JP2009001694A - Polyester for pressure-sensitive adhesive and pressure-sensitive adhesive composition containing the same - Google Patents

Abstract

The present invention provides a pressure-sensitive adhesive composition that can be suitably used for a pressure-sensitive adhesive composition capable of forming an adhesive layer excellent in tackiness, adhesion to a substrate, heat resistance, heat and humidity resistance, and optical properties. It aims at providing polyester for pressure type adhesives, and also aims at providing the laminated body which consists of a pressure sensitive adhesive composition containing this polyester for pressure sensitive adhesives, and an optical member.
A polyvalent carboxylic acid component (A) containing an aromatic dicarboxylic acid (a1), a polyol component (B) containing a diol (b1) having a hydrocarbon group in the side chain, and a polyvalent amine component (C ) And pressure sensitive adhesive polyester.
[Selection figure] None

Description

  The present invention relates to a polyester that can be used in a pressure-sensitive adhesive composition excellent in adhesiveness, heat resistance, moist heat resistance and transparency with various adherends, and more particularly suitable for laminating optical members. The present invention also relates to a pressure-sensitive adhesive composition containing the polyester and a laminate using the same.

  Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL display, light emitting diode display, etc. It has come to be used as a display device in various fields. For example, these FPDs are not only used indoors, including personal computer displays and liquid crystal televisions, but are also used in vehicles such as car navigation displays.

  A polarizing film and a retardation film are laminated on the liquid crystal cell member constituting the LCD. Also, these display devices use an antireflection film for preventing reflection from an external light source, a protective film (protection film) for preventing scratches on the surface of the display device, and the like. In addition to using the FPD as a display device, a touch panel function may be provided on the surface of the FPD to be used as an input device. A protective film, an antireflection film, an ITO vapor deposition resin film, and the like are also used for this touch panel.

  Various films used in the display device are used by being attached to an adherend with a pressure-sensitive adhesive. Since it is used for a display device, the pressure-sensitive adhesive is first required to be excellent in transparency. Therefore, a pressure-sensitive adhesive mainly composed of an acrylic resin is generally used.

  In recent years, from the viewpoint of effective use of light in the bonding process of an optical member, suppression of interface reflection based on a difference in refractive index between the optical member and the adherend is required, and the refractive index of the optical member. It is known to be advantageous to use a pressure sensitive adhesive layer having a refractive index intermediate between the refractive index of the substrate and the adherend. Incidentally, if the refractive index difference at the interface is large, the incident angle causing total reflection becomes small, and the effective utilization of light is lowered.

  However, the refractive index of the adhesive layer using the conventional acrylic resin is around 1.46, whereas the refractive index of the material forming the optical member is, for example, around 1.52 for glass, methacrylic resin 1.51 for polycarbonate resin, 1.54 for polyethylene terephthalate (PET) resin, and there is a large difference in refractive index between them. When an optical member made of a resin, a polycarbonate resin, or a PET resin is bonded, the above intermediate refractive index cannot be obtained.

  By the way, among the various films described above, the polarizing film has a three-layer structure in which both surfaces of a polyvinyl alcohol polarizer are sandwiched between triacetyl cellulose-based and cycloolefin-based protective films. Because of the characteristics of the materials that make up each layer, the polarizing film undergoes significant dimensional changes due to expansion and contraction due to heat and humidity.

  Therefore, the acrylic pressure-sensitive adhesive for sticking the polarizing film to the glass member for a liquid crystal cell is required to suppress the dimensional change of the polarizing film itself and to further increase the refractive index of the adhesive layer. For this reason, by making the adhesive layer itself hard or increasing the adhesive strength, it is possible to suppress a relatively small dimensional change or a relatively short-term dimensional change. Further, the refractive index can be improved to some extent by using an aromatic ring-containing monomer, an aromatic compound, a compound containing a sulfur atom, or an inorganic compound.

  However, with the recent increase in screen size of liquid crystal panels, the size of the polarizing film has also increased, and the amount of thermal deformation of the polarizing film has increased. When using a conventional pressure-sensitive adhesive, the stress at the time of sticking remaining in the adhesive layer is not sufficiently relaxed, so the adhesive layer cannot sufficiently follow the distortion of the polarizing film, resulting in a large liquid crystal Exposing the panel to high temperatures or high humidity causes discoloration of the polarizing film and a decrease in transparency, or the polarizing film peels off the glass substrate of the large liquid crystal cell, causing stress concentration on the polarizing film, resulting in large liquid crystals. There is also a problem that light leakage occurs in the panel or volatile gas is generated.

  Also, the polarizing film changes in dimensions while the liquid crystal panel is used over a long period of time, and the stress is accumulated in the adhesive layer. If the stress continues to accumulate in the adhesive layer, the distribution of the adhesive force between the polarizing film and the liquid crystal cell glass member becomes non-uniform. During long-term use, stress concentrates on the peripheral edge of the polarizing film, and as a result, the peripheral edge of the liquid crystal element becomes brighter or darker than the center. White spotting) occurs.

  As described above, the pressure-sensitive adhesive used for laminating a polarizing film on a glass member for a liquid crystal cell has good optical properties (transparency), heat resistance and moist heat resistance, and good stress relaxation properties. Desired. And the same performance is calculated | required also for the pressure sensitive adhesive for laminating | stacking the retardation film and the cover film of various displays.

  Conventionally, various pressure-sensitive adhesives have been proposed for these various requirements. For example, various pressure-sensitive adhesives based on acrylic resins are known (see Patent Documents 1 to 5).

However, by using an acrylic resin as a pressure-sensitive adhesive, foaming of the adhesive layer and lifting off of the polarizing plate from the liquid crystal cell can be suppressed, but stress due to dimensional change of the polarizing plate can be absorbed and relaxed. Since the stress concentrates on the peripheral edge of the polarizing plate, the brightness of the peripheral edge and the central area of the liquid crystal display device are different, and there is a problem that uneven color and light leakage occur on the surface of the liquid crystal display device. As described above, the pressure-sensitive adhesive sheet is used in various fields, the required level is increased, new requirements are added, and the conventional acrylic pressure-sensitive adhesives cannot sufficiently meet various requirements.
Japanese Patent Laid-Open No. 01-066283 JP-A-10-279907 JP 2002-121521 A JP 2003-013029 A JP 2002-014225 A

  INDUSTRIAL APPLICABILITY The present invention is for a pressure-sensitive adhesive that can be suitably used for a pressure-sensitive adhesive composition that can form an adhesive layer excellent in tack, adhesion to a substrate, heat resistance, heat and humidity resistance, and transparency. An object of the present invention is to provide a polyester, and further to provide a laminate comprising a pressure-sensitive adhesive composition containing the pressure-sensitive adhesive polyester and an optical member.

  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 present invention relates to a polyvalent carboxylic acid component (A) containing an aromatic dicarboxylic acid (a1), a polyol component (B) containing a diol (b1) having a hydrocarbon group in the side chain, and a polyvalent amine component. The present invention relates to a pressure-sensitive adhesive polyester obtained by reacting (C).

  Furthermore, this invention relates to the said polyester for pressure sensitive adhesives whose polyvalent amine component (C) is 0.1-40 mol% with respect to a polyol component (B).

  Furthermore, this invention relates to the said polyester for pressure sensitive adhesives characterized by the polyvalent carboxylic acid component (A) containing 10-80 mol% of aromatic dicarboxylic acids (a1).

  Furthermore, the present invention relates to the above polyester for pressure-sensitive adhesive, wherein the polyol component (B) contains 10 to 80 mol% of the diol (b1) having a hydrocarbon group in the side chain.

  Furthermore, the present invention provides at least one trivalent or higher functional group selected from a trivalent or higher polyvalent carboxylic acid (a2), a trivalent or higher polyol (b2), and a trivalent or higher polyvalent amine (c2). It is related with the said polyester for pressure sensitive adhesives which makes the compound which has this react.

  Furthermore, this invention relates to the said polyester for pressure sensitive adhesives whose ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is 2.0-6.0.

  Furthermore, this invention relates to the said polyester for pressure sensitive adhesives whose weight average molecular weights (Mw) are 30000-300000.

  Furthermore, this invention relates to the pressure sensitive adhesive composition containing the said polyester for pressure sensitive adhesives, and the compound (D) which has a functional group which can react with the reactive functional group in polyester.

  Furthermore, this invention relates to the said pressure sensitive adhesive composition whose compound (D) is a polyisocyanate compound.

  Furthermore, this invention relates to the said pressure sensitive adhesive composition characterized by including a silane coupling agent.

  Furthermore, this invention relates to the laminated body by which an optical member is laminated | stacked on the pressure sensitive adhesive layer formed from the said pressure sensitive adhesive composition.

  The present invention further relates to a liquid crystal cell member in which a glass member for a liquid crystal cell, a pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition, and an optical member are sequentially laminated.

  The polyester for pressure-sensitive adhesive of the present invention is a pressure-sensitive adhesive composition that can form an adhesive layer excellent in tack, adhesion to a substrate, heat resistance, heat and humidity resistance, refractive index controllability and transparency. It can be preferably used. In addition, by using the pressure-sensitive adhesive composition of the present invention, foaming or peeling occurs even under severer heat or wet heat conditions than before, particularly in optical member applications that require heat resistance and moist heat resistance. In addition to relaxing the stress concentration caused by expansion and contraction of the polarizing plate to prevent uneven color and white spots in the liquid crystal element, it is possible to provide an optical member whose refractive index can be adjusted as necessary. became.

  First, the pressure-sensitive adhesive polyester of the present invention will be described. The polyester for pressure-sensitive adhesives of the present invention comprises a polyvalent carboxylic acid component (A) containing an aromatic dicarboxylic acid (a1), a polyol component (B) containing a diol (b1) having a hydrocarbon group in the side chain, , A polyester obtained by reacting a polyvalent amine component (C).

  The present invention is characterized in that a polyester for pressure-sensitive adhesive is synthesized using a polyvalent amine component (C). By using the polyvalent amine component (C), it is possible to introduce an amide bond in addition to an ester bond into the resin main skeleton, improving mechanical properties as a resin, heat resistance and moist heat resistance, Generation of uneven color and white spots when used in a liquid crystal element can be suppressed.

The polyvalent amine component (C) of the present invention is a compound having at least two primary or secondary amino groups. As the polyvalent amine component (C) of the present invention, known compounds can be used, and examples of the compound having two primary and / or secondary amino groups in the molecule include ethylenediamine and propylenediamine. , Aliphatic polyamines such as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine;
Cycloaliphatic polyamines such as isophoronediamine and dicyclohexylmethane-4,4′-diamine;
Aromatic polyamines such as phenylenediamine and xylylenediamine are listed.

Furthermore, 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, Diamines having a hydroxyl group in the molecule such as (2-hydroxypropylethylene) diamine and (di-2-hydroxypropylethylene) diamine, MXD-PO1 (manufactured by Mitsubishi Gas Chemical Company), MXD-PO2 ( Mitsubishi Gas Chemical Co., Ltd.), MXD-EO1 (Mitsubishi Gas Chemical Co., Ltd.), MXD-EO2 (Mitsubishi Gas Chemical Co., Ltd.), 2-hydroxyethylaminopropylamine (Guangei Chemical Industry Co., Ltd.), aminoethylethanolamine, N- (2-hydroxyethyl) xylylenediamine (light Diamine having a hydroxyl group in the molecule of Chemical Industry Co., Ltd.) and the like;
Polyoxyalkylene glycol diamine having propoxyamine at both ends and represented by the following general formula (1) can be used.

General formula (1)
_{H 2 N-CH 2 -CH 2} -CH 2 -O- (C m H 2m -O) n -CH 2 -CH 2 -CH 2 -NH 2
(In the formula, m represents an arbitrary integer of 2 to 4, and n represents an arbitrary integer of 2 to 50.)

  Further, as the polyvalent amine component (C), the compound having a primary amino group in the polyvalent amine component (C) exemplified above and the compound (E) having an ethylenically unsaturated group are subjected to a Michael addition reaction. A compound having two or more secondary amino groups, which can be obtained by the above method, can also be used.

  Examples of the compound (E) having an ethylenically unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) Acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meta Acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkyl (meth) acrylates having 1 to 22 carbon atoms such as docosyl (meth) acrylate. An alkyl group-containing acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, or a corresponding methacrylate is preferable. When aiming at adjustment of leveling property, etc., it is preferable to have 6 or more carbon atoms. When the number of carbon atoms is 23 or more, depending on the purpose, the Michael addition reaction may be difficult to proceed.

Furthermore, dialkylamino group-containing unsaturated compounds such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene;
(Meth) acrylic acid dimethylaminoethyl methyl chloride salt, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride and It is obtained by quaternizing ammonium with the dialkylamino group-containing unsaturated compound such as trimethyl-3- [1- (meth) acrylamide-1,1-dimethylethyl] ammonium chloride, and Cl ⁻ , Br ⁻ as counter ions. , I ^- a halogen ion or RSO ₃ of ^-: quaternary ammonium salt group-containing unsaturated compound having a (R 1 -C 12 alkyl group carbon atoms);
Perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate , 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meta ) Perfluoroalkyl having a C 1-20 perfluoroalkyl group such as acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. (Meth) acrylates;
Perfluoroalkyl group-containing unsaturated compounds such as perfluoroalkyl, alkylenes such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene;
Unsaturated compounds having an alkoxysilyl group such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, and derivatives thereof;
Methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) Acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, Methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropyleneglycol (Meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetra A polyalkylene glycol group-containing unsaturated compound such as methylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate and the like, and an unsaturated compound having an alkoxy group at the terminal;
Phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, A polyalkylene glycol group-containing unsaturated compound such as phenoxytetrapropylene glycol (meth) acrylate, which has a phenoxy group at the terminal;
(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meta ) Acrylamide, monoalkylol (meth) acrylamide such as N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N- Di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) A) Rilamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide, N, N-di (pentoxymethyl) ) Amide-type unsaturated compounds such as dialalkylol (meth) acrylamides such as acrylamide and N-methoxymethyl-N- (pentoxymethyl) methacrylamide;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, allyl Alcohol, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meta ) Acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethyleneglycol Unsaturated compounds having a hydroxyl group, such as allyl mono (meth) acrylate;
Fatty acid vinyl alkyl group-containing unsaturated compounds such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate;
Vinyl ether-based unsaturated compounds such as butyl vinyl ether and ethyl vinyl ether, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, etc. Saturated compounds;
Allyl compounds such as allyl acetate, allylbenzene and allyl cyanide, vinyl compounds such as vinyl cyanide, vinylcyclohexane, vinylmethylketone, styrene, α-methylstyrene, 2-methylstyrene and chlorostyrene;
And ethynyl compounds such as acetylene, ethynylbenzene, and ethynyltoluene;
Is mentioned.

  Among the polyvalent amine compounds (C), the Michael addition reaction between the compound having a primary amino group and the compound (E) having an ethylenically unsaturated group is the primary in the compound having the primary amino group. 1 molar equivalent of an amino group reacts with 1 molar equivalent of an unsaturated group in the compound (E). The primary amino group is easily Michael-added to an unsaturated group having an electron-withdrawing group, but the compound (E) is preferably a (meth) acrylic compound, particularly an acrylate compound. Further, when comparing the acrylate compound and the corresponding methacrylate compound, the acrylate compound is more preferable because of the efficiency of the Michael addition reaction.

  Moreover, a well-known method can be utilized as a synthesis | combining method of the polyvalent amine component (C) obtained by the said Michael addition reaction. When the compound (E) is a (meth) acrylic compound, particularly an acrylate compound, the reaction proceeds at 10 to 100 ° C. under a catalyst as necessary. Although depending on the type of the compound (E) used, a reaction temperature of 40 to 80 ° C. is preferable. When the compound (E) does not have an electron-withdrawing group, the reaction is possible in the presence of a metal catalyst. In this case, when the reaction is carried out at 60 to 100 ° C. while heating in the presence of the catalyst, an appropriate reaction rate is obtained. This is preferable.

  Among the above polyvalent amine components (C), isophorone diamine, 2,2,4-trimethylhexamethylene diamine, and hexamethylene diamine are preferable because of easy control of the reaction and excellent hygiene.

  Further, as the polyvalent amine component (C) of the present invention, the above-described trivalent or higher polyvalent amine (c2) is preferably used. By using a trivalent or higher polyvalent amine (c2), the polyester can be branched, whereby the cohesive strength of the pressure-sensitive adhesive composition can be improved. When using a trivalent or higher polyvalent amine (c2), it is preferably used in an amount of 0.1 to 5 mol% in the polyvalent amine component (C). Mole% is more preferable. If it is less than 0.1 mol%, the cohesive force may be reduced, and the heat resistance and moist heat resistance are inferior. When used for laminating optical members, problems such as film peeling and white spots may occur. On the other hand, if it exceeds 5 mol%, the viscosity becomes high during synthesis, which may cause a problem in productivity.

  Examples of the trivalent or higher polyvalent amine (c2) having three or more primary amino groups and / or secondary amino groups in the molecule include triethylenetetramine, polyoxyethylenetriamine, diethylenetriamine, and triethylenetetramine. , Tetraethylenepentamine, pentaethylenehexamine, triaminopropane and the like.

  In the pressure-sensitive adhesive polyester of the present invention, the polyvalent amine component (C) is preferably 0.1 to 40 mol%, and 0.2 to 20 mol%, based on the polyol component (B). More preferred is 0.5 to 10 mol%. When the ratio of the polyvalent amine component (C) is less than 0.1 mol%, the ratio of amide bonds that can be introduced into the resin decreases, and heat resistance and the like may be reduced. Tack may fall that it is 40 mol% or more.

  The pressure-sensitive adhesive polyester of the present invention can use a known compound as the polyvalent carboxylic acid component (A), but is characterized by using an aromatic dicarboxylic acid (a1). By using the aromatic dicarboxylic acid (a1), the heat resistance and heat-and-moisture resistance are further improved. When used for laminating optical members, problems such as film peeling and white spots are less likely to occur. In this invention, it is preferable to use 10-80 mol% of aromatic dicarboxylic acid (a1) in a polyvalent carboxylic acid component (A) as a polyvalent carboxylic acid component (A), and 20-70 mol% is used. Is more preferable. When the amount of the aromatic dicarboxylic acid (a1) used is less than 10 mol%, the heat resistance and heat-and-moisture resistance are inferior, and when used for laminating optical members, problems such as film peeling and white spots may occur. Moreover, when it exceeds 80 mol%, adhesiveness falls and sufficient adhesive force may not be acquired.

Examples of the aromatic dicarboxylic acid (a1) in the polyvalent carboxylic acid component (A) of the present invention include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, and p-carboxyphenylacetic acid. P-phenylene diacetic acid, m-phenylene diglycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl-p, p′-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, Aromatic dicarboxylic acids such as naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid;
Aromatic dicarboxylic anhydrides such as phthalic anhydride, 1,8-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic anhydride and the like can be mentioned.

  In addition, the above aromatic dicarboxylic acid components and aromatic dicarboxylic acid anhydrides can be used as lower alcohols, for example, esterified products of alkyl alcohols having 1 to 4 carbon atoms. In the case of using an ester of an aromatic dicarboxylic acid component or a lower alcohol of an aromatic dicarboxylic anhydride, an ester bond is generated not by dehydration condensation with the polyol component (B) but by an ester exchange reaction by dealcoholization. .

  Furthermore, a compound obtained by half-esterifying an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid anhydride with a monoalcohol can be used as the aromatic dicarboxylic acid.

  Examples of the aromatic tricarboxylic acid anhydride include 1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride, 1,2,4-naphthalene tricarboxylic acid anhydride, and 1,4,5-naphthalene tricarboxylic acid. Anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8-naphthalene tricarboxylic acid anhydride, 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid Acid anhydride, 3,4,4′-biphenyltricarboxylic acid anhydride, 2,3,2′-biphenyltricarboxylic acid anhydride, 3,4,4′-biphenylmethanetricarboxylic acid anhydride, 3,4,4 ′ -Biphenyl sulfone tricarboxylic acid anhydride etc. are mentioned.

  Examples of the aromatic tetracarboxylic anhydride include pyromellitic anhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetracarboxylic acid anhydride, 2,3,6 , 7-Naphthalenetetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid anhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic acid anhydride, 3,3 ', 4,4'-Tetraphenylsilanetetracarboxylic anhydride, 1,2,3,4-furantetracarboxylic acid Water, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone anhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenylpropane anhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, Bis (phthalic acid) phenylphosphine oxide anhydride, p-phenylene-bis (triphenylphthalic acid) anhydride, m-phenylene-bis (triphenylphthalic acid) anhydride, bis (triphenylphthalic acid) -4,4 '-Diphenyl ether anhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane anhydride, 9,9-bis (3,4-dicar Xylphenyl) fluorenic anhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1- Examples include naphthalene succinic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic anhydride.

Examples of the monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, n-amyl alcohol, hexanol, heptanol, n-octanol, 2-ethylhexanol, isooctanol, nonanol, decanol, isoundecanol, lauryl alcohol, Linear or branched aliphatic alcohols such as cetyl alcohol and stearyl alcohol;
Araliphatic monoalcohols such as benzyl alcohol, α-methylbenzyl alcohol, phenethyl alcohol;
Examples include alicyclic monoalcohols such as cyclopentanol, cyclohexanol, cyclohexanemethanol, cycloheptanol, cyclooctanol, and tricyclodecane methanol.

  These aromatic dicarboxylic acids (a1) can be used alone or in combination of two or more. Among these, terephthalic acid and isophthalic acid are preferable from the viewpoint of heat resistance and wet heat resistance.

Examples of the polyvalent carboxylic acid component (A) other than the aromatic dicarboxylic acid (a1) in the polyvalent carboxylic acid component (A) of the present invention include citraconic acid, malic acid, citric acid, oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, fumaric acid, itaconic acid, maleic acid diglycolic acid, cyclohexane-3,5 -Aliphatic and alicyclic dicarboxylic acids such as diene-1,2-carboxylic acid and hexahydroterephthalic acid;
Succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic acid Anhydride, octylmaleic acid anhydride, decylmaleic acid anhydride, dodecylmaleic acid anhydride, butylglutamic acid anhydride, hexylglutamic acid anhydride, heptylglutamic acid anhydride, octylglutamic acid anhydride, decylglutamic acid anhydride, dodecylglutamic acid anhydride , Methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methyl hymic anhydride, etc. Aliphatic, alicyclic dicarboxylic acid anhydride.

  In the present invention, it is preferable to use a trivalent or higher polyvalent carboxylic acid (a2) such as trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid or anhydride thereof described above in combination. By using a trivalent or higher polyvalent carboxylic acid (a2), the polyester can be branched, and thereby the cohesive force of the pressure-sensitive adhesive composition can be improved. When using a trivalent or higher polyvalent carboxylic acid (a2), it is preferable to use 0.1 to 5 mol% in the polyvalent carboxylic acid component (A). -3 mol% is more preferable. If it is less than 0.1 mol%, the cohesive force may be reduced, and the heat resistance and moist heat resistance are inferior. When used for laminating optical members, problems such as film peeling and white spots may occur. On the other hand, if it exceeds 5 mol%, the viscosity becomes high during synthesis, which may cause a problem in productivity.

  The polyester for pressure-sensitive adhesives of the present invention can use a known polyol as the polyol component (B), but is characterized by using a diol (b1) having a hydrocarbon group in the side chain. By using the diol (b1) having a hydrocarbon group in the side chain, the wettability to the base material is improved, the heat resistance and the heat and humidity resistance are improved, and when used for laminating optical members, film peeling or whitening There is a tendency that such problems do not occur more. In this invention, it is preferable to use 10-80 mol% of diol (b1) which has a hydrocarbon group in a side chain as a polyol component (B), It is still more preferable to use 15-60 mol%. It is particularly preferable to use mol%. When the amount of the diol (b1) having a hydrocarbon group in the side chain is less than 10 mol%, the heat resistance and heat-and-moisture resistance are inferior, and problems such as film peeling and white spots occur when used for laminating optical members. There is a case. Moreover, when it exceeds 80 mol%, there exists a tendency for a tack to fall, superposition | polymerization time becomes long, and a problem may be produced in productivity.

  The hydrocarbon group in the diol (b1) having a hydrocarbon group in the side chain is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 3 to 9 carbon atoms. preferable. Examples of the diol (b1) having a hydrocarbon group in the side chain include neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2,2 -Diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4 -Diethyl-1,5-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,6-hexanediol, 2-butyl-2-methyl-1,3-propanediol 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-propyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol 2-pentyl-2-methyl-1,3-propanediol, 2-hexyl-2-methyl-1,3-propanediol, 2-hexyl-2-ethyl-1,3-propanediol, 2-butyl 2-ethyl-1,4-butanediol, 2-butyl-2-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,6-hexanediol, 2-hexyl-3-methyl- 1,4-butanediol, 2-butyl-2-ethyl-1,4-butanediol, 2-butyl-4-methyl-1,5-pentanediol, 2-propyl-4-ethyl-1,6-hexane Diol, 2-butyl-5-methyl-1,6-hexanediol, 2-hexyl-5-ethyl-1,6-hexanediol, 2,5-dibutyl-1,6-hexanediol, etc. .

  Examples of the polyol component (B) other than the diol (b1) having a hydrocarbon group in the side chain include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 1,7-heptanediol 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-bis (hydroxymethyl) cyclohesane, bisphenol A, water Bisphenol A, polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol Thiodiglycol, 1,2-bis (2-hydroxyethyl) ethane, 1,4-bis (2-hydroxyethyl thio) butane and the like.

  It is preferable to use a trivalent or higher polyol (b2) as the polyol component (B) of the present invention. By using the polyhydric polyol (b2) having three or more valences, the polyester can be branched, and thereby the cohesive force of the pressure-sensitive adhesive composition can be improved. When using a trivalent or higher valent polyol (b2), it is preferable to use 0.1 to 5 mol% in the polyol component (B), and 0.5 to 3 mol% is more preferable in consideration of use in an optical member. preferable. If it is less than 0.1 mol%, the cohesive force may be reduced, and the heat resistance and moist heat resistance are inferior. When used for laminating optical members, problems such as film peeling and white spots may occur. On the other hand, if it exceeds 5 mol%, the viscosity becomes high during synthesis, which may cause a problem in productivity.

  Examples of the trivalent or higher polyol (b2) include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6- Examples include hexanetriol.

  The polyester for pressure-sensitive adhesives of the present invention is obtained by polycondensation reaction of the above polycarboxylic acid component (A), polyol component (B) and polyvalent amine component (C) in the presence of a catalyst by a known method. It is done. The total reaction ratio of the polyol component (B) and the polyvalent amine component (C) with respect to the polyvalent carboxylic acid component (A) is 1 mol of carboxyl group (acid anhydride group) in the polyvalent carboxylic acid component (A). 1 carboxyl group is 2 mol), and the total of hydroxyl groups and amino groups in the polyol component (B) and the polyvalent amine component (C) is 1 to 2 mol, preferably 1.1 to 1 0.8 mol, more preferably 1.2 to 1.6 mol.

  The polycondensation reaction can be performed according to known conditions, and a catalyst is preferably used for the reaction. For example, titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate, antimony-based compounds such as antimony trioxide, germanium-based catalysts such as germanium oxide, zinc acetate, manganese acetate, dibutyltin oxide, perfluoroalkanesulfonic acid or its metal Examples of the catalyst include salts, halloinium salts, potassium potassium oxalate, and tin oxalate, and one or more of these are used.

  The reaction between the acid anhydride group and the hydroxyl group or amino group can be performed according to known conditions, and a catalyst is preferably used for the reaction. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene and the like.

  The polyester for pressure-sensitive adhesives of the present invention preferably has a glass transition temperature of −80 to 0 ° C. When the glass transition temperature is less than −80 ° C., the cohesive force of the pressure-sensitive adhesive layer obtained by using the polyester may be reduced, and floating may occur. On the other hand, when the glass transition temperature exceeds 0 ° C., the pressure-sensitive adhesive layer may not exhibit sufficient tack. The glass transition temperature can be measured using DSC (differential thermogravimetric measuring device).

  The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyester for pressure-sensitive adhesives of the present invention is preferably 2.0 to 6.0, and preferably 3.0 to 5.0. Is more preferable. When Mw / Mn is less than 2.0, the heat resistance and heat-and-moisture resistance are inferior, and when used for laminating optical members, problems such as film peeling and white spots may occur. On the other hand, if it exceeds 6.0, the viscosity may increase and handling may be problematic.

  The weight average molecular weight (Mw) of the polyester for pressure-sensitive adhesives of the present invention is preferably in the range of 30000-300000, more preferably in the range of 50000-200000. When Mw is less than 30000, cohesive force cannot be expressed, and heat resistance and moist heat resistance may decrease. On the other hand, if Mw exceeds 300,000, the fluidity of the resin becomes poor and it may be difficult to produce a resin laminate.

  The pressure-sensitive adhesive composition of the present invention contains the polyester for pressure-sensitive adhesive and a compound (D) having a functional group capable of reacting with a reactive functional group in the polyester as a crosslinking agent. And Examples of the reactive functional group in the polyester include a hydroxyl group and a carboxyl group. Therefore, as a functional group which the compound (D) used for this invention has, an isocyanate group, an epoxy group, an alkoxysilyl group, a methylol group, an aziridine group etc. are mentioned. Examples of the compound (D) include polyisocyanate compounds, polyfunctional silane compounds, N-methylol group-containing compounds, polyfunctional aziridine compounds, etc. Among these, in order to act as a crosslinking agent, A compound having two or more functional groups capable of reacting with a hydroxyl group in the molecule is preferably used. In particular, polyisocyanate compounds and polyfunctional silane compounds 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.

  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 of isocyanurate groups, or a modified product having two or more of these groups is used. it can. 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 moist heat resistance.

  When a polyisocyanate compound is used as the compound (D), 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 polyfunctional silane compound include a silane coupling agent. Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltributoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyl. A silane compound having two methacryloxy groups such as methyldiethoxysilane, an alkyl group and an alkoxy group;
a silane compound having two acryloxy groups, an alkyl group and an alkoxy group, such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-acryloxypropylmethyldimethoxysilane;
Silane compounds having three (meth) acryloxyalkyl groups and three alkoxy groups such as γ-methacryloxymethyltrimethoxysilane and γ-acryloxymethyltrimethoxysilane;
Alkoxysilanes having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane;
Alkoxysilanes having an alkyl group such as 5-hexenyltrimethoxysilane, 9-decenyltrimethoxysilane, styryltrimethoxysilane;
Silanes having aminoalkyl groups and alkoxy groups such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane;
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane;
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane , Phenyltrimethoxysilane, hexamethylsilazane, diphenyldimethoxysilane, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl)- Examples include 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

  The pressure-sensitive adhesive composition of the present invention preferably contains 0.001 to 20 parts by weight, preferably 0.01 to 20 parts by weight of the compound (D) with respect to 100 parts by weight of the polyester for pressure-sensitive adhesives. More preferably. When the amount of the compound (D) used exceeds 20 parts by weight, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition has a dense cross-linked structure, and the pressure-sensitive adhesive layer tends to have a reduced tack. The adhesiveness to the adherend is lowered and the flexibility is lowered, so that the stability and durability during repeated use are inferior, which is not preferable. On the other hand, when the amount is less than 0.001 part by weight, a sufficient cross-linked structure cannot be obtained. The reaction between the reactive functional group in the polyester and the functional group in the compound (D) causes the resin composition to be three-dimensionally cross-linked, not only ensuring adhesion to various substrates and adherends, but also from the past. However, since the heat resistance and heat-and-moisture resistance under severe conditions can also be improved, it can be preferably used for an optical member.

  In the pressure-sensitive adhesive composition of the present invention, various resins, coupling agents, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weathering stabilizers, as long as the effects of the present invention are not impaired. , Tackifier, plasticizer, filler, anti-aging agent and the like may be blended.

  Using the pressure-sensitive adhesive composition of the present invention, a laminated product (hereinafter referred to as “adhesive sheet”) composed of a pressure-sensitive adhesive layer and a sheet-like substrate can be obtained. For example, a pressure-sensitive adhesive sheet can be obtained by coating, drying and curing the pressure-sensitive adhesive composition of the present invention on various sheet-like substrates. Since the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet is “pressure-sensitive”, it has tack at about room temperature. When applying the pressure-sensitive adhesive composition, an appropriate liquid medium, for example, an organic solvent such as ethyl acetate, toluene, methyl ethyl ketone, isopropyl alcohol, other hydrocarbon solvents, or water is further added to increase the viscosity. It can also be adjusted, and the pressure-sensitive adhesive composition can be heated to lower the viscosity. However, care should be taken because adding water or alcohol in a large amount may cause reaction inhibition between the polyester and the compound (D).

  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. Various base materials can be used alone or in a multi-layered state in which a plurality of base materials are laminated. 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. It is below.

  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 to be volatilized, the adhesive layer in the molten state is cooled and solidified, and the adhesive layer is formed on the sheet-like substrate. 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 it 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 particular limitation on the drying method, and examples include those using hot air drying, infrared rays or a reduced pressure method. 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 has various optical properties such as a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film, so-called sheet (also referred to as a film as described above) in an optical member, The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention is laminated. 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.

  By peeling off the release-treated sheet-like substrate covering the surface of the pressure-sensitive adhesive layer from the laminate thus obtained, for example, by sticking the pressure-sensitive adhesive layer to the glass member for liquid crystal cells A liquid crystal cell member having a configuration of “sheet-like optical member / pressure-sensitive adhesive layer / glass member for liquid crystal cell” can be obtained.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.

  In addition, the weight average molecular weight (Mw) and dispersity (Mw / Mn) of each resin obtained in Examples 1-4 and Comparative Examples 1-3 were calculated | required according to the following method.

<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.

<Dispersity (Mw / Mn)>
It calculated | required by the weight average molecular weight (Mw) / number average molecular weight (Mn) from the measurement result of the said molecular weight.

[Synthesis of polyester]
(Example 1)
In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 77.1 g (0.856 mol) of 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1 , 3-propanediol 95.5 g (0.597 mol), 1,6-hexanediol 70.1 g (0.59 mol), trimethylolpropane 3.62 g (0.027 mol), hexamethylenediamine 68.6 g (0.59 mol), 214.0 g (1.29 mol) of isophthalic acid, 230.9 g (1.14 mol) of sebacic acid, 0.10 g of tetra-n-butyl titanate, and 3.75 g of tin oxalate The mixture is heated at 150 to 225 ° C. for 180 minutes for esterification and amidation reaction, and then 5 drops of phosphoric acid is added to gradually reduce the pressure of the reaction system, and after 30 minutes, the pressure is reduced to 5 mmHg or less. Further subjected to 90 minutes of reaction under continuous vacuum, to obtain a polyester. The obtained polyester (A-1) had a weight average molecular weight of 51,000 and a dispersity of 3.7, and was not crystallized.

(Example 2)
In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 70.9 g (0.788 mol) of 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1 , 3-propanediol 87.9 g (0.549 mol), 1,6-hexanediol 64.5 g (0.547 mol), trimethylolpropane 3.30 g (0.025 mol), isophoronediamine 92.3 g ( 0.542 mol), 197.0 g (1.19 mol) of isophthalic acid, 211.53 g (1.052 mol) of sebacic acid, 0.10 g of tetra-n-butyl titanate, and 3.75 g of tin oxalate, Perform esterification and amidation reaction by heating at 150 to 225 ° C. for 180 minutes, then add 5 drops of phosphoric acid and gradually reduce the pressure of the reaction system, and after 30 minutes, 5 mmHg or less Then, the reaction was continued for 90 minutes while continuing to reduce the pressure to obtain a polyester. The obtained polyester (A-2) had a weight average molecular weight of 81,000 and a dispersity of 5.5, which did not crystallize.

Example 3
In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 127.16 g (1.413 mol) of 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1 , 3-propanediol 96.95 g (0.606 mol), 1,6-hexanediol 71.18 g (0.603 mol), diethylenetriamine 9.80 g (0.095 mol), isophthalic acid 307.53 g (1. 853 mol), 124.09 g (0.614 mol) of sebacic acid, 0.41 g (0.13 mol) of trimellitic anhydride, 0.10 g of tetra-n-butyl titanate, and 3.75 g of tin oxalate, Heat at ~ 260 ° C for 150 minutes to conduct esterification and amidation, then add 5 drops of phosphoric acid and gradually reduce the pressure in the reaction system. And then, further subjected to 90 minutes of reaction under continuous vacuum, to obtain a polyester. The obtained polyester (A-3) had a weight average molecular weight of 59000 and a dispersity of 2.8, which did not crystallize.

(Example 4)
In a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 24.61 g (0.273 mol) of 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1 , 3-propanediol 39.38 g (0.246 mol), pentamethylenediamine 78.24 g (0.766 mol), 1,4-butanediol 130.44 g (1.449 mol), isophthalic acid 82.53 g ( 0.497 mol), 386.67 g (1.914 mol) of sebacic acid, 8.13 g (0.04 mol) of pyromellitic anhydride, 0.10 g of tetra-n-butyl titanate, and 3.75 g of tin oxalate are charged. The mixture is heated at 150 to 260 ° C. for 150 minutes to carry out esterification and amidation reactions, and then 5 drops of phosphoric acid is added to gradually reduce the pressure of the reaction system. The reaction was continued for 90 minutes while continuing to reduce the pressure to obtain a polyester. The obtained polyester (A-4) had a weight average molecular weight of 64,000 and a dispersity of 5.1, which did not crystallize.

  Table 1 shows the amount of each raw material charged in Examples 1 to 4 converted to mol% with respect to each component.

[Synthesis of acrylic resin]
(Comparative Example 1)
In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, condenser, and dropping funnel, 49 g of 2-ethylhexyl acrylate, 50 g of phenoxyethyl acrylate, 1 g of acrylic acid and 2,2′-azobisisobutyronitrile 0 .2 g was added together with 100 g of toluene and refluxed with nitrogen at room temperature for 1 hour. Under the nitrogen stream, the temperature was raised to 60 ° C. for 4 hours, and then heated to 80 ° C. for 2 hours. It was. After the reaction, toluene was added to adjust the solid content to 40%, and the mixture was cooled to room temperature to obtain an acrylic resin solution. The obtained acrylic resin (A-5) had a weight average molecular weight of 599000 and a dispersity of 4.8.

(Comparative Example 2)
An acrylic resin solution was obtained in the same manner as in Comparative Example 1, except that the amount of 2-ethylhexyl acrylate was 39 parts and the amount of phenoxyethyl acrylate was 60 parts. The obtained acrylic resin (A-6) had a weight average molecular weight of 959,000 and a dispersity of 6.4.

(Comparative Example 3)
In a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, condenser, and dropping funnel, 60.0 g of n-butyl acrylate, 37.0 g of 2-ethylhexyl acrylate, 1.0 g of 4-hydroxybutyl acrylate, acetone 150.0 g, 2,2′-azobisisobutyronitrile 0.06 g was charged, and the air in the reaction vessel was replaced with nitrogen gas, and then the reaction solution was stirred at 60 ° C. in a nitrogen atmosphere with stirring. The temperature was raised to 5 hours and allowed to react for 5 hours. Then, after completion of the reaction, 190 g of toluene, 0.84 g of acrylic acid and 0.50 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added, the temperature was raised to 70 ° C., and the reaction was allowed to proceed for 6 hours. It was. After the reaction, toluene was added to adjust the solid content to 20%, and the mixture was cooled to room temperature to obtain an acrylic resin solution. The obtained acrylic resin (A-7) had a weight average molecular weight of 1580000 and a dispersity of 5.5.

[Preparation of pressure-sensitive adhesive composition]
(Example 5)
To the polyester (A-1) obtained in Example 1, toluene was added and the solid content was adjusted to 40%. Further, 2.5 parts by weight of TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) was added as compound (D) and stirred well, and 3-glycidoxypropyltrimethoxy was used as a silane coupling agent. 0.5 part of silane was added and stirred well to obtain a pressure-sensitive adhesive composition of the present invention. This was coated on a release-treated polyester film (hereinafter referred to as “release film”) so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form a pressure-sensitive adhesive layer. . After drying, the pressure-sensitive adhesive layer is bonded with one side of a polarizing film having a multilayer structure in which both sides of a polyvinyl alcohol (PVA) type polarizer are sandwiched between triacetyl cellulose-based protective films (hereinafter referred to as “TAC film”), A laminate having a configuration of “release film / pressure-sensitive adhesive layer / TAC film / PVA / TAC film” was obtained. Next, the obtained laminate was aged (dark reaction) for one week under the condition of a temperature of 23 ° C. and a relative humidity of 50%, and the reaction of the adhesive layer was advanced to obtain a bonded polarizing plate (laminate).

(Examples 6-8, Comparative Examples 4-6)
Each of the polyester solutions (A-2) to (A-4) obtained in Examples 2 to 4 and the acrylic resin solutions (A-5) to (A-7) obtained in Comparative Examples 1 to 3 were solid. With respect to 50 parts per minute, as a compound (D) which is a curing agent, 2.5 parts of TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) and 3-glycidoxy as a silane coupling agent 0.5 part of propyltrimethoxysilane was added. Examples 6 to 8 were adjusted to 40% solid content with toluene, Comparative Examples 4 and 5 were adjusted to 30% solid content with toluene, and Comparative Example 6 was adjusted to 15% solid content with toluene. Stir well to obtain a pressure-sensitive adhesive composition. Further, in the same manner as in Example 1, a bonded polarizing plate (laminate) was produced.

  About the polarizing plate (laminated body) which carried out the adhesion process obtained by the Example and the comparative example, the refractive index of a coating film, heat resistance, heat-and-moisture resistance, and light leakage were evaluated with the following method. The results are shown in Table 2.

<Evaluation method of refractive index of coating film>
After the pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were coated on a release film and dried in an oven at 120 ° C. to provide a pressure-sensitive adhesive layer having a thickness of 25 μm, a polyester film A pressure-sensitive adhesive sheet was prepared by laminating and laminating. Thereafter, the Abbe refractometer “DR-M2” (manufactured by ATAGO) was irradiated with sodium D-line in an atmosphere at 25 ° C. to measure the refractive index of the adhesive layer on the adhesive sheet. Those with 1.51 or more were rated as “◯” and those with less than 1.51 as “x”.

<Evaluation methods for heat resistance, heat and humidity resistance, and light leakage>
The bonded polarizing plate (laminate) is cut into a size of 150 mm × 80 mm, the release film is peeled off, and the absorption axis of each polarizing plate is orthogonal to both surfaces of a 1.1 mm thick float glass plate. It stuck using the laminator. Subsequently, the glass plate on which the polarizing plate is attached is held in an autoclave at 50 ° C.-5 atm for 20 minutes to firmly adhere the polarizing plate to the glass plate, and the polarizing plate and the glass plate are laminated. I got a thing.

  As an evaluation of heat resistance, floating peeling after leaving the laminate at 120 ° C. for 1000 hours and light leakage when light was transmitted through the laminate were visually observed. In addition, as an evaluation of the heat and moisture resistance, floating peeling after the above laminate was allowed to stand for 1000 hours at 80 ° C. and 90% relative humidity was visually observed. Further, as an evaluation of optical properties, light leakage (white spots) when light was transmitted through the laminate was visually observed. The heat resistance and moist heat resistance were evaluated based on the following three-stage evaluation criteria.

○: “No floating peeling or light leakage was observed, and there was no problem in practical use.”
Δ: “Slightly floating peeling / light leakage is observed, but there is no practical problem”
×: “There is floating peeling and light leakage on the whole surface, which is not practical.”
Means each.

  As described above, the pressure-sensitive adhesive compositions of Examples 5 to 8 using the pressure-sensitive adhesive polyesters of Examples 1 to 4 of the present invention have heat resistance, moist heat resistance, optical characteristics, and refractive index. It turns out that it is excellent in controllability. In contrast, the pressure-sensitive adhesive compositions of Comparative Examples 4 to 6 using the resins of Comparative Examples 1 to 3 were inferior in heat resistance, moist heat resistance, and optical characteristics.

  The pressure-sensitive adhesive composition of the present invention is suitable for use as an optical member, and in addition to general labels and seals, paints, elastic wall materials, waterproof coating materials, flooring materials, tackifiers, adhesives, laminated structures Adhesives, sealing agents, molding materials, surface modification coating agents, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.), urethane foam (hard , 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, artificial Marble resin, impact resistance imparting agent for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.) , Laminated glass 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 (12)

  Reaction of the polyvalent carboxylic acid component (A) containing the aromatic dicarboxylic acid (a1), the polyol component (B) containing the diol (b1) having a hydrocarbon group in the side chain, and the polyvalent amine component (C) Polyester for pressure sensitive adhesive.   The polyester for pressure-sensitive adhesives according to claim 1, wherein the polyvalent amine component (C) is 0.1 to 40 mol% with respect to the polyol component (B).   The polyester for pressure-sensitive adhesives according to claim 1 or 2, wherein the polyvalent carboxylic acid component (A) contains 10 to 80 mol% of the aromatic dicarboxylic acid (a1).   The polyester for pressure-sensitive adhesives according to any one of claims 1 to 3, wherein the polyol component (B) contains 10 to 80 mol% of a diol (b1) having a hydrocarbon group in a side chain.   Reaction of a compound having at least one trivalent or higher functional group selected from a trivalent or higher polyvalent carboxylic acid (a2), a trivalent or higher polyol (b2), and a trivalent or higher polyvalent amine (c2) The polyester for pressure-sensitive adhesives according to any one of claims 1 to 4.   The pressure-sensitive adhesive polyester according to any one of claims 1 to 5, wherein a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2.0 to 6.0.   The polyester for pressure-sensitive adhesives according to any one of claims 1 to 6, wherein the weight average molecular weight (Mw) is 30,000 to 300,000.   A pressure-sensitive adhesive composition comprising the pressure-sensitive adhesive polyester according to claim 1 and a compound (D) having a functional group capable of reacting with a reactive functional group in the polyester.   The pressure-sensitive adhesive composition according to claim 8, wherein the compound (D) is a polyisocyanate compound.   The pressure-sensitive adhesive composition according to claim 9, further comprising a silane coupling agent.   The laminated body by which an optical member is laminated | stacked on the pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition in any one of Claims 8-10.   A glass cell member for a liquid crystal cell, a pressure sensitive adhesive layer formed from the pressure sensitive adhesive composition according to any one of claims 8 to 10, and a member for a liquid crystal cell in which an optical member is sequentially laminated.