acid, β-hydroxymyristic acid, dimethylolpropionic acid, 3,5-di-tert-butylsalicylic acid and the like.

  Alicyclic, aromatic and heterocyclic hydroxycarboxylic acids include, for example, salicylic acid, 2-oxybenzoic acid, 3-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 4-hydroxy-3-phenylbenzoic acid, 4-hydroxy-3-methoxybenzoic acid, 4-hydroxy-3,5-dimethoxybenzoic acid, 4′-hydroxy-4-carboxybiphenyl, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, Examples include 5-hydroxy-1-naphthoic acid.

  The hydroxycarboxylic acid can be used as long as it has a carboxylic acid and a hydroxyl group in one molecule of the organic compound, and is not necessarily limited to those exemplified above.

  The cyclic ester (g1) of hydroxycarboxylic acid used in the present invention is obtained by intramolecular or intermolecular condensation reaction between a hydroxyl group in the hydroxycarboxylic acid and the carboxylic acid in the hydroxycarboxylic acid. That is, it includes cyclic monomers, dimers, or multimers of trimers or more of hydroxycarboxylic acids produced by intramolecular or intermolecular condensation reactions of hydroxycarboxylic acids.

  Of the cyclic ester (g1) of hydroxycarboxylic acid used in the present invention, a lactone can be used as the cyclic monomer, and there is no particular limitation. For example, β-butyrolactone, β-propiolactone, γ-butyrolactone Γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, ε-caprolactone glycolide, pivalolactone, 7-heptanolide, 8-octonolide, 11-undecanolide, 12-dodecanolide, 15-pentadecanolide, 16-hexadodecanolide, α-methyl-β-propiolactone, β-methyl-α-propiolactone, α, α -Dimethyl-β-propiolactone and the like.

  Of the cyclic ester (g1) of hydroxycarboxylic acid used in the present invention, examples of the cyclic dimer include lactide by lactic acid and glycolide by glycolic acid.

  The cyclic ester (g1) of hydroxycarboxylic acid used in the present invention is not limited in the size of the ring, but in order to efficiently perform a ring-opening addition reaction with the hydroxyl group contained in the polyester resin (D1), Cyclic monomer lactones having 6 to 18 carbon atoms are preferred, and ε-caprolactone is more preferred.

  The cyclic ester (g1) of hydroxycarboxylic acid used in the present invention may be subjected to ring-opening addition in the form of one molecule to the polyester resin (D1) having a side chain hydroxyl group, or a plurality of cyclic esters (g1). As an embodiment of a polymer formed by ring-opening polymerization of molecules, it may be added to the polyester resin (D1).

The polyester resin (D) such as (D1) and (D2) has a glass transition point (Tg) of −80 to 0 ° C. so that it can exhibit well-balanced adhesive properties (particularly, compatibility between tack and cohesive force). The dibasic acid component (A) having no hydroxyl group, the diol (B) having no carboxyl group, the side chain functional group introduction component (C), and the cyclic ester compound (G) are selected so that It is preferable to select each component so that the glass transition point (Tg) is -60 to -10 ° C.
When the glass transition temperature of the polyester resin (D) is less than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the polyester resin is lowered, and the float-off is likely to occur. On the other hand, when the glass transition temperature exceeds 0 ° C., the pressure-sensitive adhesive layer becomes too hard and does not exhibit sufficient tack, or the adhesive strength is weak when plastics or a glass plate and a plastic film are laminated. In addition, the solubility in a solvent decreases, and the viscosity of the pressure-sensitive adhesive increases, which makes it difficult to handle at the time of coating.
The glass transition temperature is a value obtained using a DSC (differential scanning calorimeter).

  The weight average molecular weight (Mw) of the polyester resin (D) in the present invention is preferably in the range of 2,000 to 1,000,000 from the viewpoint of adhesiveness, and is in the range of 8,000 to 500,000. It is more preferable. When such a polyester resin is used, a pressure-sensitive adhesive having excellent adhesion and wettability can be obtained. If the Mw is less than 2,000, the cohesive force as the pressure-sensitive adhesive layer becomes difficult to develop, and the heat resistance and heat and humidity resistance are reduced. On the other hand, if Mw exceeds 1,000,000, the fluidity of the pressure-sensitive adhesive becomes poor even when diluted with a solvent, and the coating property is reduced when producing a pressure-sensitive adhesive sheet. Absent.

  The hydroxyl value or acid value of the polyester resin (D) having a side chain in the present invention is 0.1 to 50 mgKOH depending on the above-mentioned side chain functional group introduction component (C) and further on the cyclic ester compound (G). / G is preferably controlled within a range of 0.5 to 30 mg KOH / g. When both the hydroxyl value and the acid value are lower than 0.1 mgKOH / g, the reactivity with the reactive compound (F) described later is inferior and the cohesive force becomes insufficient. When the pressure-sensitive adhesive sheet is to be peeled off, not only is it difficult to peel off, but adhesive residue may be generated after peeling, resulting in insufficient removability. Further, when both the hydroxyl value and the acid value are higher than 50 mgKOH / g, the pot life is shortened, and workability at the time of coating and bonding is remarkably lowered, which is not preferable.

In the present invention, as the near-infrared absorbing agent, the diimonium salt compound (e1) may be used in combination with another near-infrared absorbing agent (e2) having a different absorption maximum wavelength from the diimonium salt compound (e1). is important.
The diimonium salt compound (e1) has an absorption maximum mainly at 950 to 1100 nm. Therefore, the near-infrared region can be widely covered by using another near-infrared absorbing agent (e2) having an absorption maximum wavelength different from that of the immonium salt compound (e1).

  Examples of the diimonium salt compound (e1) used in the present invention include compounds represented by the following general formula (1).

In the formula (1), R9 to R16 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a cyclic alkyl group, an alkenyl group, an aralkyl group, or a substituted aralkyl group, Alternatively, it may be any branched chain. Also, they may be the same or different. X ²⁻ represents a divalent anion.

In R9 to R16 in the general formula (1), examples of the alkyl group, substituted alkyl group, cyclic alkyl group, alkenyl group, aralkyl group or substituted aralkyl group include the following.
(1) an alkyl group;
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, iso-pentyl group, t-pentyl group , N-hexyl group, n-octyl group (preferably having 1 to 10 carbon atoms)
(2) a substituted alkyl group;
2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group 4-sulfobutyl group, 3-sulfatopropyl group, 4-sulfatebutyl group, N- (methylsulfonyl) -carbamylmethyl group, 3- (acetylsulfamyl) propyl group, 4- (acetylsulfamyl) ) Butyl group, cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2-cyanopropyl group, 4-cyanobutyl group, 3-cyanobutyl group, 2-cyanobutyl group, 5-cyanopentyl group, 4-cyanopentyl group 3-cyanopentyl group, 2-cyanopentyl group, 6-cyanohexyl group, 5-sia Nohexyl group, 4-cyanohexyl group, 3-cyanohexyl group, 2-cyanohexyl group, etc.
(3) a cyclic alkyl group;
A cyclohexyl group (4) an alkenyl group;
Vinyl group, allyl group, propenyl group, etc., as the aralkyl group, for example, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group,
(5) a substituted aralkyl group;
Examples thereof include a carboxybenzyl group, a sulfobenzyl group, and a hydroxybenzyl group. In R, an alkyl group having 3 to 6 carbon atoms or an alkyl group substituted with a cyano group is more preferably used.

As X ^2- in the general formula (1), naphthalene-1,5-disulfonic acid, R acid, G acid, H acid, benzoyl H acid, p-chlorobenzoyl H acid, p-toluenesulfonyl H acid, chloro H Acid, chloroacetyl H acid, methanyl γ acid, 6-sulfonaphthyl-γ acid, C acid, ε acid, p-toluenesulfonyl R acid, naphthalene-1,6-disulfonic acid, 1-naphthol-4,8-disulfone Naphthalenedisulfonic acid derivatives such as acid, carbonyl J acid, 4,4′-diaminostilbene-2,2′-disulfonic acid, diJ acid, naphthalic acid, naphthalene-2,3-dicarboxylic acid, diphenic acid, stilbene-4 , 4'-dicarboxylic acid, 6-sulfo-2-oxy-3-naphthoic acid, anthraquinone-1,8-disulfonic acid, 1,6-diaminoanthraquinone-2,7-disulfo Acid, 2- (4-sulfophenyl) -6-aminobenzotriazole-5-sulfonic acid, 6- (3-methyl-5-pyrazolonyl) -naphthalene-1,3-disulfonic acid, 1-naphthol-6- ( And divalent organic acid ions such as 4-amino-3-sulfo) anilino-3-sulfonic acid.

  As the other near-infrared absorbing agent (e2) used in the present invention, a compound having an absorption maximum mainly at 750 to 950 nm is preferable, and an aminium compound, an anthraquinone compound, a polymethine compound, a cyanine compound, a phthalocyanine compound, Examples include benzopyridium compounds and thiometal complex compounds. Among these, as a combination that can effectively obtain absorption performance in the wavelength region of 800 to 1200 nm by using in combination with a diimonium compound, a cyanine compound, a thiometal complex compound, or a phthalocyanine compound can be mentioned.

  Examples of the cyanine compound include compounds represented by the general formula (2).

In General Formula (2), one of Y ₁ and Y ₂ is a single bond, and the other is —O— or —CH ₂ —. It is preferable that Y ₁ is a single bond and Y ₂ is —O— or —CH ₂ —. It is also preferred that one of Y ₁ and Y ₂ is a single bond and the other is —O—. Most preferably, Y ₁ is a single bond and Y ₂ is —O—. Y ₁ and Y ₂ are each bonded to two adjacent carbon atoms of the benzene ring B. Y ₁ is bonded to the 4-position of the benzene ring B (position number in the indole ring, hereinafter the same), and Y ₂ is bonded to the 5-position of the benzene ring B, or Y ₁ is bonded to the 5-position of the benzene ring B Y ₂ is preferably bonded to the 6-position of the benzene ring B. It is particularly preferable that Y ₁ is bonded to the 5-position of the benzene ring B and Y ₂ is bonded to the 6-position of the benzene ring B.

In General Formula (2), one of Y ₃ and Y ₄ is a single bond, and the other is —O— or —CH ₂ —. It is preferable that Y ₃ is a single bond and Y ₄ is —O— or —CH ₂ —. It is also preferred that one of Y ₃ and Y ₄ is a single bond and the other is —O—. Most preferably, Y ₃ is a single bond and Y ₄ is —O—. Y ₃ and Y ₄ are each bonded to two adjacent carbon atoms of the benzene ring C. Y ₃ is bonded to the 4-position of the benzene ring C (position number in the indoline ring, the same applies hereinafter), and Y ₄ is bonded to the 5-position of the benzene ring C, or Y ₃ is bonded to the 5-position of the benzene ring C Y ₄ is preferably bonded to the 6-position of the benzene ring C. It is particularly preferable that Y ₃ is bonded to the 5-position of the benzene ring C and Y ₄ is bonded to the 6-position of the benzene ring C.

    In the general formula (2), R1 and R2 are each independently an aliphatic group. In this specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The alkyl group may be cyclic. The chain alkyl group may have a branch. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and most preferably 1 to 8 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, cyclopropyl, cyclohexyl and 2-ethylhexyl.

The alkyl part of the substituted alkyl group is the same as the above alkyl group. Examples of the substituent of the substituted alkyl group include a halogen atom, hydroxyl, carboxyl, amino, carbamoyl, ureido, mercapto, sulfo, sulfamoyl, aromatic group, heterocyclic group, -O-R, -CO-R, -CO _{-O-R, -O-CO-} R, -NHR, -NR 2, -NH-CO-R, -CO-NHR, -CONR 2, -NH-CO-NHR -, - NH-CO-NR 2 —, —NH—CO—O—R, —S—R, —SO ₂ —R, —SO ₂ —O—R, —NH—SO ₂ —R, —SO ₂ —NH—R and —SO ₂ — NR ₂ is included. Each R is an aliphatic group, an aromatic group or a heterocyclic group. The carboxyl and sulfo may be dissociated from hydrogen atoms or may be in a salt state. Examples of the substituted alkyl group include 2-hydroxyethyl, 2-carboxyethyl, 2-methoxyethyl, 2-diethylaminoethyl, 3-sulfopropyl and 4-sulfobutyl.

  The alkenyl group may be cyclic. The chain alkenyl group may have a branch. 2-20 are preferable, as for the carbon atom number of an alkenyl group, 2-12 are more preferable, and 2-8 are the most preferable. Examples of the alkenyl group include vinyl, allyl, 1-propenyl, 2-butenyl, 2-pentenyl and 2-hexenyl. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group. The substituent of the substituted alkenyl group is the same as the substituent of the substituted alkyl group. The alkynyl group may be cyclic. The chain alkynyl group may have a branch. The number of carbon atoms in the alkynyl group is preferably 2-20, more preferably 2-12, and most preferably 2-8. Examples of alkynyl groups include ethynyl and 2-propynyl.

  The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The substituent of the substituted alkynyl group is the same as the substituent of the substituted alkyl group. The alkyl part of the aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group is the same as the aryl group described later. Examples of aralkyl groups include benzyl and phenethyl. The alkyl part of the substituted aralkyl group is the same as the above alkyl group. The aryl part of the substituted aralkyl group is the same as the aryl group described later. The substituent of the alkyl part of the substituted aralkyl group is the same as the substituent of the substituted alkyl group. The substituent of the aryl part of the substituted aralkyl group is the same as the substituent of the substituted aryl group described later.

In the present invention, the aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably phenyl and naphthyl, and more preferably phenyl. The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group include a halogen atom, hydroxyl, carboxyl, amino, carbamoyl, ureido, mercapto, sulfo, sulfamoyl, cyano, nitro, aliphatic group, aromatic group, heterocyclic group, -O-R , —CO—R, —CO—O—R, —O—CO—R, —NHR, —NR ₂ , —NH—CO—R, —CO—NHR, —CO—NR ₂ , —NH—CO— NHR—, —NH—CO—NR ₂ —, —NH—CO—O—R, —S—R, —SO ₂ —R, —SO ₂ —O—R, —NH—SO ₂ —R, —SO _2- NH—R and —SO ₂ —NR ₂ are included. Each R is an aliphatic group, an aromatic group or a heterocyclic group. The carboxyl and sulfo may be dissociated from hydrogen atoms or may be in a salt state.

  In the present invention, the heterocyclic group means an unsubstituted heterocyclic group and a substituted heterocyclic group. The heterocyclic ring of the heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. Examples of heterocyclic rings (including fused rings) include pyridine ring, piperidine ring, furan ring, furfuran ring, thiophene ring, pyrrole ring, quinoline ring, morpholine ring, indole ring, imidazole ring, pyrazole ring, carbazole ring, phenothiazine Ring, phenoxazine ring, indoline ring, thiazole ring, pyrazine ring, thiadiazine ring, benzoquinoline ring and thiadiazole ring. The substituent of the substituted heterocyclic group is the same as the substituent of the substituted aryl group.

  In the general formula (2), R3, R4, R5 and R6 are each independently an aliphatic group. R3 and R4 or R5 and R6 may be bonded to each other to form a cyclopentane ring or a cyclohexane ring. In the general formula (2), L1 is a methine chain composed of 5, 7, or 9 methines. The number of methines is preferably 5 or 7, more preferably 7. Methine may have a substituent. The methine having a substituent is preferably a central (meso-position) methine. The substituent for methine is the same as the substituent for the substituted aryl group. Two substituents of the methine chain may be bonded to form a 5-membered ring, 6-membered ring or 7-membered ring.

In the general formula (2), X ₁ ^- is an anion. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonate ions, ethyl sulfate ions, PF ₆ ⁻ , BF ₄ ⁻ and ClO ₄ ⁻ . In the general formula (2), a is 0 or 1. a is 0 when the cyanine dye has an anionic substituent such as sulfo or carboxyl to form an inner salt. a is preferably 0. In the general formula (2), the benzene rings A, B, C and D may have a substituent. The substituent of the benzene ring is the same as the substituent of the substituted aryl group.

  Examples of the thiometal complex compound include a compound represented by the general formula (3).

  In the general formula (3), R17, R18, R19 and R20 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxy group, a trifluoromethyl group, an alkylthio group, an arylthio group, A nitro group, a cyano group, an alkoxy group, an aryloxy group, or an alkylamino group is represented. One aromatic ring may have a plurality of substituents, and they may be different from each other.

In R17, R18, R19, and R20 of the general formula (3), the halogen atom, alkyl group, cycloalkyl group, aryl group, alkylthio group, arylthio group, aryloxy group, and alkylamino group include the following.
(A) a halogen atom;
Fluorine atom, chlorine atom, bromine atom, iodine atom,
(B) an alkyl group;
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.
(C) a cycloalkyl group;
Cyclopentyl group, cyclohexyl group, etc.
(D) an aryl group;
Phenyl group, p-nitrophenyl group, etc.
(E) an alkylthio group;
Methylthio group, ethylthio group, butylthio group, etc.
(F) an arylthio group;
Phenylthio group, tolylthio group, etc.,
(G) an alkoxy group;
Methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, n-pentyloxy group, iso-pentyloxy group, etc.
(H) aryloxy group;
(E) alkylamino groups such as phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, naphthoxy group;
Methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, benzylamino group, dimethylamino group , Diethylamino group, di-n-propylamino group, di-iso-propylamino group, di-n-butylamino group, di-iso-butylamino group, di-n-pentylamino group, di-iso-pentylamino Groups, di-n-hexylamino groups, di-n-heptylamino groups, di-n-octylamino groups, di- (2-ethylhexyl) amino groups, dibenzylamino groups and the like (d) arylamino groups;
A diphenylamino group, a ditolylamino group, etc. are mentioned.

  Examples of the phthalocyanine compound include a compound represented by the general formula (4).

  In the general formula (4), R21 to R24 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. An aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group is represented. One aromatic ring may have a plurality of substituents, and they may be different from each other. M represents a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal.

  Examples of R21 to R24 include halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups, substituted or unsubstituted alkylthio groups. Groups, or substituted or unsubstituted arylthio groups. Specific examples include the following.

(A) a halogen atom;
Fluorine atom, chlorine atom, bromine atom, iodine atom (b) substituted or unsubstituted alkyl group;
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, iso-pentyl group, neo-pentyl group 1,2-dimethyl-propyl group, n-hexyl group, cyclo-hexyl group, 1,3-dimethyl-butyl group, 1-iso-propylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl 1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-iso-propylbutyl group, C1-C20 linear or branched alkyl groups such as 2-methyl-1-iso-propyl group, 1-t-butyl-2-methylpropyl group, n-nonyl group
Methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, γ-methoxypropyl group, γ-ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group , Alkoxyalkyl groups such as dimethoxyethyl group, diethoxyethyl group, alkoxyalkoxyalkyl group, alkoxyalkoxyalkoxyalkyl group, chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 2,2,2 -Halogenated alkyl groups such as trichloroethyl group, 1,1,1,3,3,3, -hexafluoro-2-propyl group, alkylaminoalkyl group, dialkylaminoalkyl group, alkoxycarbonylalkyl group, alkylaminocarbonyl A Kill group, an alkoxysulfonyl group such as,
(C) examples of substituted or unsubstituted alkoxy groups;
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, iso-pentyloxy group, neo-pentyloxy group, 1,2-dimethyl-propyloxy group, n-hexyloxy group, cyclo-hexyloxy group, 1,3-dimethyl-butyloxy group, 1-iso-propylpropyloxy group, 1,2- Dimethylbutyloxy group, n-heptyloxy group, 1,4-dimethylpentyloxy group, 2-methyl-1-iso-propylpropyloxy group, 1-ethyl-3-methylbutyloxy group, n-octyloxy group, 2-ethylhexyloxy group, 3-methyl-1-iso-propylbutyloxy A linear or branched alkoxy group having 1 to 20 carbon atoms such as a group, 2-methyl-1-iso-propyloxy group, 1-t-butyl-2-methylpropyloxy group, n-nonyloxy group,
Methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, γ-methoxypropyloxy group, γ-ethoxypropyloxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, dimethoxymethoxy group, diethoxy Alkoxyalkoxy groups such as methoxy group, dimethoxyethoxy group and diethoxyethoxy group, alkoxyalkoxyalkoxy groups such as methoxyethoxyethoxy group, ethoxyethoxyethoxy group and butyloxyethoxyethoxy group, alkoxyalkoxyalkoxyalkoxy groups, chloromethoxy group, 2 , 2,2-trichloroethoxy group, trifluoromethoxy group, 2,2,2-trichloroethoxy group, 1,1,1,3,3,3, -hexafluoro-2-propyl group Halogenated alkoxy group such as a group, dimethylaminoethoxy group, an alkylamino alkoxy group such as a diethylamino ethoxy group, etc. dialkylaminoalkoxy group,
(D) a substituted or unsubstituted aryl group;
Phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, fluorinated phenyl group, halogenated phenyl group such as iodinated phenyl group, tolyl group, xylyl group, mesityl group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group, A pyridyl group etc. are mentioned. Examples of the substituted or unsubstituted aryloxy group include phenoxy group, naphthoxy group, alkylphenoxy group, etc.
(E) a substituted or unsubstituted alkylthio group;
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, iso-pentylthio group, neo-pentylthio group 1,2-dimethyl-propylthio group, n-hexylthio group, cyclo-hexylthio group, 1,3-dimethyl-butylthio group, 1-iso-propylpropylthio group, 1,2-dimethylbutylthio group, n-heptylthio group Group, 1,4-dimethylpentylthio group, 2-methyl 1-iso-propylpropylthio group, 1-ethyl-3-methylbutylthio group, n-octylthio group, 2-ethylhexylthio group, 3-methyl-1 -Iso-propylbutylthio group, 2-methyl-1-iso-propylthio group A linear or branched alkylthio group having 1 to 20 carbon atoms such as 1-t-butyl-2-methylpropylthio group and n-nonylthio group,
Methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group, propoxyethylthio group, butoxyethylthio group, γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, Alkoxyalkylthio groups such as dimethoxymethylthio group, diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group, alkoxyalkoxyalkylthio group, alkoxyalkoxyalkoxyalkylthio group, chloromethylthio group, 2,2,2-trichloroethylthio group Halogenoalkylthio groups such as trifluoromethylthio group, 2,2,2-trichloroethylthio group, 1,1,1,3,3,3, -hexafluoro-2-propylthio group, dimethylaminoethyl Group, alkylaminoalkyl thio group such as diethylaminoethyl thio group, such as dialkylaminoalkyl thio group,
(F) examples of substituted or unsubstituted arylthio groups;
Phenylthio group, naphthylthio group, alkylphenylthio group and the like.

Further, as M, there are the following.
(A) a divalent metal;
Cu (II), Zn (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), 1d (II), Hg (II), Pb (II), Sn (II) and the like.
(B) Examples of monosubstituted trivalent metals;
Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, Ga-Br, 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), _{In-C 6 H 5, Mn} (OH), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Fe-Cl, Ru-Cl, etc.,
(C) a disubstituted tetravalent metal;
CrC 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 [where R is an alkyl group, a phenyl group , A naphthyl group or a group derived therefrom), 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 or a group derived therefrom], Sn (SR ″) ₂ , Ge (SR ") ₂ (R" represents an alkyl group, a phenyl group, a naphthyl group or a group derived therefrom), etc.
(D) Examples of oxymetals;
VO, MnO, TiO etc. are mentioned.

In the present invention, the diimonium salt compound (e1) and the other near infrared absorbing agent (e2) are preferably used in a total amount of 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyester resin (D). More preferably, 0.1 to 10 parts by weight are used. If it is less than 0.01 part by weight, the near-infrared absorption function cannot be expected, and if it exceeds 20 parts by weight, the transparency of the polyester resin (D) or a laminate obtained by using the resin is lowered. It is not preferable.
In the present invention, the ratio of the diimonium salt compound (e1) to the other near infrared absorbing agent (e2) is preferably (e1) :( e2) = 2: 8 to 8: 2. : 6 to 6: 4 is more preferable.
Further, the extinction coefficient of the diimonium salt compound (e1) and the other near-infrared absorbing agent (e2) is preferably 20,000 or more, and more preferably 50,000 or more. If the extinction coefficient is 20,000 or more, the thickness can be reduced when the near-infrared absorbing pressure-sensitive adhesive is layered, which is preferable.

In the pressure-sensitive adhesive of the present invention, it is important to contain a reactive compound (F) capable of reacting with the side chain functional group in the polyester resin (D).
The reactive compound (F) used in the present invention is a compound having in its molecule a functional group capable of reacting with a side chain hydroxyl group or a side chain carboxyl group in the polyester resin (D). Examples of the compound include polyisocyanate compounds, polyfunctional silane compounds, N-methylol group-containing compounds, epoxy compounds, amine compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, melamine compounds, and metal chelate compounds. Among these, In order to act as a crosslinking agent, a compound having at least two functional groups capable of reacting with a hydroxyl group or a carboxyl group in the polyester resin (D) is preferably used. In particular, when the hydroxyl value of the polyester resin (D) is 0.1 to 50 mgKOH / g, the polyisocyanate compound is used. When the acid value is 0.1 to 50 mgKOH / g, an epoxy compound, An aziridine compound, a carbodiimide compound, an oxazoline compound, or a metal chelate compound is preferably used. These are preferably used because they are excellent in the adhesion of the resin composition after the crosslinking reaction and the adhesion to the coating layer.

  For example, examples of the polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', Examples thereof include 4 "-triphenylmethane triisocyanate.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and dodeca. Examples include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene. 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Examples thereof include methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

Moreover, the trimethylol propane adduct body of the said polyisocyanate, the trimer which has an isocyanurate ring, etc. can be used.
Furthermore, polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and polyisocyanate modified products thereof can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group selected from isocyanurate groups, or a modified product having two or more of these groups can be used. .
A reaction product of polyol and diisocyanate can also be used as polyisocyanate.

  Among these polyisocyanate compounds, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate), xylylene diisocyanate, 4,4 ′ Use of a non-yellowing or hard yellowing polyisocyanate compound such as methylenebis (cyclohexyl isocyanate) (also known as hydrogenated MDI) is particularly preferred from the viewpoint of weather resistance, heat resistance, and heat and humidity resistance.

  When a polyisocyanate compound is used as the reactive compound (F), a known catalyst can be used as necessary to accelerate the reaction. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it is possible to use a single compound or plural compounds.

  Examples of the epoxy compound as the reactive compound (F) include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N ′ -Diglycidylaminomethyl) cyclohexane and the like.

  Examples of the aziridine compound as the reactive compound (F) include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1 -Aziridinecarboxite), bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N'-hexamethylene-1,6-bis (1-aziridinecarboxite) , Trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5 -Triazine, trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-a Dilidinyl) butyrate], trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], 2,2 ′ -Bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'-ethyleneurea, 1,6 -Hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide, etc. Is mentioned.

  As the carbodiimide compound as the reactive compound (F), a compound having two or more carbodiimide groups (—N═C═N—) in the molecule is preferably used, and a known polycarbodiimide can be used.

Moreover, as a carbodiimide compound, the high molecular weight polycarbodiimide produced | generated by carrying out the decarboxylation condensation reaction of diisocyanate in presence of a carbodiimidization catalyst can also be used.
Examples of such compounds include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.
As the diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3′-dimethyl-4,4′-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4′- One of dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or a mixture thereof can be used.

  As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.

  An example of such a high molecular weight polycarbodiimide is a carbodilite series manufactured by Nisshinbo Industries, Ltd. Of these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.

  As the oxazoline compound as the reactive compound (F), a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′-ethylene is used. Bis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-propylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline) 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-p -Phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-Fe Renbis (4-phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'- m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-phenylenebis-2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline) ), 2,2'-o-phenylenebis (4-methyl-2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like. Alternatively, vinyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline and other monomers that can be copolymerized with these vinyl monomers. It may be a copolymer with a monomer.

  Examples of the metal chelate compound as the reactive compound (F) include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, and the like. Examples thereof include compounds coordinated with ethyl acetate.

  These reactive compounds (F) may be used alone or in combination.

The near-infrared absorbing pressure-sensitive adhesive of the present invention preferably contains 0.001 to 20 parts by weight of the reactive compound (F) with respect to 100 parts by weight of the polyester resin (D). It is more preferable to contain part. When the amount of the reactive compound (F) used exceeds 20 parts by weight, the adhesiveness of the near-infrared absorbing pressure-sensitive adhesive tends to decrease, the cohesive strength of the resin layer is low, and stability during repeated use It is inferior in durability and is not preferable. On the other hand, when the amount is less than 0.001 part by weight, a sufficient cross-linked structure cannot be obtained, so that the cohesive force is lowered and the heat resistance and heat-and-moisture resistance tend to be lowered.
The resin composition is three-dimensionally cross-linked by the reaction between the hydroxyl group or carboxylic acid group in the polyester resin (D) and the functional group in the reactive compound (F) to ensure adhesion to various substrates and adherends. In addition, since the heat resistance and heat-and-moisture resistance under conditions severer than before can be improved, it can be preferably used for an optical member.

  The near-infrared absorbing pressure-sensitive adhesive composition of the present invention includes a neon light absorbing compound appropriately selected from squarylium compounds, porphyrin compounds, cyanine compounds, quinacrine compounds, etc. having a maximum absorption wavelength at 550 to 620 nm. (H) can be contained.

  Examples of the cyanine compound include compounds represented by the general formula (5).

In the general formula (5), Z ₁ and Z ₂ are each independently a nonmetallic atom group that forms a 5-membered or 6-membered nitrogen-containing heterocycle. The nitrogen-containing heterocycle may be condensed with another heterocycle, aromatic ring or aliphatic ring. The nitrogen-containing heterocycle is preferably a 5-membered ring rather than a 6-membered ring. More preferably, a 5-membered nitrogen-containing heterocycle is condensed with a benzene ring or a naphthalene ring. Examples of nitrogen-containing heterocyclic rings and condensed rings include oxazole ring, isoxazole ring, benzoxazole ring, naphthoxazole ring, oxazolocarbazole ring, oxazodibenzofuran ring, thiazole ring, benzothiazole ring, naphthothiazole ring, indolenine Ring, benzoindolenin ring, imidazole ring, benzimidazole ring, naphthimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, furopyrrole ring, indolizine ring, imidazoquinoxaline ring and quinoxaline ring. An oxazodibenzobenzofuran ring is particularly preferred. The nitrogen-containing heterocyclic ring and the condensed ring may have a substituent. The example of a substituent is the same as the example of the substituent of benzene ring AD of General formula (2).
In the general formula (5), R7 and R8 are each independently an aliphatic group or an aromatic group. The aliphatic group and the aromatic group are the same as the aliphatic group and the aromatic group described in the general formula (2). In the general formula (5), L ₂ is a methine chain composed of one or three methines. The methine chain may have a substituent. The substituent is preferably bonded to the central (meso) methine. Examples of the substituent of the methine chain are the same as the examples of the substituent of the benzene rings A to D in the general formula (2). In the formula (5), b, c and d are each independently 0 or 1. b and c are each preferably 0. d becomes 0 when the cyanine dye has an anionic substituent such as sulfo or carboxyl to form an inner salt.
In the general formula (5), X ₂ ⁻ is an anion. Examples of anions include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), p-toluenesulfonic acid ions, ethyl sulfate ions, PF ₆ ⁻ , BF ₄ ⁻ and ClO ₄ ⁻ . The cyanine dye represented by the general formula (5) preferably has carboxyl or sulfo as a substituent.

  As a squarylium type compound, the diphenyl squarylium type compound which is a compound represented by General formula (6) is preferable.

  Examples of the alkyl group represented by R1 in the general formula (6) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group. , A linear, branched or cyclic group having 1 to 20 carbon atoms such as a pentadecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl group. Examples of the alkoxy group for R1 include: Methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, pentadecyloxy group, etc. Straight chain or branched chain having 1 to 20 carbon atoms Examples of the aryl group for R1 include a phenyl group and a naphthyl group. Examples of the aryloxy group for R1 include a phenoxy group and a naphthyloxy group. Examples of the halogen atom for R1 include fluorine. An atom, a chlorine atom, a bromine atom, etc. are mentioned.

  Examples of the substituent for the alkyl group, alkoxy group, aryl group and aryloxy group include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, cyclopropyl Group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and other alkyl groups having 1 to 10 carbon atoms, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyl Examples thereof include an alkoxy group having 1 to 10 carbon atoms such as an oxy group and a decyloxy group, a hydroxyl group, or a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom.

  In addition, the R1 is a group of alkanediyl groups such as propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, methylenedioxy group, ethylenedioxy group, propylenedioxy group, etc. An alkylenedioxy group may be formed. Examples of R1 include 1) a linear or branched alkyl group optionally having an alkoxy group, a hydroxyl group, or a halogen atom as a substituent, and 2) a linear or optionally having an alkoxy group as a substituent. A branched alkoxy group, 3) an alkyl group, an alkoxy group, or an aryl group or aryloxy group optionally having a halogen atom as a substituent, and 4) a halogen atom, preferably a straight chain having 1 to 8 carbon atoms. Alternatively, a branched alkyl group or a linear or branched alkoxy group having 1 to 8 carbon atoms is preferable.

  As the monovalent substituent of R2 in the general formula (6), for example, the same alkyl group as mentioned for the alkyl group in R1, the same alkoxy group as mentioned as the alkoxy group in R1, the R1 The same aryl group as mentioned for the aryl group in R 1, the same aryloxy group as mentioned for the aryloxy group in R 1, an amino group, and a 3-pyridyl group, 2-furyl group, 2-tetrahydrofuryl group And heterocyclic groups such as 2-thienyl group.

  Examples of the substituent for the alkyl group, alkoxy group, aryl group, aryloxy group and heterocyclic group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or the aryl group. Examples of the substituent for the amino group include an alkyl group and an aryl group. Examples of R2 include 1) a cycloalkyl group, an alkoxy group, an aryl group, or a linear or branched alkyl group optionally having a halogen atom as a substituent, 2) an alkoxy group, 3) a linear or branched chain A cycloalkyl group optionally having an alkyl group as a substituent, 4) an aryl group or an aryloxy group optionally having an alkyl group, an alkoxy group or a halogen atom as a substituent, 5) a substituent having an alkyl group It is preferably an amino group which may have as, or 6) a heterocyclic group, and further a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkoxy group having 1 to 8 carbon atoms. Group, cyclohexyl group, phenyl group, phenoxy group, amino group, 2-furyl group, or 2-tetrahydrofuryl group are preferable. -8 linear or branched alkyl groups are preferred.

G ₁ in the general formula (6) is a group represented by —NR 3 — such as NH group, methylamino group, ethylamino group (wherein R 3 is a hydrogen atom or an alkyl group) or an oxygen atom. Of these, a group represented by -NR3- is preferred, and an NH group is particularly preferred. The _{G 2} in the general formula (6), a sulfonyl group are preferable.

As the group represented by G ₁ -G ₂ -R ₂ , particularly preferred substituents are alkylsulfonylamino group, haloalkylsulfonylamino group, arylsulfonylamino group, haloarylsulfonylamino group, alkylarylsulfonylamino group, alkoxyaryl. A sulfonylamino group is mentioned. n is an integer of 1 or more, m and p are integers of 0 or more, m + n + p is 5 or less, and 1 is preferably 1 or more.

Furthermore, in the present invention, these substituents on the benzene ring may be different from each other with respect to the other benzene ring, and when m and n are 2 or more in one benzene ring, R1 And the group represented by G ₁ -G ₂ -R ₂ may be different from each other with respect to other substituents in the same ring, but as the diphenyl squarylium compound represented by the general formula (6) Are preferably left and right objects with a squarylium group in between.

  In the present invention, the neon light absorbing compound (H) is preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyester resin (D). .

In the near-infrared absorbing pressure-sensitive adhesive of the present invention, a compound (J) such as an ultraviolet absorber, a light stabilizer, or a fluorescent brightening agent is added to the polyester resin (D) 100 parts by weight as necessary. It can contain in the ratio of 001-20 weight part. These are used for reliably shielding ultraviolet rays having a wavelength of 380 nm or less. If the amount is less than 0.001 part by weight, an ultraviolet shielding auxiliary function cannot be expected, and if it is 20 parts by weight or more, a polyester resin ( The transparency of the laminate obtained using D) or the resin (D) is lowered, and coloring due to the color of the compound itself becomes a problem.
In addition, the compound which has several effects as compounds (J), such as said ultraviolet absorber, a light stabilizer, and a fluorescent whitening agent, can also be used.

Here, the ultraviolet absorber is a compound having an effect of generally absorbing ultraviolet rays having a wavelength of about 200 to 380 nm and changing them into energy such as heat or infrared rays and releasing them.
As the ultraviolet absorber, for example, metal oxide fine particles such as titanium dioxide, zinc oxide, iron oxide, cerium oxide, thallium oxide, lead oxide, and zirconium oxide can be used as an inorganic compound. Of these, zinc oxide is preferable from the viewpoint of colorlessness and transparency.
Examples of organic compounds include benzotriazole, triazine, benzoxazine, salicylic acid ester, diphenylmethanone, 2-cyanopropenoic acid ester, anthranilate, cinnamic acid derivative, camphor derivative, Benzalmalonate derivatives, resorcinols, oxalinides, coumarin derivatives, etc. can be used.

  Examples of the benzotriazole series include 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2- (2H- Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- ( tert-butyl) phenol and the like.

  Examples of triazines include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4,6-tris- (diisobutyl 4 '-Amino-benzalmalonate) -s-triazine, 4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy -4- Decyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

  Examples of diphenylmethanone include diphenylmethanone, methyldiphenylmethanone, 4-hydroxydiphenylmethanone, 4-methoxydiphenylmethanone, 4-octoxydiphenylmethanone, 4-decyloxydiphenylmethanone, 4- Dodecyloxydiphenylmethanone, 4-benzyloxydiphenylmethanone, 4,2 ', 4'-trihydroxydiphenylmethanone, 2'-hydroxy-4,4'-dimethoxydiphenylmethanone, 4- (2-ethylhexyloxy) ) -2-hydroxy-diphenylmethanone, methyl o-benzoylbenzoate, benzoin ethyl ether and the like.

  Examples of 2-cyanopropenoic acid esters include ethyl α-cyano-β, β-diphenylpropenoic acid ester, isooctyl α-cyano-β, β-diphenylpropenoic acid ester, and the like.

Examples of the salicylic acid ester include isocetyl salicylate, octyl salicylate, glycolic salicylate, and phenyl salicylate.
Examples of the anthranilate type include menthyl anthranilate.
Cinnamic acid derivatives include, for example, ethylhexylmethoxycinnamate, isopropylmethoxycinnamate, isoamylmethoxycinnamate, diisopropylmethylcinnamate, glyceryl-ethylhexanoate dimethoxycinnamate, methyl-α-carbomethoxycinnamate, methyl- Examples include α-cyano-β-methyl-p-methoxycinnamate.

Examples of the camphor derivative include benzylidene camphor, benzylidene camphor sulfonic acid, camphor benzalkonium methosulfate, terephthalylidene dicamphor sulfonic acid, polyacrylamide methyl benzylidene camphor, and the like.
Examples of the resorcinol type include dibenzoyl resorcinol and bis (4-tert-butylbenzoyl resorcinol).
Examples of the oxalinide series include 4,4′-di-octyloxy oxanilide, 2,2′-diethoxyoxy oxanilide, 2,2′-di-octyloxy-5,5′-di-tert. -Butyl oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl oxanilide, 2-ethoxy-2'-ethyl oxanilide, N, N'-bis (3 -Dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxyoxanilide and the like.
Examples of the coumarin derivative system include 7-hydroxycoumarin.

The light stabilizer is a compound having an effect of reducing auto-oxidative decomposition due to radicals generated by light energy and suppressing resin degradation.
As the light stabilizer, a hindered amine compound (abbreviated as “HALS”) or the like can be used. Examples of hindered amines include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5. -Triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] 2,2′-thiobis (4-t-octylphenolate) alkylamine nickel, dibutylamine, 1,3,5-triazine, N, N-bis (2,2,6,6-tetramethyl-4- Examples thereof include a polycondensate of piperidyl-1,6-hexamethylenediamine.N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine.

The fluorescent whitening agent is a kind of dye and is a compound that has the effect of absorbing white light and converting it into pale light (fluorescence) to increase whiteness.
Examples of the optical brightener include benzoxazole, triazine, pyrazoline, and coumarin compounds.

  The near-infrared absorbing pressure-sensitive adhesive of the present invention includes various resins, silane coupling agents, softeners, dyes, pigments, antioxidants, and tackifiers as long as the effects of the present invention are not impaired. Plasticizers, fillers, anti-aging agents, and the like may be blended.

The near-infrared absorbing pressure-sensitive adhesive sheet of the present invention will be described.
The near-infrared absorptive pressure-sensitive adhesive sheet of the present invention is provided with a near-infrared absorptive pressure-sensitive adhesive layer formed from the above-described near-infrared absorptive pressure-sensitive adhesive on at least one surface of a sheet-like substrate.
For example, a near-infrared-absorbing pressure-sensitive adhesive sheet can be obtained by coating, drying and curing the near-infrared-absorbing pressure-sensitive adhesive of the present invention on various sheet-like substrates.

  When applying a pressure sensitive adhesive, an appropriate liquid medium, for example, a hydrocarbon solvent such as toluene, xylene, hexane or heptane; an ester solvent such as ethyl acetate or butyl acetate; a ketone solvent such as acetone or methyl ethyl ketone A halogenated hydrocarbon solvent such as dichloromethane or chloroform; an ether solvent such as diethyl ether, methoxytoluene, or dioxane; or an organic solvent such as other hydrocarbon solvent can be added to adjust the viscosity; The near-infrared absorbing pressure sensitive adhesive can be heated to lower the viscosity. However, when an isocyanate is used as the reactive compound (F), a solvent containing a hydroxyl group cannot be used.

  As a sheet-like base material, those having a flat shape such as cellophane, various plastic sheets, glass plates and the like can be mentioned, and when applied to PDP, those having excellent transparency are preferable. Moreover, various base materials can also be used independently, and the thing in the multilayer state formed by laminating | stacking a several thing can also be used. Further, the surface can be peeled off.

  Various plastic sheets are also called various plastic films, such as polyvinyl alcohol film, triacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, polyolefin resin film such as ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate. , Polyester resin film such as polyethylene naphthalate, Polycarbonate resin film, Polynorbornene resin film, Polyarylate resin film, Acrylic resin film, Polyphenylene sulfide resin film, Polystyrene resin film, Vinyl Resin film, polyamide resin film, polyimide resin film, epoxy resin film, etc. And the like.

After applying the near-infrared absorbing pressure-sensitive adhesive to the sheet-like base material by an appropriate method according to a conventional method, when the near-infrared absorbing pressure-sensitive adhesive contains a liquid medium such as an organic solvent or water, If the liquid medium is removed or the near-infrared absorbing pressure-sensitive adhesive does not contain a liquid medium that should be volatilized, the adhesive layer in the molten state is cooled and solidified, and then placed on the sheet-like substrate. A near-infrared absorbing pressure-sensitive adhesive layer can be formed.
The thickness of the near-infrared absorbing pressure-sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 1 μm to 100 μm. If the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and if the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

The method for applying the near-infrared absorbing pressure-sensitive adhesive of the present invention to a sheet-like substrate is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater. Various coating methods such as knife coater, reverse coater, spin coater and the like can be mentioned.
There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although it depends on the cured form of the adhesive, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

In the present invention, before providing the near-infrared absorbing pressure-sensitive adhesive layer on the plastic film, a layer having various functions such as an ultraviolet absorbing layer, an electromagnetic wave absorbing layer, an anti-scratch layer, an antireflection layer, a color tone correction layer, and the like. What was laminated | stacked at least one layer previously can also be used as a base material.
Alternatively, after providing the near-infrared absorbing pressure-sensitive adhesive layer, at least one layer having various functions such as an ultraviolet absorbing layer, an electromagnetic wave absorbing layer, a scratch preventing layer, an antireflection layer, and a color tone correcting layer can be further laminated.

The near-infrared absorbing pressure-sensitive adhesive sheet of the present invention is
(A) A near-infrared-absorbing pressure-sensitive adhesive is applied to the release-treated surface of the release-treated sheet-like substrate, dried, and the non-release-treated sheet-like substrate is applied to the surface of the near-infrared-absorbing pressure-sensitive adhesive layer. Or laminated to
(A) A near-infrared absorbing pressure-sensitive adhesive is applied to a sheet-like base material that has not been subjected to release treatment, dried, and the release-treated surface of the release-like sheet-like base material is laminated on the surface of the pressure-sensitive adhesive layer. It can be obtained by doing.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

<Manufacture of polyester (D)>
(Synthesis Example 1)
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a polymerization tank equipped with a nitrogen introduction tube, and a dropping apparatus, the following dibasic acid-based component (A) having no hydroxyl group, diol having no carboxyl group (B) and the side chain functional group-introducing component (C) were respectively charged at the following ratios.

[Polymerization tank]
Trimethylolpropane (c1) 2.5 parts Neopentyl glycol (B) 57 parts 1,4-butanediol (B) 30 parts 1,6-hexanediol (B) 26 parts Isophthalic acid (A) 116 parts Sebacic acid ( A) 61 copies

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere while stirring. After maintaining at 100 ° C. for 1 hour, dehydration reaction was performed by gradually raising the temperature to 180 to 240 ° C. over about 8 hours. Next, when the acid value became 15 or less, 0.1 part of tetrabutyl titanate was added as a catalyst, the pressure was gradually reduced, the reaction was carried out at 1 to 3 torr and 260 ° C. for 5 hours, the solution was gradually cooled, and toluene The reaction was terminated by dissolving in a solution / ethyl acetate mixed solution (weight ratio = 1/3).
This reaction solution is light yellow and transparent, has a nonvolatile content of 50.1% by weight, a viscosity of 4,700 mPa · s, an acid value of a polyester resin of 0.3 mgKOH / g, a hydroxyl value of 10.2 mgKOH / g, and a glass transition temperature of −30 ° C. The weight average molecular weight was 90,000, the number average molecular weight was 30,000, and the degree of dispersion was 3.

(Synthesis Example 2)
Instead of the trimethylolpropane (c1) used as the side chain functional group introduction component (C) in Synthesis Example 1, 3 parts of trimellitic anhydride (c2) was used, and the amount of sebacic acid (A) was 50. The reaction was the same as in Synthesis Example 1 except that the amount was changed to 5 parts, dissolved in a toluene / ethyl acetate mixed solution (weight ratio = 1/3), light yellow and transparent, nonvolatile content of 50.2 wt%, viscosity of 5, A solution of a polyester resin of 600 mPa · s was obtained. The polyester resin had an acid value of 5.5 mg KOH / g, a hydroxyl value of 1.5 mg KOH / g, a glass transition temperature of −30 ° C., a weight average molecular weight of 105,000, a number average molecular weight of 30,000, and a dispersity of 3.5.

(Synthesis Example 3)
Synthesis example except that 13.4-parts of 1,4-butanediol diglycidyl ether (c3) was used instead of trimethylolpropane (c1) used as component (C) for side chain functional group introduction in synthesis example 1. 1 and react with a toluene / ethyl acetate mixed solution (weight ratio = 1/3) to prepare a solution of a polyester resin having a pale yellow transparent, non-volatile content of 50.0% by weight and a viscosity of 4,500 mPa · s. Obtained. The polyester resin had an acid value of 0.5 mg KOH / g, a hydroxyl value of 11.7 mg KOH / g, a glass transition temperature of −40 ° C., a weight average molecular weight of 85,000, a number average molecular weight of 34,000, and a dispersity of 2.5.

(Synthesis Example 4)
Aside from using 8.1 parts of 2,2-bis (hydroxymethyl) butanoic acid (c4) instead of trimethylolpropane (c1) used as the side chain functional group introduction component (C) in Synthesis Example 1 It reacts in the same manner as in Synthesis Example 1 and dissolves in a toluene / ethyl acetate mixed solution (weight ratio = 1/3), and is a pale yellow transparent polyester resin having a nonvolatile content of 50.1 wt% and a viscosity of 4,000 mPa · s. A solution was obtained. The acid value of the polyester resin was 4.2 mgKOH / g, the hydroxyl value was 1.2 mgKOH / g, the glass transition temperature was −40 ° C., the weight average molecular weight was 82,000, the number average molecular weight was 20,500, and the degree of dispersion was 4.0.

(Synthesis Example 5)
Instead of trimethylolpropane (c1) used as the side chain functional group introduction component (C) in Synthesis Example 1, 6.7 parts of 2-hydroxybutanedioic acid (c5) was used, and sebacic acid (A) The reaction was the same as in Synthesis Example 1 except that the amount was changed to 50.5 parts, dissolved in a toluene / ethyl acetate mixed solution (weight ratio = 1/3), light yellow and transparent with a nonvolatile content of 50.0% by weight. A polyester resin solution having a viscosity of 4,300 mPa · s was obtained. The polyester resin had an acid value of 0.3 mg KOH / g, a hydroxyl value of 10.5 mg KOH / g, a glass transition temperature of −40 ° C., a weight average molecular weight of 80,000, a number average molecular weight of 40,000, and a dispersity of 2.0.

(Synthesis Example 6)
To 100 parts of the polyester resin (D) solution obtained in Synthesis Example 1, 6 parts of ε-caprolactone (g1) was added as the cyclic ester compound (G), and 0.1 part of tetrabutylammonium tetrahydroborate was added as a catalyst. After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere with stirring and reacted for 10 hours. Next, after cooling, dissolve in a toluene / ethyl acetate mixed solution (weight ratio = 1/3) to obtain a pale yellow transparent polyester resin (D2) solution having a nonvolatile content of 50.1 wt% and a viscosity of 4,600 mPa · s. Obtained. The polyester resin had an acid value of 0.1 mg KOH / g, a hydroxyl value of 5.3 mg KOH / g, a glass transition temperature of −45 ° C., a weight average molecular weight of 88,000, a number average molecular weight of 35,200, and a dispersity of 2.5.

(Synthesis Example 7)
6 parts of ε-caprolactone (g1) as a cyclic ester compound (G) was added to 100 parts of the polyester resin (D) solution obtained in Synthesis Example 3, and reacted in the same manner as in Synthesis Example 6 to produce a pale yellow transparent, non-volatile A solution of polyester resin (D2) having a content of 50.1% by weight and a viscosity of 4,800 mPa · s was obtained. The polyester resin had an acid value of 0.1 mgKOH / g, a hydroxyl value of 4.8 mgKOH / g, a glass transition temperature of −45 ° C., a weight average molecular weight of 95,000, a number average molecular weight of 38,000, and a dispersity of 2.5.

(Synthesis Example 8)
6 parts of ε-caprolactone (g1) as a cyclic ester compound (G) was added to 100 parts of the polyester resin (D) solution obtained in Synthesis Example 5 and reacted in the same manner as in Synthesis Example 6, resulting in a pale yellow transparent and non-volatile A solution of a polyester resin (D2) having a content of 50.1% by weight and a viscosity of 4,600 mPa · s was obtained. The polyester resin had an acid value of 0.1 mgKOH / g, a hydroxyl value of 4.2 mgKOH / g, a glass transition temperature of −45 ° C., a weight average molecular weight of 86,000, a number average molecular weight of 21,500, and a dispersity of 4.0.

(Synthesis Example 9)
The polymerization tank and the dropping device of the polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube have polyester polyol, acid anhydrides, and two cyclic ether groups in the molecule. The compound (c3), the cyclic ester compound (g1), the catalyst and the organic solvent were charged in the following ratios.

[Polymerization tank]
Polyester diol * (B) 376 parts
* Kuraray polyol P4010 (Kuraray)
Succinic anhydride (A) 18 parts Toluene 76 parts Ethyl acetate 30 parts Tetrabutylammonium tetrahydroborate (catalyst) 0.5 part [Drip device]
Bisphenol A diglycidyl ether (c3) 34 parts ε-caprolactone (g1) 32 parts Tetrabutylammonium tetrahydroborate (catalyst) 1 part Ethyl acetate 47 parts

After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere while stirring, and the reaction was performed for 8 hours. Subsequently, the said mixture was dripped at constant velocity over 1 hour from the dripping apparatus.
After completion of the addition, 1 part of tetrabutylammonium tetrahydroborate was added after 8 hours with further stirring, and after further aging for 8 hours, 39 parts of phenyl isocyanate was added dropwise at a constant rate over 1 hour in order to reduce excess hydroxyl groups. . After completion of the dropping, the mixture was further aged for 6 hours with stirring, and then a toluene / ethyl acetate mixed solution was added and cooled to room temperature to obtain a solution of a polyester resin (D2).
This reaction solution is light yellow and transparent with a non-volatile content of 50.3% by weight and a viscosity of 12,000 mPa · s. The acid value of the resin is 0.2 mgKOH / g, the hydroxyl value is 17.8 mgKOH / g, the glass transition temperature is −20 ° C. The weight average molecular weight was 130,000, the number average molecular weight was 20,000, and the degree of dispersion was 6.5.

(Synthesis Example 10)
The reaction was performed in the same manner as in Synthesis Example 1 except that the trimethylolpropane (c1) used as the component (C) for introducing a side chain functional group in Synthesis Example 1 was not used, and a toluene / ethyl acetate mixed solution (weight ratio = 1/3) ) To obtain a polyester resin solution having a pale yellow transparent, non-volatile content of 50.0% by weight and a viscosity of 3,800 mPa · s. The acid value of the polyester resin was 0.2 mgKOH / g, the hydroxyl value was 1.5 mgKOH / g, the glass transition temperature was −30 ° C., the number average molecular weight was 27,000, and the weight average molecular weight was 65,000.

<Manufacture of acrylic resin>
(Synthesis Example 11)
The following acrylic monomers were charged at the following ratios into a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.

[Polymerization tank]
N-butyl acrylate 19.5 parts methyl methacrylate 4 parts 4-hydroxybutyl acrylate 1.5 parts ethyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [drip apparatus]
N-butyl acrylate 19.5 parts methyl methacrylate 4 parts 4-hydroxybutyl acrylate 1.5 parts ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the reaction was started at a reflux temperature in a nitrogen atmosphere while stirring. When the polymerization rate reached about 70%, the dropping of the mixture of the acrylic monomer, the polymerization initiator and the organic solvent was started from the dropping device. After completion of dropping, the mixture was further aged for 8 hours with stirring, and then toluene was added and cooled to room temperature to obtain a transparent solution containing an acrylic resin.
This reaction solution is colorless and transparent, has a nonvolatile content of 30.0% by weight, a viscosity of 7,000 mPa · s, an acid value of the resin of 0.1 mgKOH / g, a hydroxyl value of 12.8 mgKOH / g, a glass transition temperature of −40 ° C., several The average molecular weight was 200,000 and the weight average molecular weight was 800,000.

  About the polyester resin (D) obtained in Synthesis Examples 1 to 10 and the acrylic resin obtained in Synthesis Example 11, the appearance of the solution, the nonvolatile content, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin, The glass transition temperature (Tg), acid value (AV) and hydroxyl value (OHV) were determined according to the following methods, and the results are shown in Table 1.

<< Solution appearance >>
The appearance of each resin solution was visually evaluated.

<< Measurement of non-volatile content (TS) >>
About 1 g of each resin solution was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, the residue was weighed, and the remaining rate was calculated to obtain a nonvolatile content concentration (solid content) (unit:%).

<< Measurement of solution viscosity (Vis) >>
Each resin solution was measured with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 25 ° C. under conditions of 12 rpm and 1 minute rotation (unit: mPa · s).

<< Measurement of Number Average Molecular Weight (Mn) and Weight Average Molecular Weight (Mw) >>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used.
GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size, and the number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined in terms of polystyrene.

<< Measurement of glass transition temperature (Tg) >>
The measurement was performed by connecting a “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) to a robot DSC (differential scanning calorimeter) “RDC220” (manufactured by Seiko Instruments Inc.).
About 10 mg of sample was weighed in an aluminum pan and set in a DSC apparatus (reference: the same type of aluminum pan without sample). After heating at 300 ° C. for 5 minutes, using liquid nitrogen − Rapid cooling was performed to 120 ° C. Thereafter, the temperature was raised at 10 ° C./min, and the glass transition temperature (Tg) was calculated from the obtained DSC chart (unit: ° C.).

<Measurement of acid value (AV)>
About 1 g of a sample (resin solution: about 50%) is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. To this is added phenolphthalein reagent as an indicator and held for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The acid value was determined by the following formula. The acid value was a numerical value of the dry state of the resin (unit: mgKOH / g).
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<< Measurement of hydroxyl value (OHV) >>
About 1 g of a sample (resin solution: about 50%) is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula. The hydroxyl value was a numerical value in the dry state of the resin (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.25} / S] / (Nonvolatile content concentration / 100) + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
D: Acid value (mgKOH / g)

Example 1
IRG-068 (maximum absorption wavelength: Nippon Kayaku Co., Ltd.) as the diimonium salt compound (e1) with respect to 100 parts of the solution (solid content: about 50%) of the polyester resin (D) obtained in Synthesis Example 1. 1 part of 1100 to 1150 nm), 1 part of phthalocyanine IR-10A (absorption maximum wavelength: about 838 nm) manufactured by Nippon Shokubai Co., Ltd. as another near-infrared absorbing agent (e2), and 25 parts of toluene were further added. As a functional compound (F), 2.5 parts of TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) was added and stirred well to obtain a near infrared absorbing pressure-sensitive adhesive of the present invention. This was coated on a release-treated polyester film (hereinafter referred to as “release film”) so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form a resin layer.
A near-infrared absorbing agent-containing resin layer is laminated with a polyester film that has not been subjected to a release treatment on the formed near-infrared absorbing agent-containing resin layer and aged for one week at a temperature of 23 ° C. and a relative humidity of 50% (dark reaction). The cross-linking reaction between the polyester resin (D) and the reactive compound (F) is advanced to obtain a near-infrared-absorbing pressure-sensitive adhesive sheet having a laminate structure of release film / near-infrared absorbing pressure-sensitive adhesive layer / polyester film, The heat resistance and heat-and-moisture resistance of a near-infrared absorption function, and a refractive index were evaluated by the method shown below. The results are shown in Table 2.

(Near infrared absorption heat resistance test)
About each near-infrared absorptive pressure-sensitive-type adhesive sheet in 500 degree environment in the temperature of 80 degreeC, the Haze value before and behind a test and the transmittance | permeability T (%) before and after a test in 850 nm and 950 nm were calculated | required.

(Moisture and heat resistance test of near infrared absorption function)
The heat resistance test for 24 hours and 48 hours at a temperature of 80 ° C. and a humidity of 80% is performed, and the transmittance of the maximum absorption wavelength is measured for each near-infrared absorbing pressure-sensitive adhesive sheet before and after the test, and the difference (ΔT) Was calculated (%).

<< Evaluation method of refractive index of near-infrared absorbing pressure-sensitive adhesive layer >>
The release film was peeled off from the near-infrared absorbing pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, and sodium D rays were irradiated with an Abbe refractometer “DR-M2” (manufactured by ATAGO) in an atmosphere of 25 ° C. Then, the refractive index of the adhesive layer on the adhesive sheet was measured.

[Examples 2 and 4]
Instead of the solution of the polyester resin (D) of Synthesis Example 1 (solid content of about 50%) used in Example 1, the solution of the polyester resin (D) obtained in Synthesis Examples 2 and 4 (solid content of about 50%) ) And HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) 0.25 parts by weight was used as the reactive compound (F). Thus, a near-infrared absorbing pressure-sensitive adhesive and a near-infrared absorbing pressure-sensitive adhesive sheet were obtained and evaluated in the same manner.

[Examples 3 and 5-9]
Instead of the solution of the polyester resin (D) of Synthesis Example 1 used in Example 1 (solid content: about 50%), the polyester resin (D) obtained in Synthesis Examples 3, 5, 6, 7, 8, and 9 A near-infrared absorbing pressure-sensitive adhesive and a near-infrared absorbing pressure-sensitive adhesive sheet were obtained and evaluated in the same manner as in Example 1 except that the solution was used.

[Example 10]
Instead of IR-10A manufactured by Nippon Shokubai Co., Ltd. used as the other near-infrared absorbing agent (e2) in Example 1, 1 part of Dithio Ni dye MIR101 (absorption maximum wavelength: 852 nm) manufactured by Midori Chemical Co., Ltd. Except having used, it carried out similarly to Example 1, and obtained the near-infrared absorptive pressure-sensitive adhesive and the near-infrared absorptive pressure-sensitive adhesive sheet, and evaluated it similarly.

[Examples 11 to 12]
Instead of Nippon Kayaku Co., Ltd. IRG-068 used as the diimonium salt compound (e1) in Example 1, Nippon Carlit Co., Ltd. diimmonium CIR-1081 (absorption maximum wavelength: 1100-1150 nm, Example 11) , Nippon Carlit Co., Ltd. diimonium CIR-1085 (absorption maximum wavelength: 1100-1150 nm, Example 12) was used in the same manner as in Example 1 except that two parts were used, and a near-infrared absorbing pressure-sensitive adhesive, and A near-infrared absorbing pressure-sensitive adhesive sheet was obtained and evaluated in the same manner.

[Example 13]
In addition to the diimonium salt compound (e1) and the other near-infrared absorbing agent (e2) used in Example 1, 2,4-bis (2,4-dimethylphenyl)- Similar to Example 1 except that 0.5 part of 6- [2-hydroxy-4- (3-nonyloxy-2-hydroxypropyloxy) -5-α-cumylphenyl] -s-triazine was used. An infrared-absorbing pressure-sensitive adhesive and a near-infrared-absorbing pressure-sensitive adhesive sheet were obtained and evaluated in the same manner.

[Comparative Examples 1-2]
2 parts of IRG-068 manufactured by Nippon Kayaku Co., Ltd. (Comparative Example 1) with respect to 100 parts by weight of the solution (solid content: about 50%) of the polyester resin (D) obtained in Synthesis Example 1, other near infrared absorption A near-infrared-absorbing pressure-sensitive adhesive and a near-infrared-absorbing pressure-sensitive adhesive sheet in the same manner as in Example 1 except that 1 part (Comparative Example 2) of phthalocyanine IR-10A manufactured by Nippon Shokubai Co., Ltd. was used as the adhesive agent (e2). Obtained and evaluated in the same manner.

(Comparative Example 3)
Instead of the polyester resin (D) obtained in Synthesis Example 1, the polyester resin (D) obtained in Synthesis Example 10 was adjusted to a solid content of 50% with a toluene / ethyl acetate mixed solvent (weight ratio = 1/3). A near-infrared-absorbing pressure-sensitive adhesive and a near-infrared-absorbing pressure-sensitive adhesive sheet were obtained and evaluated in the same manner as in Example 1 except that the solution so dissolved was used.

(Comparative Example 4)
Instead of the polyester resin (D) used in Example 1, 100 parts of the acrylic resin solution prepared in Synthesis Example 11 was used, and IRG-068 manufactured by Nippon Kayaku Co., Ltd. was used as the diimonium salt compound (e1). 2 parts, 1 part of phthalocyanine IR-10A manufactured by Nippon Shokubai Co., Ltd. and 15 parts of toluene are added as other near-infrared absorbing agent (e2), and TDI / TMP (tolrange) is further added as the reactive compound (F). (Isocyanate trimethylolpropane adduct) 1.5 parts by weight was added and stirred well to obtain a near-infrared absorbing pressure-sensitive adhesive and a near-infrared absorbing pressure-sensitive adhesive sheet in the same manner as in Example 1. Evaluated.

  Since the near-infrared absorbing pressure-sensitive adhesive of the present invention contains a polyester resin that can form a pressure-sensitive adhesive layer rich in cohesion after crosslinking, the heat resistance of the near-infrared absorbing function than when an acrylic resin is used, It can improve heat and humidity resistance. Furthermore, the near-infrared absorbing pressure-sensitive adhesive of the present invention can form a pressure-sensitive adhesive layer having a higher refractive index than when an acrylic resin is used, so that the refractive index is about 1.50 to 1.58. When adhering the adherend and the substrate, the refractive index difference at the laminated interface can be reduced, and the transmitted light can be effectively utilized.

Claims (7)

A polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain, a diimonium salt compound (e1), and a diimonium salt compound (e1) having a glass transition temperature in the range of −80 to 0 ° C. A near-infrared-absorbing pressure-sensitive adhesive containing another near-infrared absorbing agent (e2) having a different wavelength and a reactive compound (F) capable of reacting with a hydroxyl group and / or a carboxyl group in the resin (D). The other near-infrared absorbing agent (e2) is at least one selected from the group consisting of aminium compounds, anthraquinone compounds, polymethine compounds, cyanine compounds, phthalocyanine compounds, benzopyridium compounds, and thiometal complex compounds. The near-infrared absorptive pressure-sensitive adhesive according to claim 1. 0.01 to 20 weights in total of the diimonium salt compound (e1) and the other near-infrared absorbing agent (e2) with respect to 100 parts by weight of the polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain The near-infrared absorptive pressure-sensitive adhesive according to claim 1 or 2, comprising 0.001 to 20 parts by weight of the reactive compound (F). A polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain,
A dibasic acid component (A) having no hydroxyl group;
A diol (B) having no carboxyl group;
A trihydric or higher polyhydric alcohol (c1), a trihydric or higher polyhydric carboxylic acid (c2), a compound having two cyclic ether groups in the molecule (c3), two hydroxyl groups and one carboxyl group in one molecule At least one component for introducing a side chain functional group selected from the group consisting of dioxycarboxylic acid (c4) having the above and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule ( The near-infrared absorbing pressure-sensitive adhesive according to any one of claims 1 to 3, which is a polyester resin (D1) obtained by reacting C). A polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain is added to the side chain functional group in the polyester resin (D1) having a hydroxyl group and / or a carboxyl group in the side chain, and a cyclic ester compound ( A polyester resin (D2) having a ring-opening portion of the cyclic ester compound (G) formed by ring-opening addition of G) as a side chain and a hydroxyl group at the terminal of the ring-opening portion. Item 5. The near-infrared absorbing pressure-sensitive adhesive according to Item 4. 6. The near infrared ray according to claim 1, wherein the reactive compound (F) has two or more functional groups capable of reacting with the side chain functional group in the polyester resin (D) in one molecule. Absorbent pressure sensitive adhesive. A near-infrared absorptive pressure-sensitive adhesive layer formed by laminating a near-infrared absorptive pressure-sensitive adhesive layer formed from the near-infrared absorptive pressure-sensitive adhesive according to any one of claims 1 to 6 on at least one surface of a sheet-like substrate. Adhesive sheet.