JP2008308620A - Ultraviolet blocking pressure-sensitive adhesive composition and ultraviolet blocking pressure-sensitive adhesive sheet using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ultraviolet blocking pressure-sensitive adhesive composition excellent in weather resistance and used by applying to a film, etc. and an ultraviolet blocking adhesive sheet produced by using the composition. <P>SOLUTION: The ultraviolet blocking pressure-sensitive adhesive composition comprises (D) a polyester-based resin having -80 to 0°C glass transition temperature and having a hydroxyl group and/or a carboxyl group on a side chain, (E) an organic ultraviolet-blocking compound and (F) a reactive compound capable of reacting with the hydroxyl group and/or the carboxyl group in the resin (D). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a UV-blocking pressure-sensitive adhesive composition excellent in weather resistance and applied to a film or the like, and a UV-blocking pressure-sensitive adhesive sheet using the same.

  Conventionally, polyester films, especially biaxially stretched films of polyethylene terephthalate and polyethylene naphthalate have excellent mechanical properties, heat resistance, and chemical resistance, so magnetic tape, ferromagnetic thin film tape, photographic film, packaging film, It is widely used as a sheet-like base material for electronic component films, electrical insulating films, and metal plate laminating films, and as a protective film to be attached to the surface of cathode ray tube type displays and various members.

  Furthermore, in recent years, polyester films have been widely used as materials for various optical films. In particular, it is used as a sheet-like substrate such as a prism lens sheet, a touch panel, a backlight, etc., a sheet-like substrate of an antireflection film, and an explosion-proof sheet of a display. When used in such optical film members, excellent transparency and adhesion, heat resistance, moisture resistance, etc. are required not only for sheet-like substrates but also for pressure-sensitive adhesive layers used for pasting. The

  A pressure-sensitive adhesive has adhesiveness at room temperature and can be attached to an adherend simply by applying pressure, and acrylic adhesives are used in electrical and electronic parts and in terms of excellent weather resistance. Widely used in other fields. For example, a plasma display (PDP) used for a large thin television, a thin display, etc., is laminated with an adhesive layer in which a large number of various functional sheet materials expressing various functions are formed from a pressure-sensitive adhesive composition. The

By the way, in a plasma display, for example, a film or a coating film having a property of absorbing near infrared rays, which are heat rays, is used and has an important function. That is, in a plasma display or the like, near infrared rays are emitted from the screen, which acts on peripheral electronic devices such as remote control devices using the near infrared rays and causes malfunctions. In the plasma display, the near infrared ray radiated from the screen is blocked by forming a near infrared absorption layer that absorbs near infrared rays and transmits visible light. Usually, it will be formed of a near-infrared absorbing resin composition.
However, the near-infrared absorbing dye used in the near-infrared blocking layer is not only easily decomposed and discolored by invisible ultraviolet (UV) radiation having a wavelength of 290 to 380 nm such as sunlight. The material such as an acrylic resin and additive compounding agent used as a pressure-sensitive adhesive used in such a structure is decomposed or collapsed. In order to shorten the service life of the plasma display, the above-mentioned fading and decomposition are desired to protect from ultraviolet exposure as the most important.

As a conventional pressure-sensitive adhesive, for example, a pressure-sensitive adhesive composition containing an acrylic resin having a hydroxyl group and a crosslinking agent, which also contains a volatile acid, is disclosed. (For example, refer to Patent Document 1).
In addition, for example, a sheet for forming a surface protective film for a display having a surface protective layer containing at least an ultraviolet blocking agent, an adhesive layer, and a separator in this order on a peelable substrate is disclosed (for example, Patent Document 2). reference.).
However, these pressure-sensitive adhesive compositions are not set so as to be applicable to plasma displays, and therefore those obtained by adding an organic ultraviolet blocking agent to the pressure-sensitive adhesive as described above. Even when mixed uniformly in solution, it may bleed out over time, causing hygiene problems, and depending on the type of UV blocker, it may be yellowish and show an old appearance there were. Occasionally, it was crystallized in a pressure-sensitive adhesive, resulting in a flickering appearance, or the acrylic resin itself deteriorated, resulting in a reduction in commercial value.

For example, a transparent product that has an ultraviolet shielding effect by containing ultrafine zinc oxide particles in an organic or inorganic binder and using it as a coating material on substrates such as films, fibers, resin plates, glass and paper Is disclosed (see, for example, Patent Document 3).
Further, for example, the zinc oxide ultrafine particles can be obtained by heating and vaporizing a zinc raw material by a direct current arc plasma method, oxidizing and cooling the zinc vapor, and the pH of a 20 wt% aqueous dispersion is 6. A non-aqueous dispersion of zinc oxide ultrafine particles by dispersing rod-shaped hexagonal zinc oxide ultrafine particles having an average particle diameter of 5 to 70 nm in an organic solvent together with a dispersant. Is disclosed (see, for example, Patent Document 4).

However, based on the above suggestion, for example, a commercially available zinc oxide ultrafine particle dispersion liquid having a transparent appearance such as zinc oxide as described above is added to a pressure-sensitive adhesive composition comprising an acrylic copolymer composition as a binder. When added, the zinc oxide ultrafine particles are aggregated together in the pressure-sensitive adhesive to become coarse particles, and the pressure-sensitive adhesive becomes opaque, sometimes gels and loses fluidity.
JP 2002-241732 A JP-A-9-166963 Japanese Patent Laid-Open No. 9-59591 JP 11-278838 A

  An object of this invention is to provide the ultraviolet-blocking adhesive composition excellent in the weather resistance used by apply | coating to a film etc., and the ultraviolet-blocking adhesive sheet which forms a plasma display etc. using the same.

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, an organic ultraviolet blocking compound (E) and a glass transition temperature in the range of −80 to 0 ° C. The present invention relates to a UV-blocking pressure-sensitive adhesive composition comprising a reactive compound (F) capable of reacting with a hydroxyl group and / or a carboxyl group in the resin (D).

  In the second invention, the organic ultraviolet blocking compound (E) is a benzotriazole derivative, p-aminobenzoic acid derivative, anthranilic acid derivative, salicylic acid derivative, cinnamic acid derivative, benzophenone derivative, coumaric acid derivative, cyanoacrylate. The ultraviolet-blocking pressure-sensitive adhesive composition according to the first invention, which is at least one selected from a derivative and an amino acid compound.

  Moreover, 3rd invention is 0.1-40.0 weight part of organic type ultraviolet-blocking compounds (E) with respect to 100 weight part of polyester-type resin (D) which has a hydroxyl group and / or a carboxyl group in a side chain, and It is related with the ultraviolet-blocking pressure-sensitive-type adhesive composition as described in 1st or 2nd invention characterized by including 0.001-20 weight part of reactive compounds (F).

  Further, in the fourth invention, the polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain comprises a dibasic acid component (A) having no hydroxyl group and a diol (B) having no carboxyl group. A trihydric or higher polyhydric alcohol (c1), a trivalent or higher polyhydric carboxylic acid (c2), a compound having two cyclic ether groups in the molecule (c3), two hydroxyl groups and a carboxyl group in one molecule For introducing at least one side chain functional group selected from the group consisting of dioxycarboxylic acid (c4) having one or more and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule. The ultraviolet blocking pressure-sensitive adhesive composition according to any one of the first to third inventions, which is a polyester resin (D1) obtained by reacting the component (C).

  Further, the fifth invention provides the side chain functional group in the polyester resin (D1) having a hydroxyl group and / or a carboxyl group in the side chain and in the polyester resin (D1) having a hydroxyl group and / or a carboxyl group in the side chain. A polyester resin (D2) having a ring opening portion of the cyclic ester compound (G) as a side chain and a hydroxyl group at the terminal of the ring opening portion. The present invention relates to a UV-blocking pressure-sensitive adhesive composition according to the fourth invention.

  The sixth invention is characterized in that 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 ultraviolet blocking pressure-sensitive adhesive composition according to any one of the fifth inventions.

  According to a seventh aspect of the invention, there is provided an ultraviolet blocking pressure-sensitive adhesive layer formed from the ultraviolet blocking pressure-sensitive adhesive composition according to any one of the first to sixth inventions on at least one surface of a plastic film. The present invention relates to a laminated ultraviolet blocking pressure-sensitive adhesive sheet.

  By using the pressure-sensitive adhesive resin composition of the present invention, it has become possible to provide an ultraviolet blocking adhesive composition having excellent weather resistance and an ultraviolet blocking adhesive sheet using the same.

  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, '- ester such as monoalcohol trifunctional or more polycarboxylic acids and anhydrides thereof such as methanol or ethanol, such as biphenyl tetracarboxylic acid and the like.

  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 added as appropriate to prepare a pressure-sensitive adhesive composition.
(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 added as appropriate to prepare a pressure-sensitive adhesive composition.
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 composition can also be obtained by using a polyester resin (D2) having a ring-opened portion as a side chain and a hydroxyl group at the end of the ring-opened 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 increase the 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 aspect of the polymer formed by ring-opening polymerization of the molecule, 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. Therefore, the polyester resin (D) is used. In addition to being difficult to peel off the laminated body obtained, for example, a glass member for organic electroluminescence, an 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.

  Examples of the organic ultraviolet blocking compound (E) used in the present invention include benzotriazole derivatives, p-aminobenzoic acid derivatives, anthranilic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, coumaric acid derivatives, cyanoacrylate derivatives and Examples include amino acid compounds.

  Examples of the benzotriazole derivatives include 2- (2′-hydroxy-5′-tert-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′- Hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-) 3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- {2′-hydro Cis-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl} benzotriazole, 2,2methylenebis {4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol}, 2- (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole and the like.

  Examples of p-aminobenzoic acid derivatives include esters of p-aminobenzoic acid with ethyl, propyl, butyl, isobutyl, monoglyceride, etc., p-dimethylaminobenzoic acid and esters thereof with ethyl or amyl, p-diethylaminobenzoic acid, etc. Examples include acids and esters thereof with ethyl or amyl, and 2-ethylhexyl ester of p-dimethylaminobenzoic acid.

  Examples of anthranilic acid derivatives include esters of anthranilic acid, and in particular, anthranilic acid menthyl ester.

  The salicylic acid derivative is preferably an ester of salicylic acid, and among them, phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2-ethylhexyl salicylate, homomenthyl salicylate, and each ester of salicylic acid with ethylene glycol, glycerin, etc. Further, triethanolammonium salt of salicylic acid is more preferable.

  Examples of cinnamic acid derivatives include sinoxate, p-methoxycinnamic acid diethanolamine, p-methoxycinnamic acid 2-ethylhexyl ester, p-acetamidocinnamic acid isopropyl ester, and the like.

  The benzophenone derivatives include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy- 4-methoxybenzophenone, 2,2′-dihydroxy 4,4′-dimethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 4-phenylbenzophenone-2-carboxylic acid-isooctyl ester, 2-hydroxy Examples include benzophenone and 2,2′-4,4′-tetrahydroxybenzophenone.

  Examples of the coumarinic acid derivative include 7-ethylamino-4-methylcoumarin, 7,8-dihydroxycoumarin, 6,7-dihydroxycoumarin, 7-hydroxycoumarin, 4-methyl-7-hydroxycoumarin and the like.

  Examples of the cyanoacrylate derivative include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and the like.

  Examples of amino acid compounds include urocanic acid, tributamine derivatives, and glutamic acid derivatives.

  The pressure-sensitive adhesive composition of the present invention preferably contains 0.1 to 40.0 parts by weight of the organic ultraviolet blocking compound (E) with respect to 100 parts by weight of the polyester resin (D). It is more preferable to contain 2 to 20 parts by weight. When the amount of the organic ultraviolet blocking compound (E) used exceeds 40 parts by weight, the adhesiveness of the resulting pressure-sensitive adhesive composition tends to decrease and the cohesive force of the resin layer decreases, which is not preferable. Moreover, if it is less than 0.1 weight part, since it exists in the tendency for the effect containing the organic type ultraviolet blocking compound (E) to be hard to be exhibited, it is unpreferable.

In the pressure-sensitive adhesive composition of the present invention, if necessary, the light stabilizer (G) or the fluorescent brightening agent (H) is added in an amount of 0.001 to 20 parts by weight with respect to 100 parts by weight of the polyester resin (D). It can contain in the ratio. Any of these compounds can be used as an auxiliary to the compound (E) in order to reliably block ultraviolet rays having a wavelength of 380 nm or less. However, if the amount is less than 0.001 part by weight, the ultraviolet ray blocking auxiliary function is expected. However, if it is 10 parts by weight or more, the transparency of the resin (D) or a laminate obtained by using the resin is lowered, or coloring due to the color of the compound itself becomes a problem.
A compound having a plurality of effects as the light stabilizer and the fluorescent brightening agent can also be used. 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.

In the pressure-sensitive adhesive composition 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 these polyisocyanate modified products 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 pressure-sensitive adhesive composition 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), and 0.01 to 10 parts by weight. It is more preferable to contain. When the amount of the reactive compound (F) used exceeds 20 parts by weight, the adhesiveness of the resulting pressure-sensitive adhesive composition tends to decrease, the cohesive strength of the resin layer is low, and stability and durability during repeated use. It is inferior in property and 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 resin composition of the present invention is suitable as an optical pressure-sensitive adhesive composition, and preferably contains an organic solvent.
In addition, the resin composition of the present invention has various resins, silane coupling agents, softeners, dyes, pigments, antioxidants, tackifiers, plasticizers, fillers, as long as the effects of the present invention are not impaired. You may mix | blend an agent, an antioxidant, etc.

By using the pressure-sensitive adhesive composition of the present invention, a laminated product (hereinafter referred to as “adhesive sheet”) composed of an adhesive layer and a sheet-like substrate can be obtained.
For example, an adhesive sheet can be obtained by coating, drying and curing the pressure-sensitive adhesive composition of the present invention on various sheet-like substrates.

  When applying a pressure-sensitive adhesive composition, 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 such as acetone or methyl ethyl ketone Viscosity can be adjusted by adding organic solvents such as halogenated hydrocarbon solvents such as dichloromethane and chloroform; ether solvents such as diethyl ether, methoxytoluene and dioxane, and other hydrocarbon solvents. In addition, the pressure-sensitive adhesive composition can be heated to reduce the viscosity. However, a solvent containing a hydroxyl group cannot be used.

  Examples of the sheet-like base material include cellophane, various plastic sheets, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plate, metal plate, wood and the like in a flat shape. 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.

When the pressure-sensitive adhesive composition contains a liquid medium such as an organic solvent or water after the pressure-sensitive adhesive composition is applied to the sheet-like base material by an appropriate method according to a conventional method, the liquid medium If the pressure-sensitive adhesive composition does not contain a liquid medium that should be volatilized, the adhesive layer in the molten state is cooled and solidified, and pressure-sensitive adhesive is applied to the sheet-like substrate. An agent layer can be formed.
The thickness of the 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 pressure-sensitive adhesive composition 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 a knife coater, a reverse coater, and a spin coater can be used.
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 composition, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

The laminate of the present invention is a so-called sheet (also referred to as “film” as described above) optical member having various optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film. And a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention. On the other surface of the pressure-sensitive adhesive layer, a sheet-like base material subjected to a release treatment can be laminated.
The laminate of the present invention is
(A) A pressure-sensitive adhesive composition is applied to the release-treated surface of the release-treated sheet-like substrate, dried, and a sheet-like optical member is laminated on the surface of the pressure-sensitive adhesive layer,
(A) A pressure-sensitive adhesive composition is applied to a sheet-like optical member, dried, and the release-treated surface of the peeled sheet-like substrate is laminated on the surface of the pressure-sensitive adhesive layer. be able to.

  Since the pressure-sensitive adhesive of the present invention is composed of a polyester resin, it has improved adhesion to a substrate, has excellent plasticizer resistance and low-temperature adhesion, and adheres to a substrate such as a foam. It is also preferably used for applications that require safety. In particular, since an aromatic ring can be contained in the main chain skeleton, the refractive index after drying and / or curing of the pressure-sensitive adhesive composition can be maintained at 1.45 or more. As described above, the refractive index of the material used for the optical member such as the optical member film or glass is about 1.50 to 1.58, and the pressure-sensitive adhesive composition is dried and dried. If the refractive index after curing is less than 1.45, the difference in refractive index between the optical film and the optical member increases. Therefore, for example, when an adhesive layer obtained from the pressure-sensitive adhesive composition is provided on a film light guide plate which is a kind of optical film, total reflection occurs at a shallow angle, and effective use of light is achieved. May decrease. Moreover, in order to reduce the refractive index difference with an optical film or an optical member, the refractive index after drying and / or curing of the pressure-sensitive adhesive composition of the present invention is controlled in the range of 1.49 to 1.60. What you can do is also important. In particular, control is possible in the range of 1.50 to 1.58.

  The pressure-sensitive adhesive composition of the present invention has optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, an ultraviolet absorption film, and a window film used for liquid crystal cell members. It can also be used for optical members in the form of so-called sheets (also referred to as films as described above).

  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.

(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 mgKOH / g, a hydroxyl value of 1.5 mgKOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 105,000.

(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 mgKOH / g, a hydroxyl value of 11.7 mgKOH / g, a glass transition temperature of −40 ° C., and a weight average molecular weight of 85,000.

(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., and the weight average molecular weight was 82,000.

(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., and a weight average molecular weight of 80,000.

  For the polyester resins (D) obtained in Synthesis Examples 1 to 5, the appearance of the solution, nonvolatile content, weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV) and hydroxyl value (OHV) are as follows. 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 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 in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by the difference in molecular size, and the weight average molecular weight (Mw) is 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 (polyester resin solution: solid content of about 50%) is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixture. . 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 (polyester resin solution: solid content of about 50%) is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixture. . 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
A benzotriazole derivative (trade name: TINUVIN 326, Nippon Ciba Geigy) is used as an organic ultraviolet blocking compound (E) with respect to 100 parts by weight of the polyester resin (D) solution (solid content: about 50%) obtained in Synthesis Example 1. 10 parts by weight and 25 parts by weight of toluene, and 2.5 parts by weight of TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) may be added as the reactive compound (F). The pressure-sensitive adhesive composition of the present invention was obtained by stirring. 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.
One side of the antireflection film was brought into contact with the formed resin layer to obtain a laminate having a configuration of release film / resin layer / antireflection film.
Next, the obtained laminate is aged for 1 week at a temperature of 23 ° C. and a relative humidity of 50% (dark reaction) to advance the crosslinking reaction of the resin layer, and the anti-reflection plate (laminate) subjected to pressure-sensitive adhesion processing Obtained.

(Examples 2 to 5)
In the same manner as in Example 1 except that the polyester resin (D) solution obtained in Synthesis Examples 2 to 5 was used in place of the polyester resin (D) solution used in Example 1, respectively. An antireflection plate (laminate) subjected to pressure bonding was obtained.

(Example 6)
Instead of the benzotriazole derivative used in Example 1, a benzophenone derivative (trade name: CHIMASSORB81, manufactured by Ciba-Geigy Corporation) was used as the organic ultraviolet blocking compound (E) in the same manner as in Example 1. Thus, an antireflection plate (laminate) subjected to pressure-sensitive adhesion processing was obtained.

(Example 7)
The pressure-sensitive adhesive was the same as in Example 6 except that the polyester resin (D) solution obtained in Synthesis Example 2 was used instead of the polyester resin (D) solution used in Example 6. A processed antireflection plate (laminate) was obtained.

(Comparative Example 1)
Implemented except that Byron RV550 (manufactured by Toyobo Co., Ltd.) having a hydroxyl group at the end of the main chain and having no hydroxyl group in the side chain was used instead of the polyester resin (D) used in Example 1. In the same manner as in Example 1, an antireflection plate (laminate) subjected to pressure-sensitive adhesion processing was obtained.

(Comparative Example 2)
Implementation was conducted except that Byron RV550 (manufactured by Toyobo Co., Ltd.) having a hydroxyl group at the terminal of the main chain and having no hydroxyl group in the side chain was used instead of the polyester resin (D) used in Example 6. In the same manner as in Example 1, an antireflection plate (laminate) subjected to pressure-sensitive adhesion processing was obtained.

  About the anti-reflective board (laminated body) which carried out the pressure-sensitive adhesion process obtained by the Example and the comparative example, the heat resistance performance, heat-and-moisture resistance performance, and the optical characteristic (haze) were evaluated with the following method. The results are shown in Table 2.

<Evaluation method for heat and moisture resistance>
The antireflection plate (laminated body) subjected to pressure-sensitive adhesion processing was cut into a size of 150 mm × 80 mm, the release film was peeled off, and each was stuck to both surfaces of a 1.1 mm thick float glass plate using a laminator. Subsequently, the glass plate to which the antireflection plate was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to adhere the antireflection plate to the glass plate. Further, the laminate of the antireflection plate and the glass plate is left to stand for 1000 hours in an environment of 120 ° C. (heat resistance), and the floating after being left for 1000 hours in an environment of 80 ° C. and 90% relative humidity. The peel (wet heat resistance) was visually observed and evaluated in three stages.
○: “No floating peeling or film whitening is observed. No problem in practical use”
Δ: “Slightly floating peeling or film whitening is observed, but there is no practical problem”
×: “Floating peeling, film whitening, and impractical use”

<< Evaluation Method of Optical Properties (Haze) >>
The resin compositions obtained in each Example and Comparative Example were applied to a release-treated polyester film and dried, and after a resin layer having a thickness of 25 μm was provided, the release-treated polyester film was further covered. . The resin layer sandwiched between the release-treated polyester films was aged at a temperature of 23 ° C. and a relative humidity of 50% for 1 week, then the release-treated polyester film was removed, the appearance of the resin layer alone was visually judged, and haze was “ NDH-300A ”(manufactured by Nippon Denshoku Industries Co., Ltd.).
○: “No problem in practical use. Haze: less than 1”
Δ: “No cloudiness or the like is observed. Haze: 1 or more and less than 3. No problem in practical use.”
X: “Slightly cloudy is recognized and there is a problem in practical use. Haze: 3 or more.”

<Method for evaluating UV shielding ability>
The antireflection plate subjected to pressure-sensitive adhesion processing obtained in each Example and Comparative Example was cut to a size of 25 mm × 150 mm, the release film was peeled off, and a laminator was used on one surface of a 1.1 mm thick float glass Then, it was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to adhere to the glass plate to obtain a laminate of the antireflection plate and the glass plate (initial stage).
This laminate was allowed to stand for 1000 hours in a 120 ° C. environment (high temperature storage).
The initial laminate was left for 1000 hours in an environment of 80 ° C. and 90% relative humidity (high temperature and high humidity).
About each laminated body, the ultraviolet shielding ability below 380 nm was evaluated in the following three steps using Ubest V-570 "(made by JASCO Corporation) on the conditions of 23 degreeC relative humidity 50%.
○: “Each laminate has an ultraviolet cut rate of 380 nm or less of 100%, and there is no problem in practical use.”
Δ: “Each laminate has a cut rate of ultraviolet rays of 380 nm or less of 95% or more and less than 100%, which is problematic in practical use.”
X: “A cut rate of ultraviolet rays of 380 nm or less of any one or more laminates is less than 95%, which is impractical.”

  The pressure-sensitive adhesive composition of the present invention cannot form an acrylic resin because it can form a polymer in which an aromatic ring or an alicyclic ring is introduced into the main chain skeleton while maintaining a cohesive force peculiar to a polyester resin. The adhesive properties can be expressed. Further, the pressure-sensitive adhesive composition of the present invention is suitable as a resin composition for optical members, as well as paints, elastic wall materials, waterproof coating materials, flooring materials, tackifiers, adhesives, and adhesives for laminated structures. Agent, sealing agent, molding material, coating agent for surface modification, binder (magnetic recording medium, ink binder, casting binder, fired brick binder, graft material, microcapsule, glass fiber sizing, etc.), urethane foam (rigid, semi-rigid) , Soft), urethane RIM, UV / EB cured resin, high solid paint, thermosetting elastomer, microcellular, textile processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, resin for artificial marble , Impact resistance agent for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.), laminated glass Use resin, reactive diluent, various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather, can also very effectively used as various resin additives and a raw material thereof or the like.

Claims (7)

A polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain, a glass transition temperature in the range of −80 to 0 ° C., an organic ultraviolet blocking compound (E), and a hydroxyl group in the resin (D) And / or a reactive compound (F) capable of reacting with a carboxyl group, and a UV-blocking pressure-sensitive adhesive composition. The organic ultraviolet blocking compound (E) is selected from benzotriazole derivatives, p-aminobenzoic acid derivatives, anthranilic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, coumaric acid derivatives, cyanoacrylate derivatives and amino acid compounds. The ultraviolet blocking pressure-sensitive adhesive composition according to claim 1, wherein at least one kind is used. 0.1 to 40.0 parts by weight of the organic ultraviolet blocking compound (E) and 0.1% by weight of the reactive compound (F) 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 ultraviolet blocking pressure-sensitive adhesive composition according to claim 1 or 2, comprising 001 to 20 parts by weight. The polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain comprises a dibasic acid component (A) having no hydroxyl group, a diol (B) having no carboxyl group, and a trivalent or higher polyvalent number. Alcohol (c1), trivalent or higher polyvalent carboxylic acid (c2), compound (c3) having two cyclic ether groups in the molecule, dioxy having two hydroxyl groups and one or more carboxyl groups in one molecule Reacting carboxylic acid (c4) with at least one side chain functional group-introducing component (C) selected from the group consisting of carboxylic acid (c4) and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule The ultraviolet ray blocking pressure-sensitive adhesive composition according to claim 1, wherein the composition is a polyester resin (D1). 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 ( The polyester resin (D2) having a ring-opening portion of the cyclic ester compound (G) formed by ring-opening addition as a side chain and having a hydroxyl group at the terminal of the ring-opening portion. 3. UV-blocking pressure-sensitive adhesive composition according to 3. 6. The ultraviolet blocker according to claim 1, wherein the reactive compound (F) has two or more functional groups capable of reacting with side chain functional groups in the polyester resin (D) in one molecule. Pressure-sensitive adhesive composition. An ultraviolet blocking pressure-sensitive adhesive sheet, wherein an ultraviolet blocking pressure-sensitive adhesive layer formed from the ultraviolet blocking pressure-sensitive adhesive composition according to claim 1 is laminated on at least one surface of a plastic film.