JP2009040849A - Re-peelable pressure-sensitive adhesive composition and its re-peelable adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: The present invention does not increase the adhesive strength with time after being applied to plastics, metals, glass plates, etc., and in particular, the peeling strength (adhesive strength) does not increase extremely even if the peeling speed is increased. It is an object to provide a releasable pressure-sensitive adhesive having excellent removability and a releasable pressure sensitive adhesive having excellent tack, adhesion to a substrate, heat resistance, moist heat resistance and transparency that can form the sheet. And
A glass transition obtained by reacting a dibasic acid component (A) having no hydroxyl group, a diol (B) having no carboxyl group, and a specific side chain functional group-introducing component (C). Reaction with the hydroxyl group and / or carboxyl group in the polyester resin (D), the cellulose compound (E) and the resin (D) having a temperature of −80 to 0 ° C. and having a hydroxyl group and / or carboxyl group in the side chain. A releasable pressure-sensitive adhesive composition comprising a reactive compound (F) that can be removed.
[Selection figure] None

Description

  The present invention relates to a releasable pressure-sensitive adhesive composition that is excellent in adhesion to various adherends, heat resistance, moist heat resistance and transparency, and also excellent in removability, particularly when it is desired to peel off after sticking. The present invention relates to a pressure-sensitive adhesive and a releasable adhesive sheet that are suitable for re-peeling applications that can be peeled off and used repeatedly, and in which the peel force hardly changes depending on the peel speed and the removability does not deteriorate.

Conventional re-peelable pressure-sensitive adhesives use acrylic resins, urethane resins, and rubber resins, increase the molecular weight of the resin, or crosslink and cure the resin using an appropriate crosslinking agent to form a coating gel. The removability is secured by increasing the fraction and increasing the cohesive force, or the adhesive area is reduced by maintaining the removability by making the pressure sensitive adhesive spherical.
In addition, an activator is added to the pressure-sensitive adhesive, or the pressure-sensitive adhesive layer is foamed by heating after sticking to reduce the peeling force, or the adhesiveness is deactivated by irradiating ultraviolet rays. In order to secure removability, various measures have been taken.

However, any pressure-sensitive adhesive has the following drawbacks.
That is, not only is there a limit to increasing the molecular weight, but increasing the molecular weight increases the viscosity of the pressure-sensitive adhesive, resulting in poor workability at the time of coating, and easily affects leveling.
When the degree of crosslinking is increased by increasing the amount of the crosslinking agent, it becomes difficult to design a pressure-sensitive adhesive layer having low adhesive strength. In addition, when a large amount of a crosslinking agent is blended, the pot life (potential time) is shortened, and the performance at the time of sticking of the formed pressure-sensitive adhesive sheet is great due to the passage of time until coating after blending. There were obstacles such as being easily affected.

In addition, a so-called microsphere-based pressure-sensitive adhesive, which makes the resin constituting the pressure-sensitive adhesive spherical, is one of the microspheres when the pressure-sensitive adhesive sheet is peeled off from the adherend when a heat history is applied after sticking. The part may be transferred to the adherend, or the microspheres may be fused with each other by pressure applied before or after sticking, and the adhesive properties and removability may be lowered.
In addition, when an activator is added, appearance defects and physical property changes due to impregnation into the paper substrate are observed. Also, when using foaming due to heating or using adhesive deactivation due to UV irradiation, the treatment cannot be done without a special device. Once treated, the adhesive properties change greatly, and once peeled off, it is repeated. There were problems such as inability to use.

In Patent Document 1, cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) are added to a monomer having (meth) acrylic acid ester as a main component, dissolved, and polymerized with a radical initiator. Pressure sensitive adhesive
In Patent Document 2, it is possible to add a water-soluble compound such as methylcellulose, carbomethoxymethylcellulose, and hydroxyethylcellulose as a thickener to an aqueous pressure-sensitive adhesive.
Further, Patent Document 3 discloses a composition in which an acrylic resin microsphere having a sphere diameter of 20 to 70 μm and a specific tackifier or ethyl cellulose are dispersed in an aerosol dispersion medium for the purpose of improving the adhesive force. ing.

However, in the adhesive described in Patent Document 1, the peeling force is affected by the peeling speed.
In addition, all of the celluloses described in Patent Document 2 are for increasing the viscosity of the liquid and improving the coating property, and cannot adjust the adhesive force or the peeling force at all.
Furthermore, in the system using nitrocellulose or ethylcellulose disclosed in Patent Document 3, in applications where heat is applied, the physical properties are lowered by decomposition, or the commercial value is lowered by yellowing. Moreover, even if it does not heat, it discolors remarkably with time. Therefore, applicable fields are limited.

  By the way, because of good chemical resistance and workability, adhesives other than pressure-sensitive adhesives (hereinafter referred to as fiber coatings, paints, food packaging laminates and metal plates and plastic films) Polyester adhesives have been used in various technical fields such as adhesives). However, in the technical field of pressure-sensitive adhesives, it seems that polyester-based pressure-sensitive adhesives have been studied in the course of training, but practically they have not been studied. Occupied the majority.

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. Pressure-sensitive adhesive is not only the pressure-sensitive adhesive layer has a tack at the moment when the pressure-sensitive adhesive layer touches the adherend during sticking, but it is completely different from the adhesive. It is necessary to have a cohesive force for maintaining the sticking state while having a tack and appropriate hardness without solidifying. The cohesive force greatly depends on the molecular weight.

Since the acrylic resin is formed by addition polymerization, one having a molecular weight of several hundred thousand or more can be easily formed. On the other hand, since a polyester resin is formed by polycondensation, it is practically impossible to form such a high molecular weight resin. 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.
Therefore, in order to develop cohesion while having tack, the main component is an acrylic resin that has a relatively large molecular weight and easily develops cohesion, and a relatively small amount of a crosslinking agent is used for the main component. It can be said that an acrylic pressure-sensitive adhesive that easily develops tack is suitable. On the other hand, a polyester resin having a relatively small molecular weight can be said to be suitable as an adhesive for firmly bonding with a relatively large amount of a curing agent to develop adhesive performance.

Moreover, the raw material of the polyester resin is more expensive than the raw material of the acrylic resin. Furthermore, since the polycondensation reaction is a sequential reaction, it takes inevitably a long time to increase the molecular weight as compared with addition polymerization. As a result, the polyester resin is more expensive than the acrylic resin.
Thus, for many years, polyester resins have been applied to adhesives, and acrylic resins have been applied to pressure sensitive adhesives.

  However, there are various fields where pressure-sensitive adhesive sheets are used, and the required level is increased, new requirements are added, and the conventional acrylic pressure-sensitive adhesives are not fully meeting various requirements. Therefore, application of polyester resins to pressure-sensitive adhesives has been studied.

  For example, a sensitivity obtained by blending various crosslinking agents with a polyester resin having a glass transition temperature (Tg) of −60 to 0 ° C. formed from dimer acid and a glycol component having an alkyl group in a side chain of 30 mol% or more. A pressure-type adhesive is known (see, for example, Patent Document 4).

Also known is a pressure-sensitive adhesive comprising a unit in which an ester of a glycol having a methyl group in the side chain and a carboxylic acid linked by a polyisocyanate is repeated and an aliphatic polyester having a Tg of -40 ° C. or lower. (For example, see Patent Document 5).
The pressure-sensitive adhesive disclosed in Patent Document 5 is intended for biodegradability and is an aliphatic polyester pressure-sensitive adhesive, so that it is easy to obtain tack and a relatively flexible pressure-sensitive adhesive layer is obtained. However, the heat resistance is insufficient. For example, when used as a pressure-sensitive adhesive for laminating a glass member or polarizing film for liquid crystal cells for the purpose of surface protection, if it is placed under high temperature or high temperature and high humidity for a long time after sticking, Peeling occurs.

  Also, polycondensation of a dicarboxylic acid component containing an aromatic dicarboxylic acid, a diol component containing a glycol having a hydrocarbon group in the side chain, a trihydric or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid. A polyester resin in which a structural portion derived from a trihydric or higher polyhydric alcohol and / or trihydric or higher polycarboxylic acid is contained in an amount of 0.1 to 5 mol% in the polyester resin. A pressure-sensitive adhesive characterized by containing a resin is known (for example, see Patent Document 6).

  And a polycondensation of a carboxylic acid component containing 10 mol% or more and less than 50 mol% of an aromatic dicarboxylic acid and a polyhydric alcohol component containing 5 mol% or more of a glycol having a hydrocarbon group in the side chain, and A pressure-sensitive adhesive characterized by containing a polyester resin having a number average molecular weight of 5000 or more is known (see, for example, Patent Document 7).

The polyester-based pressure-sensitive adhesives disclosed in these patent documents are not satisfactory as a re-peelable pressure-sensitive adhesive because adhesive residue or cloudiness occurs on the adherend when the adhesive sheet is peeled off. It was. Further, the peeling force is also affected by the peeling speed.
JP-A-57-174367 Japanese Unexamined Patent Publication No. 57-87481 Japanese Patent Laid-Open No. 9-328667 Japanese Patent Laid-Open No. 04-328186 Japanese Patent Laid-Open No. 11-021340 JP 2007-099879 A JP 2007-045914 A

  In the present invention, after being applied to plastics, metals, glass plates, etc., the adhesive strength does not increase over time, and the peel strength (adhesive strength) does not increase extremely even when the peel rate is increased. It is to provide a releasable pressure-sensitive adhesive excellent in tackiness, adhesion to a substrate, heat resistance, moist heat resistance and transparency, which can form the sheet.

  In order to solve such a problem, the present inventors have conducted extensive studies, and as a result, when a releasable pressure-sensitive adhesive containing a polyester resin (D) and a cellulose compound (E) is used, various adhesive sheets are attached. When it peels after sticking to a body, even if it changed peeling speed, it discovered that peeling force was not influenced so much and completed this invention.

  That is, the first invention relates to a dibasic acid component (A) having no hydroxyl group, a diol (B) having no carboxyl group, a trihydric or higher polyhydric alcohol (c1), a trivalent or higher polyvalent. Carboxylic acid (c2), compound (c3) having two cyclic ether groups in the molecule, dioxymonocarboxylic acid (c4) having two hydroxyl groups and one carboxyl group in one molecule, and hydroxyl group in one molecule And at least one side-chain functional group-introducing component (C) selected from the group consisting of oxydicarboxylic acid (c5) having 2 carboxyl groups and a glass transition temperature of −80 to 0 ° C. Yes, a polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain, a cellulose compound (E), and a reaction capable of reacting with a hydroxyl group and / or a carboxyl group in the resin (D) To include compounds (F) about peelable pressure sensitive adhesive composition characterized.

  In the second invention, 0.001 to 60 parts by weight of the cellulose compound (E) and 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 re-peelable pressure-sensitive adhesive composition according to the first invention, comprising 0.001 to 20 parts by weight.

  A third invention relates to the releasable pressure-sensitive adhesive composition according to the first or second invention, wherein the polyester resin (D) has a weight average molecular weight of 20,000 to 1,000,000.

  4th invention is the said cyclic ester formed by ring-opening addition of the cyclic ester compound (b) to the said side chain functional group in the polyester-type resin (D) which has a hydroxyl group and / or a carboxyl group in a side chain. The re-peeling according to any one of the first to third inventions, comprising a polyester resin (D1) having a ring-opening portion of the compound (b) as a side chain and a hydroxyl group at the terminal of the ring-opening portion. Relates to a pressure-sensitive adhesive composition.

  A fifth invention is characterized in that 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. The present invention relates to a releasable pressure-sensitive adhesive composition according to any of the inventions.

  A sixth aspect of the present invention is a removable adhesive comprising a removable pressure sensitive adhesive layer formed from the removable pressure sensitive adhesive composition according to any one of the first to fifth aspects of the invention. Regarding the sheet.

  In accordance with the present invention, when an adhesive sheet that can form a pressure-sensitive adhesive layer excellent in tack, adhesion to a substrate, heat resistance, moist heat resistance and transparency is attached to various adherends, it is peeled off. It has become possible to obtain a re-peelable polyester-based pressure-sensitive adhesive whose peel force is not significantly affected even when the speed is changed.

  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 a crosslinking agent, a completely solidified adhesive layer can be formed, but the molecular weight is relatively low. A pressure-sensitive adhesive layer that needs to have tack and moderate hardness during bonding is formed simply by reacting the hydroxyl group or carboxyl group at the end of the main chain of a polyester resin with a small amount with a relatively small amount of a crosslinking 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, diglycerol, triglycerol, polyglycerol, ditrimethylolethane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, inositol, tetrakishydroxymethylphosphonium chloride, sorbitan, Examples include tetravalent or higher alcohols such as sorbitol, mannitol, saccharose, and cellulose.
These trivalent or higher valent alcohols (c1) can be used alone or in combination at any desired ratio. The trihydric or higher polyhydric alcohol (c1) reacts with the dibasic acid component (A) having no hydroxyl group as the hydroxyl component in the same manner as the diol (B) having no carboxyl group, so that only the main chain end is reacted. Instead, a hydroxyl group is introduced into the side chain.

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

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

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

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

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

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

  The compound (c3) having two cyclic ether groups in the molecule can be used either alone or in combination at an arbitrary quantitative ratio. When the dibasic acid component (A) and the diol (B) undergo a polycondensation reaction, the cyclic ether group of the compound (c3) having two cyclic ether groups in the molecule undergoes a ring-opening addition reaction to form a side chain. Secondary hydroxyl groups are introduced. Since the secondary hydroxyl group of the side chain has a low activity of the esterification reaction, a three-dimensional reaction is unlikely to occur during the esterification reaction. As a result, the resulting polyester resin (D) is difficult to partially agglomerate, is excellent in uniformity, exhibits good fluidity, and further has a cohesive strength after crosslinking when a reactive compound (E) described later is blended. 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 (E) is also low. Accordingly, 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 can be effectively mixed with the cellulose compound (E) described later and difficult to bleed, and therefore can have effective removability. Furthermore, it crosslinks with a reactive compound (E) described later to form a pressure-sensitive adhesive layer, which 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 have a high molecular weight. By introducing an ester bond into the side chain, an improvement in adhesive properties (particularly tack) is expected. The obtained polyester-based resin (D2) can be adjusted for non-volatile content by appropriately adding an organic solvent after cooling.

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

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

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

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

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

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

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

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

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

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

The polyester resin (D) in this invention selects each structural component so that the aromatic ring structure derived from the said dibasic-acid type component (A) and diol (B) may be contained 5-50 mol%, 10-30 mol%. It is more preferable.
When the component containing the aromatic ring structure of the polyester resin (D) is less than 5 mol%, the heat resistance and refractive index of the pressure-sensitive adhesive layer obtained using the polyester resin are lowered. On the other hand, when it exceeds 50 mol%, the wettability of the pressure-sensitive adhesive layer is lowered, and it becomes difficult to express sufficient tack, which is not preferable.

The weight average molecular weight (Mw) of the polyester resin (D) in the present invention is more preferably 20,000 to 1,000,000, 40,000 to 500,000, and further preferably 60,000 to 300,000. Weight average molecular weight (Mn) = 10,000 to 500,000, 15,000 to 200,000 are more preferable, and 20,000 to 300,000 are more preferable. The dispersity (Mw / Mn) is preferably 2 to 50, more preferably 2.5 to 30, and still more preferably 3 to 15. 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 20,000, the cohesive force as the pressure-sensitive adhesive layer becomes difficult to develop, and the heat resistance and heat-and-moisture resistance decrease. 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. Further, when the dispersity (Mw / Mn) is less than 2, the stress relaxation property of the pressure-sensitive adhesive layer is lowered, and stress is concentrated particularly on the peripheral portion of the polarizing film during long-term use. Color unevenness and white spots occur on the surface of the liquid crystal element such that the peripheral edge of the liquid crystal element is brighter or darker than the center. On the other hand, when the dispersity (Mw / Mn) exceeds 50, the low molecular weight component is relatively increased, and thus heat resistance and moist heat resistance are deteriorated.

  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 laminate obtained, for example, a glass member for a liquid crystal cell, 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.

The cellulose compound (E) in the present invention is added to improve the removability function of the pressure-sensitive adhesive layer. Cellulose butyrate, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxypropyl methylcellulose acetate Phthalate, triphenylmethylcellulose, trimethylsilylcellulose, tosylated cellulose, carboxymethylcellulose, cellulose xanthate, cellulose propionate, cellulose tris (4-methylbenzoate), cellulose acetate, cellulose acetate butyrate (hereinafter also referred to as CAB), cellulose Any one of acetate propionate (hereinafter also referred to as CAP), preferably CAB or CAP. And can also.
As cellulose, the use of nitrocellulose (hereinafter also referred to as NC), methylcellulose, ethylcellulose, or the like can be expected to have an effect of reducing the peeling rate dependency, but yellowing occurs when a thermal history of 160 ° C. or higher is received. NC or the like can also be used for fields / uses that do not receive heat history, or fields / uses that do not see yellowing as a problem.

The pressure-sensitive adhesive of the present invention preferably contains 1 to 60 parts by weight, more preferably 10 to 50 parts by weight of the cellulose compound (E) with respect to 100 parts by weight of the resin (D).
When the cellulose compound (E) is less than 1 part by weight, the peeling force at a high speed peeling of 30 m / min tends to be remarkably larger than that of the peeling speed of 0.3 m / min. Workability may be reduced. On the other hand, when it exceeds 60 parts by weight, the peeling force itself is hardly affected by the peeling speed, but the pressure-sensitive adhesive layer itself becomes too hard and it is difficult to ensure the performance as a pressure-sensitive adhesive.
If the cellulose compound (D) is contained in an amount of 1 to 60 parts by weight with respect to 100 parts by weight of the resin (D), the peeling force is less affected by the peeling speed. For example, the peeling force ratio = [30 (m / m). Min) at a high speed peeling] / [peeling force at a low speed peeling of 0.3 (m / min)] can be controlled to 30 times or less.
Moreover, it is preferable that the peeling force at the time of low speed peeling is in the range of 10 to 500 mN / 25 mm, and more preferably in the range of 15 to 200 mN / 25 mm.

  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 polyisocyanate modified products thereof can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group selected from isocyanurate groups, or a modified product having two or more of these groups can be used. .
A reaction product of polyol and diisocyanate can also be used as polyisocyanate.

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

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

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

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

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

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

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

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

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

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

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

The 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 strength is lowered and the heat resistance, moist heat resistance, and re-peelability 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 heat resistance and heat-and-moisture resistance under conditions severer than before can be improved, it can be preferably used as a re-peeling application.

The resin composition of the present invention is suitable as a removable 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, when an isocyanate compound is used as the reactive compound (F), 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 adhesive sheet of the present invention is a state in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention is laminated on the so-called sheet (also referred to as “film” as described above). belongs to. 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) The pressure-sensitive adhesive composition is applied to the release-treated surface of the release-treated sheet-like base material, dried, and the sheet-like base material is laminated on the surface of the pressure-sensitive adhesive layer.
(A) A pressure-sensitive adhesive composition is applied to a sheet-like base material, dried, and the release-treated surface of the peel-like sheet-like base material 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 suitably used as a surface protective film for applications that require high performance. 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 as a surface protective film for a so-called sheet (also referred to as a film as described above) optical member.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Synthesis Example 10)
Polymerization tank, stirrer, thermometer, reflux condenser, polymerization tank equipped with a nitrogen introduction tube and a dropping apparatus, polycarbonate diol (Daicel Chemical Industries, PLACEL CD220PL, hydroxyl value: 55.1 KOH mg / g) ) 200.0 parts by weight, 19.8 parts by weight of sebacic acid, 0.1 parts by weight of tetra-n-butyl titanate as a catalyst, and in the presence of a small amount of xylene as a solvent for discharging water as a reaction byproduct The temperature of the liquid in the flask was raised to 180 ° C. while stirring was started, and a polymerization reaction was carried out for 20 hours to obtain polyester (a). This polyester (a) had a number average molecular weight of 27000 and a dispersity of 1.9.

<Manufacture of acrylic resin>
(Synthesis Example 11)
The following acrylic monomers were charged at the following ratios into a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube, respectively.
[Polymerization tank]
N-butyl acrylate 19.5 parts methyl methacrylate 4 parts 4-hydroxybutyl acrylate 1.5 parts ethyl acetate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [drip apparatus]
N-butyl acrylate 19.5 parts methyl methacrylate 4 parts 4-hydroxybutyl acrylate 1.5 parts ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

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

  About the polyester resin (D) obtained by the synthesis examples 1-10, and the acrylic resin obtained by the synthesis example 11, the external appearance of a solution, a non volatile matter, the weight average molecular weight (Mw) of a polyester resin, and a glass transition temperature (Tg) The acid value (AV) and the hydroxyl value (OHV) were determined according to the following method, and the results are shown in Table 1.

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

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

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

<< Measurement of weight average molecular weight (Mw) >>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used.

  GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size, and the weight average molecular weight (Mw) and number average molecular weight (Mn) are determined in terms of polystyrene.

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

<Measurement of acid value (AV)>
About 1 g of a sample (polyester resin solution with a nonvolatile 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 with a nonvolatile 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
Cellulose acetate butyrate resin “CAB551-0.2 (Eastman Kodak Company) as the cellulose compound (E) with respect to 100 parts of the polyester resin (D) solution (solid content: about 50%) obtained in Synthesis Example 1. 20 parts by weight) and 25 parts by weight of toluene, and 2.5 parts by weight of TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) as a reactive compound (F) are added and stirred well. Thus, a pressure-sensitive adhesive composition of the present invention was obtained. 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.
After drying, a 50 μm-thick PET film was laminated on the adhesive layer and aged (dark reaction) at room temperature for 1 week to obtain a releasable pressure-sensitive adhesive sheet using the PET film as a support.
About the obtained adhesive sheet, heat resistance performance, wet heat resistance performance, removability, etc. were evaluated according to the methods and criteria described below. The results are shown in Table 2.

(Comparative Example 1)
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the cellulose compound (E) was not used in Example 1, and was similarly evaluated.

(Comparative Example 2)
Instead of the polyester resin (D) used in Example 1, 100 parts of the polyester resin prepared in Synthesis Example 10 was used, except that the cellulose compound (E) used in Example 1 was used. In the same manner as in Example 1, an attempt was made to perform pressure-sensitive adhesive processing, but although the coating could be performed, the adhesive layer did not exhibit tack (initial adhesiveness), and an adhesive sheet could not be produced.

(Comparative Example 3)
Instead of the polyester resin (D) used in Example 1, 100 parts of the acrylic resin prepared in Synthesis Example 11 was used, 12 parts of the cellulose compound (E) used in Example 1, 15 parts of toluene, and reaction A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that 1.5 part of the functional compound (F) was used, and evaluated in the same manner.

(Example 2)
Instead of using the cellulose acetate butyrate resin used in Example 1 as the cellulose compound (E), cellulose acetate propionate resin “CAP504-0.2, manufactured by Eastman Kodak Co., Ltd.” was used. In the same manner as in Example 1, a pressure-sensitive adhesive sheet was obtained and evaluated in the same manner.

(Examples 3 to 8)
Instead of using the cellulose compound (E) used in Example 1 in place of the polyester resin (D) used in Example 1, 100 parts of the acrylic resin prepared in Synthesis Examples 3, 5 to 9 was used. In the same manner as in Example 1, a pressure-sensitive adhesive sheet was obtained and evaluated in the same manner.
(Examples 9 and 10)
Instead of TDI / TMP which is the reactive compound (B) used in Example 1, XDI / TMP (trimethylolpropane adduct of xylylene diisocyanate) (Example 9), HMDI / burette (hexamethylene diisocyanate) The pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that 2.5 parts by weight of each of the burette adduct body (Example 10) was used. Using these, in the same manner as in Example 1, a pressure-sensitive adhesive sheet was obtained and evaluated in the same manner.

(Examples 11 and 12)
To 100 parts by weight of the polyester resin (D) solution obtained in Synthesis Examples 2 and 4, 25 parts of toluene was added, and further cellulose acetate butyrate resin “CAB551-0.2 (yeast) as cellulose compound (E). 20 parts by weight of Mankodak Co., Ltd.) and 25 parts of toluene were added, and HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) was added as the reactive compound (F). 0.25 part by weight was added and stirred well to obtain a pressure sensitive adhesive composition of the present invention. In the same manner as in Example 1, a pressure-sensitive adhesive sheet was obtained and evaluated in the same manner.

(Examples 13 to 14)
20 parts by weight of cellulose acetate butyrate resin “CAB551-0.2 (manufactured by Eastman Kodak)” and toluene with respect to 100 parts by weight of each of the addition-type polyester resin solutions obtained in Synthesis Examples 2 and 4 25 parts was added, and TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine) 0.25 parts by weight was further added as the reactive compound (F), and the mixture was stirred well. A pressure sensitive adhesive composition was obtained. Using this, an adhesive sheet subjected to pressure-sensitive adhesive processing was obtained in the same manner as in Example 1 and evaluated in the same manner.

(Examples 15 to 16)
20 parts by weight of cellulose acetate butyrate resin “CAB551-0.2 (manufactured by Eastman Kodak)” and toluene with respect to 100 parts by weight of each of the addition-type polyester resin solutions obtained in Synthesis Examples 2 and 4 Add 25 parts, and further add 0.25 parts by weight of “carbodilite V-05” (Nisshinbo Co., Ltd.), which is a carbodiimide compound, as the reactive compound (F) and stir well to pressure-sensitive adhesive of the present invention. An agent composition was obtained. Using this, an adhesive sheet subjected to pressure-sensitive adhesive processing was obtained in the same manner as in Example 1 and evaluated in the same manner.

(Examples 17 to 18)
20 parts by weight of cellulose acetate butyrate resin “CAB551-0.2 (manufactured by Eastman Kodak)” and 100% by weight of 100 parts by weight of each of the addition-type polyester resin solutions obtained in Synthesis Examples 2 and 4 25 parts of alcohol (IPA) is added, and 0.25 parts by weight of Al chelate (aluminum tris (acetylacetonate)) is further added as the reactive compound (F), and the mixture is stirred well, and the pressure-sensitive adhesive composition of the present invention. I got a thing. Using this, an adhesive sheet subjected to pressure-sensitive adhesive processing was obtained in the same manner as in Example 1 and evaluated in the same manner.

  Pot life and coating processability of pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples, optical properties of adhesive processed adhesive sheets, and basic three physical properties related to adhesion (adhesive strength, holding power, ball tack) The heat resistance and removability were evaluated by the following methods. The results are shown in Table 2.

<Evaluation method of pot life>
About the pressure sensitive adhesive composition obtained by each Example and the comparative example, it is a viscosity on condition of 12 rpm and rotation for 1 minute in a B-type viscometer (made by Tokyo Keiki Co., Ltd.) every 10 hours at 25 ° C. Was measured, and pot life (pot life) was evaluated in three stages.
○: “No problem at all. The rate of increase in viscosity up to 8 hours is less than 2 times.”
Δ: “Slight increase in viscosity is observed and the rate of increase in viscosity up to 5 hours is less than 2 times.”
X: “A sudden increase in viscosity was observed and gelled in less than 5 hours.

<Evaluation method of coating processability>
The pressure-sensitive adhesive composition obtained in each Example and Comparative Example was applied to a release-treated polyester film at a speed of 2 m / min with a comma coater so that the thickness after drying was 25 μm. It dried in 100 degreeC oven, the 50-micrometer-thick polyester film was bonded together and laminated | stacked, and the pressure sensitive adhesive sheet was produced. The state of the coated surface was visually observed and evaluated in three stages.
○: “No problem at all”
Δ: “Slight repellency and foaming are recognized at the end of the coated surface, but there is no practical problem.”
×: “Repelling, foaming and streaking are recognized on the coated surface, and there are practical problems.”

<< Evaluation method of optical characteristics >>
The pressure-sensitive adhesive composition obtained in each Example and Comparative Example was applied to a release-treated polyester film and dried, and after a pressure-sensitive adhesive layer having a thickness of 25 μm was provided, it was further subjected to a release treatment. A polyester film was laminated. After aging the pressure-sensitive adhesive layer sandwiched between the peel-treated polyester films at a temperature of 23 ° C. and a relative humidity of 50% for one week, both the peel-treated polyester films were removed, and the pressure-sensitive adhesive layer alone was removed. While visually judging the appearance, HAZE was measured by “NDH-300A” [manufactured by Nippon Denshoku Industries Co., Ltd.].
○: “No problem in practical use. HAZE: less than 1.”
Δ: “No cloudiness is observed, and HAZE: 1 or more and less than 3”
X: “Slight fogging is observed, optical interference unevenness is observed, or HAZE: 3 or more.

<Evaluation method of basic three physical properties related to adhesion>
(1) Adhesive sheet was affixed to a stainless steel plate (SUS304) with a thickness of 2 mm under the conditions of a sample width of 25 mm and a temperature of 23 ° C. and a relative humidity of 50%. The peel strength (180 degree peel, tensile speed 0.3 m / min) was measured with a mold peel tester to obtain an adhesive strength evaluation value (mN / 25 mm).

  (2) The pressure-sensitive adhesive sheet was bonded to a 2 mm thick stainless steel plate (SUS304) so that the bonding area would be 25 mm × 25 mm, and 2 kg of roll was pressure-bonded according to JIS0237 and left at 40 ° C. for 20 minutes. A load of 1 kg was applied, and the number of seconds until dropping or the deviation (mm) after 60 minutes was measured to obtain a holding force evaluation value. However, it is NC when there is no gap.

  (3) Also peel off the polyester film from which the pressure-sensitive adhesive sheet has been peeled off. The ball was measured by the Dow rolling ball method at a temperature of 23 ° C. and a relative humidity of 50% to obtain a ball tack (BT) value.

<Method for evaluating heat resistance>
Similar to the adhesive force measurement, the adhesive sheet was attached to a stainless steel plate (SUS304) in a 25 mm width and 23 ° C. and 50% atmosphere, and 2 kg roll-bonded according to JIS0237, and the temperature was 23 ° C. and the relative humidity was 50%. After being left for 24 hours, left in an oven at 160 ° C. for 1 hour, taken out, and then measured for adhesive strength (180 degree peel, pulling speed 0.3 m / min) with a shopper type peel tester. The evaluation value (mN / 25 mm) was used. Moreover, the external appearance (hue change) was confirmed visually.

<Evaluation method of removability>
Similar to the measurement of adhesive strength, the adhesive sheet was attached to a stainless steel plate (SUS304) in a 25 mm width and 23 ° C. and 50% atmosphere, and 2 Kg roll pressed in accordance with JIS0237, and the temperature was 23 ° C. and the relative humidity was 50%. After leaving for 24 hours, using a shopper type peel tester, peel at two peel rates (low peel rate (0.3 m / min) and high peel rate (30 m / min) peel rate) (180 degree peel) Then, the adhesive strength (mN / 25 mm) and the appearance such as adhesive residue were compared.
○: “No adhesive residue after peeling. No problem in practical use”
×: “There is adhesive residue after peeling.
Moreover, using the same sample as the re-peeling test, the pressure-sensitive adhesive sheet was peeled off by hand at a peeling speed of about 30 m / min, and the feeling of peeling at that time was compared.
○: “Peeling feeling is good. Does not feel heavy. No problem in practical use”
×: “Poor peeling feeling. It feels quite heavy.

As mentioned above, it turns out that the pressure sensitive adhesive composition of this invention is excellent in transparency, heat resistance, transparency, and removability.
On the other hand, the comparative example 1 which does not contain a cellulosic compound has a high adhesive force, and cannot be easily peeled off. On the other hand, it can be seen that Comparative Example 2 does not function as a pressure-sensitive adhesive because it originally contains a cellulose resin in a low tack resin. Also, the cohesive force cannot be maintained. Moreover, it turns out that the comparative example 3 using an acrylic resin cannot maintain heat resistance, and is remarkably inferior.

  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. Examples thereof include heat resistance and optical characteristics of the adhesive sheet as in the present invention. Furthermore, by containing a cellulose compound, it can be used for re-peeling applications in particular, and as a countermeasure to recent environmental problems, it can be used for labels, tapes, package seals, protective sheets, etc. that can be peeled off when necessary. It can be used and has great social significance.

  Further, the pressure-sensitive adhesive composition of the present invention is suitable as a releasable pressure-sensitive adhesive, 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 curable 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 (6)

Dibasic acid component (A) having no hydroxyl group, diol (B) having no carboxyl group, trihydric or higher polyhydric alcohol (c1), trivalent or higher polyvalent carboxylic acid (c2), intramolecular (C3) having two cyclic ether groups, dioxymonocarboxylic acid (c4) having two hydroxyl groups and one carboxyl group in one molecule, and two hydroxyl groups and two carboxyl groups in one molecule A glass transition temperature obtained by reacting with at least one side chain functional group-introducing component (C) selected from the group consisting of oxydicarboxylic acid (c5) is −80 to 0 ° C., and a side chain has a hydroxyl group and / or Or a polyester-based resin (D) having a carboxyl group, a cellulose-based compound (E), and a reactive compound (F) capable of reacting with a hydroxyl group and / or a carboxyl group in the resin (D). Peelable pressure sensitive adhesive composition characterized. 0.001 to 60 parts by weight of the cellulose compound (E) and 0.001 to 20 parts 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 re-peelable pressure-sensitive adhesive composition according to claim 1, comprising a part. The releasable pressure-sensitive adhesive composition according to claim 1 or 2, wherein the polyester-based resin (D) has a weight average molecular weight of 20,000 to 1,000,000. Opening of the cyclic ester compound (b), wherein the cyclic ester compound (b) is further subjected to ring-opening addition to the side chain functional group in the polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain. The releasable pressure-sensitive adhesive composition according to any one of claims 1 to 3, comprising a polyester resin (D1) having a ring part as a side chain and a hydroxyl group at the terminal of the ring-opening part. The re-peeling according to any one of claims 1 to 4, wherein the reactive compound (F) has two or more functional groups capable of reacting with the side chain functional groups in the polyester resin (D) in one molecule. Pressure-sensitive adhesive composition. A re-peelable pressure-sensitive adhesive layer formed from the re-peelable pressure-sensitive adhesive composition according to claim 1, wherein the re-peelable pressure-sensitive adhesive layer is provided.