JP2009013201A - Pressure-sensitive adhesive composition and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive composition excellent in heat resistance and the anchoring property on a substrate, and a laminated body using the pressure-sensitive adhesive composition. <P>SOLUTION: The pressure-sensitive adhesive composition includes a polyester-based resin D having a glass transition temperature in a range of -80-0°C and having a hydroxy group and/or a carboxy group at a side chain; a silane compound E including a functional group selected from an amino group, a vinyl group, a glycidyl group, a mercapto group, and β-ketoester group, and an alkoxy group; and a reactive compound F reactive with the hydroxy group and/or the carboxy group in the resin D. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pressure-sensitive adhesive composition having excellent adhesion to various adherends and heat resistance, and excellent adhesion to a substrate, and particularly excellent adhesion to a foam substrate. The present invention relates to a polyester-based pressure-sensitive adhesive composition and a laminate using the same.

Reflecting the recent trend of environmental considerations, interest in noise and vibration, which are one of the environmental problems, has increased, and many efforts have been made to solve this problem. In particular, with regard to noise, related laws such as the Noise Regulation Law have been put into practice, centering on automobile noise, and have been put into practice. Therefore, material development for noise prevention is thriving.
For example, a double-sided vibration-sensitive pressure-sensitive adhesive comprising a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition on both sides of a sheet-like base material having vibration damping properties and rich in viscoelasticity. Efforts have been made to suppress and prevent noise and vibration by sandwiching the sheet between metal layers, between metal and plastic, or between plastic layers. Specifically, examples of the core material of the layer having vibration damping properties and rich in viscoelasticity include rubber sheets and foams such as natural rubber, chloroprene rubber, EPDM rubber, and butyl rubber.
The vibration-damping sheet-like base material often has not only functions of vibration damping and soundproofing but also functions such as heat insulation and sealing properties. Using such a sheet-like substrate, a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition can be provided on one surface of the sheet-like substrate to obtain a single-sided heat-insulating pressure-sensitive adhesive sheet. These vibration-damping or heat-insulating pressure-sensitive adhesive sheets are being used or examined for use in applications such as automobile oil pans, stairs, doors, flooring, roofing materials, and motor and compressor covers.

  The performance of such a vibration-damping or heat-insulating pressure-sensitive adhesive sheet such as vibration damping and heat insulation often depends greatly on the performance of the sheet-like substrate. For example, when the damping performance is represented by a loss factor (η), η has a characteristic that shows a peak at a certain temperature, and the damping pressure-sensitive adhesive sheet is used in the vicinity of the characteristic temperature at which this η shows a peak. Is known to be most effective.

  As a material of the sheet-like base material of the vibration-damping or heat-insulating pressure-sensitive adhesive sheet, conventionally, polyurethane resin, polyester resin, polyamide resin, polyisobutylene resin, ethylene / α-olefin resin, EVA resin, cross-linked polyolefin resin, Polyvinyl acetal resins and the like have been studied (Patent Documents 1 to 8), and asphalt, synthetic rubber, acrylic resin, epoxy resin, and the like are also known to have vibration damping performance. Many of these are foams for the purpose of vibration damping or heat insulation.

  The problem here is the adhesion to the foam substrate. There are many bubbles on the surface of the foam, and there are many irregularities. Therefore, there are fine voids at the interface between the pressure-sensitive adhesive layer and the foam substrate, and the pressure-sensitive adhesive layer and the bonding area are relatively smaller than in the case of a sheet substrate without voids. It is difficult to ensure the adhesion of the pressure sensitive adhesive layer to the substrate. And when the adhesiveness is extremely bad, when the pressure-sensitive adhesive sheet receives a thermal history, the foam base material and the pressure-sensitive adhesive are peeled off, and the pressure-sensitive adhesive layer is effectively applied to various adherends. It will transfer. Usually, pressure-sensitive adhesives used for vibration-damping or heat-insulating pressure-sensitive adhesive sheets include pressure-sensitive adhesives such as acrylic resins, isobutylene rubber, and EVA. In order to increase the adhesion to the foam substrate, the method of lowering the Tg of the resin, lowering the degree of crosslinking, or adding a tackifying resin is often used. The result of getting worse has been forced.

Accordingly, various proposals have been made for pressure-sensitive adhesive compositions using acrylic resins.
For example, in an acrylic pressure-sensitive adhesive composition containing an acrylic polymer and a tackifying resin as main components, the tackifying resin is a resin acid ester obtained by reacting a resin acid and a polyhydric alcohol, In addition, an acrylic pressure-sensitive adhesive composition is disclosed in which the hydroxyl value of the resin acid ester is 50 to 100 (see Patent Document 9).
Further, for example, after adding phenols to an acrylic polymer and an aromatic petroleum fraction and / or an aromatic coal fraction having a boiling point of 140 to 240 ° C., polymerization is performed using a Friedel-Crafts catalyst. An acrylic pressure-sensitive adhesive comprising a hydrocarbon resin having a hydroxyl value of 40 to 130 and a softening point of 60 to 150 ° C. is disclosed (see Patent Document 10).
Further, for example, a pressure-sensitive adhesive composition comprising an acrylic polymer, a tackifier, a curing agent, and an organic solvent, wherein the glass transition point of the dry film of the pressure-sensitive adhesive composition is −20 ° C. to 15 ° C. The elastic modulus at 150 ° C. is 1 × 10 ⁵ dyne / cm ² or more, the loss tangent (tan δ) is 0.5 or less, and the hydroxyl value is 60 to 100 or the acid value is 30 with respect to 100 parts by weight of the acrylic polymer. There is disclosed a pressure-sensitive adhesive composition characterized in that it contains 10 to 40 parts by weight of -50 rosin tackifiers (see Patent Document 11).

However, although the heat resistance is considerably improved by the pressure-sensitive adhesive composition disclosed in these documents, there is a drawback in the adhesion to the substrate.
Excellent surface adhesion, high in a wide temperature range from near room temperature to high temperature, which can be used in fields where high damping performance is required in a wide temperature range from near room temperature to high temperature, such as parts around automobile bodies Pressure-sensitive adhesive that has vibration-damping performance and has strong adhesion performance that can follow molding processes such as punching and bending of vibration-damping materials, and that does not easily deteriorate even when exposed to high temperatures and high humidity. Yes, not yet found.

  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 curing 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 curing 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 12).

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 13).
The pressure-sensitive adhesive disclosed in Patent Document 13 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, heat resistance is insufficient.

Patent Documents 14 and 15 disclose that a polyester resin is a main ingredient and that aromatic dicarboxylic acid in a polyester resin is introduced to increase heat resistance.
In order to increase the cohesive force of the pressure-sensitive adhesive layer, it is considered necessary to increase these aromatic rings in the polyester resin. However, the adhesiveness with respect to the sheet-like base material having a fine uneven surface such as a foam is insufficient, and its adhesion performance deteriorates when exposed to high temperature and high humidity.

Patent Documents 16 and 17 disclose an invention relating to a pressure-sensitive adhesive composition containing a lactic acid resin and a tackifier. However, when the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition disclosed in these documents is exposed to high temperature and high humidity, its adhesive performance is degraded.
JP-A-47-019277 JP 50-143880 A Japanese Patent Laid-Open No. 51-079146 JP-A-54-033251 Japanese Patent Laid-Open No. 55-084655 JP-A-57-034949 JP 59-152847 A Japanese Patent Laid-Open No. 60-088149 Japanese Patent Laid-Open No. 03-281487 Japanese Patent Publication No. 07-065020 JP 09-263742 A Japanese Patent Laid-Open No. 04-328186 Japanese Patent Laid-Open No. 11-021340 JP 2007-099879 A JP 2007-045914 A JP 2001-049098 A JP 2006-070091 A

  An object of the present invention is to provide a pressure-sensitive adhesive composition excellent in heat resistance and substrate adhesion, a pressure-sensitive adhesive composition suitable for foams, and a pressure-sensitive adhesive composition using the pressure-sensitive adhesive composition It is to provide an adhesive sheet.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the first invention is a polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain, having a glass transition temperature in the range of −80 to 0 ° C., amino group, vinyl group, glycidyl group, mercapto. And a silane compound (E) having a functional group selected from a β-ketoester group represented by the following general formula (1) and an alkoxy group, and a hydroxyl group and / or a carboxyl group in the resin (D). The present invention relates to a pressure-sensitive adhesive composition comprising a reactive compound (F) to be obtained.

(In the general formula (1), R ¹ represents an alkyl group.)

  The second invention relates to the pressure-sensitive adhesive composition according to the first invention, wherein the silane compound (E) is a compound represented by the following general formula (2).

(In the general formula ^{(2), R 1, R} 2, R 5 each independently represents an alkyl group, m is .a and b represents an integer of 0 or more represent independently of 1~3, a + b + c = 4)

  The third invention relates to the pressure-sensitive adhesive composition according to the second invention, wherein the silane compound (E) is a compound represented by the following general formula (3) or (4): .

(In the general formulas (3) and (4), R ^{1 to} R ⁵ each independently represents an alkyl group, and m represents an integer of 0 or more.)

  In the fourth invention, 0.01 to 10 parts by weight of the silane compound (E) and 0.1 part 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 pressure-sensitive adhesive composition according to any one of the first to third inventions, comprising 001 to 20 parts by weight.

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

  According to a sixth aspect of the present invention, the side chain functional group in the polyester resin (D1) having a hydroxyl group and / or carboxyl group in the side chain and a polyester resin (D1) having a hydroxyl group and / or a carboxyl group in the side chain. And a polyester resin (D2) obtained by ring-opening addition of the cyclic ester compound (G), wherein the ring-opening portion of the cyclic ester compound (G) has a side chain and a hydroxyl group at the terminal of the ring-opening portion. This relates to a pressure-sensitive adhesive composition according to the fifth invention.

  The seventh invention is characterized in that the reactive compound (F) has two or more functional groups capable of reacting with a side chain functional group in the polyester resin (D) in one molecule. The present invention relates to a pressure-sensitive adhesive composition according to any of the inventions.

  According to an eighth aspect of the present invention, there is provided a one-sided feeling in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of the first to seventh inventions is laminated on one surface of a sheet-like substrate. The present invention relates to a pressure-sensitive adhesive sheet.

  A ninth invention is a double-sided pressure-sensitive adhesive in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of the first to seventh inventions is laminated on both surfaces of a sheet-like substrate. Regarding the sheet.

  A tenth invention relates to the pressure-sensitive adhesive sheet according to the eighth or ninth invention, wherein the sheet-like substrate is a foam.

  With the pressure-sensitive adhesive composition of the present invention, a pressure-sensitive adhesive sheet excellent in heat resistance and substrate adhesion can be provided. In particular, even when a foam having a small contact area and difficult to ensure adhesion is used as a sheet-like substrate, excellent adhesion performance can be maintained.

  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.

  As described in the background section, the pressure-sensitive adhesive layer does not completely solidify during sticking, and has cohesive strength to maintain the sticking state while having a tack and appropriate hardness. It is necessary to enlarge it. However, since the polyester resin is formed by polycondensation, there is a limit to increasing the cohesive force of the pressure-sensitive adhesive layer by increasing the molecular weight. Further, when a hydroxyl group or a carboxyl group at the end of the main chain of a polyester resin having a relatively small molecular weight is reacted with a relatively large amount of a curing agent, the polyester resin is completely solidified. Or, by reacting the hydroxyl group or carboxyl group at the end of the main chain of a polyester resin having a relatively small molecular weight with a relatively small amount of curing agent, crosslinking (curing) is sparse and sufficient cohesive force cannot be expressed. A pressure-sensitive adhesive layer that needs to have tack and moderate hardness during sticking could not be formed. In the present invention, an appropriate cross-linked (cured) state can be formed by using a polyester resin (D) having a functional group such as a hydroxyl group or a carboxyl group not only at the end of the main chain but also at the side chain. .

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the trivalent or higher polyvalent carboxylic acid (c2) used in the present invention include trimellitic acid, pyromellitic acid, 4-methylcyclohexene-1,2,3-tricarboxylic acid, trimesic acid, and 1,2. , 3,4-Butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, cyclopentanetetracarboxylic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, ethylene glycol bistrimellitate carboxylic acid, 9,9-bis (3,4-dicarboxyphenyl) fluorene diacid, 2,2 ′ , 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, 3,3 ′, 4, '- ester such as monoalcohol trifunctional or more polycarboxylic acids and anhydrides thereof such as methanol or ethanol, such as biphenyl tetracarboxylic acid and the like.

  These trivalent or higher polyvalent carboxylic acids (c2) can be used singly or in combination in any quantity ratio. The trivalent or higher polyvalent carboxylic acid (c2) reacts with the diol (B) not having a carboxyl group as a carboxyl group component in the same manner as the dibasic acid component (A) having no hydroxyl group, A carboxyl group is introduced not only at the terminal but also in the side chain.

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

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

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

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

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

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

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

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

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

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

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

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

The well-known oxydicarboxylic acid (c5) used for this invention can be used individually or in combination of 2 or more types, respectively.
Since the oxydicarboxylic acid (c5) has two carboxyl groups, it is polycondensed with the diol (B) as a COOH component in the same manner as the dibasic acid component (A) having no hydroxyl group, and used in the present invention. A polyester resin (D) is produced. And the hydroxyl group derived from oxydicarboxylic acid (c5) turns into a hydroxyl group of the side chain of a polyester resin (D).
It is preferable that the two carboxyl groups in the oxydicarboxylic acid (c5) are both primary in terms of rich activity during the esterification reaction. On the other hand, when the oxydicarboxylic acid (c5) functions as an OH component during the esterification reaction, it easily undergoes a three-dimensional reaction during the reaction, and gelation is likely to occur, or the polyester resin (D) is obtained without gelation. Even if it is done, it is easy to partly aggregate. Therefore, in the esterification reaction, the hydroxyl group in the oxydicarboxylic acid (C) is secondary or tertiary so that the oxydicarboxylic acid (c5) functions exclusively as a COOH component and not as an OH component. Preferably there is. Since the activity of the esterification reaction is low, the oxydicarboxylic acid (c5) can have one or more secondary or tertiary hydroxyl groups in one molecule.
In the case of the oxydicarboxylic acid (c5) having an aromatic ring, an OH group directly bonded to the aromatic ring is preferable in terms of low esterification activity, but also has low reaction activity with the reactive compound (F). Therefore, the hydroxyl group of the oxydicarboxylic acid (c5) is preferably a secondary or tertiary hydroxyl group that is not directly connected to the aromatic ring.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the present invention, the cyclic ester compound (G) is further subjected to ring-opening addition to the hydroxyl group or carboxyl group of the side chain introduced using the side chain functional group introduction component (C), and the cyclic ester compound (G) A pressure-sensitive adhesive composition can also be obtained by using a polyester resin (D2) having a ring-opened portion as a side chain and a hydroxyl group at the end of the ring-opened portion. When the ring-opening addition of the cyclic ester compound (G), the side chain functional group of the polyester resin (D1) is preferably a hydroxyl group in terms of reactivity. That is, it is preferable to further utilize the side chain hydroxyl group introduced by (c1), (c3) or (c5) in the side chain functional group introduction component (C).
For example, the polyester resin (D1) obtained by the above method (1) or (2) and the cyclic ester compound (G) are mixed together and then reacted together, or the polyester resin (D1). The polyester-based resin (D2) can be obtained by reacting while adding the cyclic ester compound (G) or by adding the polyester resin (D1) to the cyclic ester compound (G). Alternatively, the cyclic ester compound (G) may be added and reacted during the reaction of the polyester resin (D1). The polyester resin (D1) is preferably used in a solution state. For example, the ring-opening addition reaction is preferably performed at 20 to 220 ° C, more preferably 60 to 180 ° C. By opening the cyclic ester compound (G), an ester bond can be introduced into the side chain of the polyester resin (D1). Further, the cyclic ester compound (G) can be further subjected to ring-opening addition to the added hydroxyl group at the end of the ring-opening portion, and the side chain can be lengthened to 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) used in the present invention preferably contains 5 to 50 mol% of an aromatic ring structure, and more preferably 10 to 35 mol%. Constituent components such as the above-mentioned dibasic acid component (A) and diol component (B) having no carboxyl group can be appropriately selected so as to contain the aromatic ring structure in such a range. When the aromatic return structure is less than 5 mol%, the heat resistance of the pressure-sensitive adhesive layer obtained using the polyester resin is lowered. On the other hand, if the fragrance returning structure exceeds 50 mol%, the wettability of the pressure-sensitive adhesive layer is lowered, and it becomes difficult to express sufficient tack.

  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. Number average molecular weight (Mn) = 10,000 to 500,000 and 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. When the pressure-sensitive adhesive sheet is to be peeled off, not only is it difficult to peel off, but adhesive residue may be generated after peeling, resulting in insufficient removability. Further, when both the hydroxyl value and the acid value are higher than 50 mgKOH / g, the pot life is shortened, and workability at the time of coating and bonding is remarkably lowered, which is not preferable.

The pressure-sensitive adhesive composition of the present invention is a silane compound having an alkoxy group and a functional group selected from an amino group, a vinyl group, a glycidyl group, a mercapto group, and a β-ketoester group represented by the general formula (1) It is important to contain (E).
The alkoxy group in the silane compound (E) improves the wettability of the pressure-sensitive adhesive layer with respect to the substrate and the adherend, and improves the adhesion (throwing property). That is, when a foam having excellent vibration damping properties, heat insulating properties, and soundproofing properties is used as a sheet-like substrate, the pressure-sensitive adhesive sheet is coated with a pressure-sensitive adhesive composition on a peelable sheet as will be described later. A foam is placed on the surface of the pressure-sensitive adhesive layer that is dried and close to the solid that is being formed, and the pressure-sensitive adhesive layer is cured. Therefore, in order to ensure strong adhesion, it is important that the pressure-sensitive adhesive layer in a state close to a solid wets and foams the foam surface. And when sticking a pressure-sensitive-type adhesive sheet to a to-be-adhered body, it is important that a pressure-sensitive-type adhesive layer has sufficient affinity for the surface of a to-be-adhered body similarly.
Examples of the alkoxy group include an ethoxy group and a methoxy group. In the present invention, a methoxy group is preferable. In addition, 1 to 3 alkoxy groups are present per molecule of the silane compound. The number is preferably two or more. More preferably, it is three.

In the present invention, it is important that the silane compound has a functional group selected from an amino group, a vinyl group, a glycidyl group, a mercapto group, and a β-ketoester group. When these functional groups chemically bond with other components in the pressure-sensitive adhesive composition or generate hydrogen bonds, bleeding out of the silane compound after sticking can be suppressed / prevented. As a result, even if it is exposed to high temperature or high temperature and high humidity for a long time with the pressure-sensitive adhesive sheet attached to the adherend, it will remain firmly attached to the adherend without causing lifting or peeling. Can do.
Furthermore, in the present invention, the functional group of the silane compound (E) is preferably a glycidyl group or a β-ketoester group from the balance of stability over time as a pressure-sensitive adhesive solution and improved adhesion of the pressure-sensitive adhesive layer. .

Among the silane compounds (E) used in the present invention, examples of the silane compound having an amino group include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl) -3- Examples include aminopropylmethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like.
Examples of the silane compound having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.

  Among the silane compounds (E) used in the present invention, examples of the silane compound having a methacryloxy group include γ-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane.

  Among the silane compounds (E) used in the present invention, examples of the silane compound having a glycidyl group include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltri Examples include methoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Among the silane compounds (E) used in the present invention, examples of the silane compound having a mercapto group include 3-mercaptopropyltrimethoxysilane.

  Among the silane compounds (E) used in the present invention, the silane compound having a β-ketoester group is a compound having a structure represented by the following general formula (1) and an alkoxy group.

In the general formula (1), R ¹ represents an alkyl group. Specifically, the compound represented by the following general formula (2) can be exemplified.

In the general formula (2), R ¹ , R ² and R ⁵ each independently represents an alkyl group, and m represents an integer of 0 or more. a and b each independently represent 1 to 3, and a + b + c = 4. R ¹ , R ² and R ⁵ are each independently preferably an alkyl group having 1 to 6 carbon atoms, R ¹ and R ⁵ are preferably methyl groups, and R ² is preferably a methyl group or an ethyl group. Further, a is preferably 1, and c is preferably 0 or 1. m is preferably an integer of 0 to 20, and more preferably 1 to 6.

  More specifically, a silane compound represented by the following general formula (3) or (4) is exemplified.

In the general formulas (3) and (4), R ^{1 to} R ⁵ each independently represents an alkyl group, and m represents an integer of 0 or more. R ^{1 to} R ⁵ are preferably an alkyl group having 1 to 6 carbon atoms, R ¹ is preferably a methyl group, and R ^{2 to} R ⁴ are more preferably a methyl group or an ethyl group. m is preferably from 0 to 20, and more preferably from 1 to 6.

  More specifically, the following compounds (1) and (2) can be exemplified.

The pressure-sensitive adhesive composition of the present invention preferably contains 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight of the silane compound (E) with respect to 100 parts by weight of the polyester resin (D). More preferably. If the amount is less than 0.01 parts by weight, improvement in adhesion cannot be expected. On the other hand, if it exceeds 10 parts by weight, it is not preferable because it tends to peel off from the adherend. In the pressure-sensitive adhesive composition of the present invention, the reactivity capable of reacting with the side chain functional group in the polyester resin (D). It is important to contain the compound (F).
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 force is lowered and the heat resistance and heat-and-moisture resistance tend to be lowered.
The resin composition is three-dimensionally cross-linked by the reaction between the hydroxyl group or carboxylic acid group in the polyester resin (D) and the functional group in the reactive compound (F) to ensure adhesion to various substrates and adherends. In addition, since heat resistance and heat-and-moisture resistance under conditions severer than before can be improved, it can be preferably used as a vibration damping member.

  The resin composition of the present invention has various resins, tackifiers, softeners, dyes, pigments, antioxidants, plasticizers, fillers, anti-aging agents, etc., as long as the effects of the present invention are not impaired. May be blended.

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.

  Various foams include polyethylene foam, polypropylene foam, various plastic foams such as polyurethane foam, natural rubber foam, styrene-butadiene rubber foam, chloroprene rubber foam, acrylonitrile-butadiene rubber foam, etc. Various rubber-based foams and the like can be mentioned, and any of these can be suitably used. When obtaining a vibration-damping pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition of the present invention, it is preferable to use various foams having excellent vibration damping properties as the sheet-like substrate.

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 pressure-sensitive adhesive sheet of the present invention can be a vibration-damping pressure-sensitive adhesive sheet by using a sheet-like substrate having a damping function as a sheet-like substrate having no peelability.
For example, (a) a pressure-sensitive adhesive composition is applied to the release-treated surface of a release-treated sheet-like substrate, dried, and a sheet-like substrate having a vibration damping function is laminated on the surface of the pressure-sensitive adhesive layer By doing so, a vibration-damping single-sided pressure-sensitive adhesive sheet can be obtained.

  Alternatively, (a) a pressure-sensitive adhesive composition is applied to the release-treated surface of the release-treated sheet-like substrate and dried to form a first pressure-sensitive adhesive layer, which is separately subjected to another release treatment. The pressure-sensitive adhesive composition is applied to the release-treated surface of the sheet-like substrate and dried to form a second pressure-sensitive adhesive layer, and the first and second sheet-like substrates having a vibration damping function are formed. By sandwiching between the pressure-sensitive adhesive layers, a vibration-damping double-sided pressure-sensitive adhesive sheet can be obtained.

  The peel-off sheet-like substrate covering the surface of the adhesive layer is peeled off from the vibration-damping pressure-sensitive adhesive sheet thus obtained, and the adherend is used for applications where vibration damping, soundproofing, and heat insulation are required. Can be attached to and used.

The adhesive layer prepared from the pressure-sensitive adhesive composition of the present invention has a shear storage modulus at 120 ° C. of 1 × 10 ^{5 to} 5 × 10 ⁶ dyn / cm ² , preferably 5 × 10 ⁵ to. An adhesive layer of 2 × 10 ⁶ dyn / cm ² can be formed. The shear storage modulus can be measured using a viscoelastic spectrometer “RDS-II” manufactured by Rheometric Scientific F.E.
When the shear storage modulus at 120 ° C. of the adhesive layer is smaller than 1 × 10 ⁵ dyn / cm ² , the vibration-damping pressure-sensitive adhesive sheet is attached to an adherend that requires damping properties, and then exposed to high temperature. In such a case, the adhesive layer is softened and heat resistance, creep resistance, etc. are insufficient, and foaming, swelling, and peeling are likely to occur. On the other hand, when the shear storage modulus at 120 ° C. of the adhesive layer is larger than 5 × 10 ⁶ dyn / cm ² , the heat resistance is sufficiently high, but the adhesive layer is hard at room temperature, and the adhesive laminate is damped. When adhering to a member for use, the surface adhesion of the adhesive layer is inferior, so that it does not sufficiently adhere to the surface of the vibration damping member, resulting in a decrease in adhesive strength.

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

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

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

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

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

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

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

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

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

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

After the air in the polymerization tank was replaced with nitrogen gas, the temperature was raised to 100 ° C. in a nitrogen atmosphere while stirring, and the reaction was performed for 8 hours. Subsequently, the said mixture was dripped at constant velocity over 1 hour from the dripping apparatus.
After completion of the addition, 1 part of tetrabutylammonium tetrahydroborate was added after 8 hours with further stirring, and after further aging for 8 hours, 30 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 Then, 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. Then, a toluene / ethyl acetate mixed solution was added and cooled to room temperature to obtain a polyester resin solution.
This reaction solution is light yellow and transparent, has a nonvolatile content of 50.0% by weight, a viscosity of 3,200 mPa · s, an acid value of the resin of 0.1 mgKOH / g, a hydroxyl value of 2.2 mgKOH / g, a glass transition temperature of −30 ° C., The weight average molecular weight was 51,300, the number average molecular weight was 27,000, and the degree of dispersion was 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 2-hydroxyethyl methacrylate 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 2-hydroxyethyl methacrylate 1.5 parts ethyl acetate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the reaction was started at a reflux temperature in a nitrogen atmosphere while stirring. When the polymerization rate reached about 70%, the dropping of the mixture of the acrylic monomer, the polymerization initiator and the organic solvent was started from the dropping device. After completion of dropping, the mixture was further aged for 8 hours with stirring, and then toluene was added and cooled to room temperature to obtain a transparent solution containing an acrylic resin.
This reaction solution is colorless and transparent, has a nonvolatile content of 30.0% by weight, a viscosity of 6,500 mPa · s, an acid value of the resin of 0.1 mgKOH / g, a hydroxyl value of 13.8 mgKOH / g, a glass transition temperature of −40 ° C., a weight The average molecular weight was 750,000.

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

<Aromatic ring content>
Aromatic rings contained in each resin by ¹ H-NMR, ¹³ C-NMR (all manufactured by JEOL Ltd .: ECX-400) and pyrolysis GC-MS using a derivatization method (JEOL Ltd .: DX303HF) The content (mol%) of was determined.

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

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

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

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

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

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

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

Example 1
S510 (3-glycidoxypropyltrimethoxysilane: manufactured by Chisso Corporation) as a silane compound (E) with respect to 100 parts of the solution (solid content: about 50%) of the polyester resin (D) obtained in Synthesis Example 1 0.05 parts of toluene and 25 parts of toluene, and further 2.5 parts by weight of TDI / TMP (trimethylolpropane adduct of tolylene diisocyanate) as a reactive compound (F) were added and stirred well. The pressure sensitive adhesive composition of the present invention was obtained.
About the pressure sensitive adhesive layer formed from the obtained pressure sensitive adhesive composition, the storage elastic modulus (G ') in 120 degreeC was calculated | required by the method mentioned later.
Further, the obtained pressure-sensitive adhesive composition was applied onto a release-treated polyester film so that the thickness after drying was 65 μm, and dried at 80 ° C. for 5 minutes to form an adhesive layer. After drying, one side of a urethane foam sheet having a thickness of 8 mm was bonded to the adhesive layer to obtain a laminate having a configuration of “peelable film / adhesive layer / foam sheet”. Next, the obtained laminate was aged for 1 week under the condition of a temperature of 23 ° C. and a relative humidity of 50% (dark reaction), the reaction of the adhesive layer was advanced, and a vibration-damping material (laminate) that was bonded was obtained. According to the method described later, the adhesive strength to the stainless steel plate (initial and after wet heat aging), high temperature holding power, and anchoring property were evaluated. The results are shown in Table 2.

(Examples 2 to 7)
The same procedure as in Example 1 except that the polyester resin (D) solution obtained in Synthesis Examples 3, 5, 6 to 9 was used instead of the polyester resin (D) solution used in Example 1. Thus, a pressure-sensitive adhesive composition was obtained, and a vibration-damping material that was similarly bonded was produced and evaluated.

(Examples 8 and 9)
Instead of the polyester resin (D) solution used in Example 1, 100 parts by weight of the polyester resin (D) solution obtained in Synthesis Examples 2 and 4, S510; 0.05 part, toluene 25 parts Further, 0.25 parts by weight of HBAP (2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate]) is added as a reactive compound (F), and the mixture is stirred well. A pressure sensitive adhesive composition was obtained. In the same manner as in Example 1, a vibration-damping material subjected to pressure-sensitive adhesion processing was obtained and evaluated in the same manner.

(Example 10)
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that 0.05 part of the compound (1) was used instead of S510 used as the silane compound (E) in Example 1. Then, a vibration-damping material bonded and processed was prepared and evaluated.

Example 11
Instead of the polyester resin (D) solution used in Example 1, the polyester resin (D) solution obtained in Synthesis Example 9 was used, and 0.05 part of the compound (1) was used as the silane compound (E). Except for the above, a pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, and a vibration-damping material bonded and processed in the same manner was prepared and evaluated.

(Comparative Example 1)
In place of the polyester resin (D) used in Example 1, a polyester resin solution having a hydroxyl group at the end of the main chain prepared in Synthesis Example 10 and having no hydroxyl group in the side chain was used. In the same manner as in No. 1, a pressure-sensitive adhesive composition was obtained, and a vibration-damping material bonded in the same manner was prepared and evaluated.

(Comparative Example 2)
Byron RV550 (manufactured by Toyobo Co., Ltd., number average molecular weight: 28000, glass transition) having a hydroxyl group at the end of the main chain and having no hydroxyl group in the side chain instead of the polyester resin (D) used in Example 1 A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that a non-volatile content 50% solution having a temperature of -15 ° C, an acid value of 2 mgKOH / g or less, and a hydroxyl value of 4 mgKOH / g) was used. Similarly, a vibration-damping material bonded and processed was prepared and evaluated.

(Comparative Example 3)
In place of the polyester resin (D) used in Example 1, a lactic acid resin having a hydroxyl group at the end of the main chain and having no hydroxyl group in the side chain: Pyroecol HYD-035 (manufactured by Toyobo Co., Ltd., number In the same manner as in Example 1, except that a 50% non-volatile solution having an average molecular weight of 25000, a glass transition temperature of −5 ° C., an acid value of 2 mgKOH / g or less, and a hydroxyl value of 200 mgKOH / g) was used. A pressure-sensitive adhesive composition was obtained. Although the increase in viscosity was remarkable, it could be coated on a peelable film. However, streaks and the like were observed on the coated surface, and there was no tack on the surface of the pressure-sensitive adhesive layer, and the urethane foam sheet could not be bonded, and a vibration damping material could not be produced. .

(Comparative Example 4)
Instead of the polyester resin (D) used in Example 1, 100 parts of the acrylic resin solution (solid content: about 30%) prepared in Synthesis Example 11 was used as a silane compound (E), and S510 (3-glycidoxy 0.05 parts of propyltrimethoxysilane (manufactured by Chisso Corporation) and 15 parts of toluene, and as a reactive compound (F), 1.5 parts by weight of TDI / TMP are added and stirred well to pressure-sensitive adhesion. An agent composition was obtained. In the same manner as in Example 1, a vibration-damping material subjected to adhesion processing was produced and evaluated.

(Comparative Example 5)
In the same manner as in Example 1 except that 0.05 part of D021A (dimethyldimethoxysilane: manufactured by Chisso Corporation) was used instead of S510 used as the silane compound (E) in Example 1, a pressure-sensitive adhesive. A composition was obtained, and a vibration-damping material bonded in the same manner was prepared and evaluated.

(Comparative Example 6)
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that S510 used as the silane compound (E) in Example 1 was not used. ,evaluated.

(Examples 12 and 13)
Instead of TDI / TMP used as the reactive compound (F) in Example 1, XDI / TMP (trimethylolpropane adduct of xylylene diisocyanate) (Example 12), HMDI / burette (hexamethylene diisocyanate) A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1 except that 2.5 parts by weight of each (burette adduct body) (Example 13) was used. Using these, vibration damping materials bonded and processed in the same manner as in Example 1 were prepared and evaluated.

<< Measurement of shear storage modulus (G ') >>
The pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were coated on a release-treated polyester film and dried in an oven at 150 ° C. to provide an adhesive layer having a thickness of about 0.3 mm. Thereafter, the adhesive layers were repeatedly pasted and laminated to make the thickness of the adhesive layer about 2 mm. This was punched out into a disk shape having a diameter of 8 mm with a punch, and used as a sample for measuring the shear storage modulus. Using a viscoelastic spectrometer “RDS-II” manufactured by Rheometric Scientific F.E., the frequency was 1 Hz, the shear strain was 0.1π radians, and the temperature was 120 ° C. The unit of the shear storage modulus (G ′) is dyne / cm ² (= 0.1 Pa).

<< Evaluation method for adhesion to stainless steel (SUS) plate >>
A test sample having a width of 25 mm was cut out from the vibration damping material (laminate) having the configuration of “peelable film / adhesive layer / foamed sheet” obtained in each example and comparative example, the peelable film was peeled off, and the SUS plate The film was attached to a 2 kg roller and reciprocated once, followed by pressure bonding, and then left for 20 minutes at a temperature of 23 ° C. and a relative humidity of 50%.
Next, using a Tensilon type tensile tester, the 90-degree angle peel strength was measured at a pulling speed of 300 mm / min, and the initial SUS adhesive strength (N / 25 mm) was determined.
In addition, the sample after being left for 20 minutes under the condition of a temperature of 23 ° C. and a relative humidity of 50% is left for 7 days in an atmosphere of a temperature of 60 ° C. and a relative humidity of 95% RH, and then taken out. The adhesion to the SUS plate after aging was determined.

<Evaluation method of anchorage>
A test sample having a width of 25 mm was cut out from the vibration damping material (laminate) having the configuration of “peelable film / adhesive layer / foamed sheet” obtained in each example and comparative example, the peelable film was peeled off, and the SUS plate The film was attached to the substrate and reciprocated once by a 2 kg roller, and then allowed to stand for 24 hours at a temperature of 23 ° C. and a relative humidity of 50%. Thereafter, the interface between the foam and the adhesive layer was forcibly peeled off, and for the peeled-off material, the 90 ° angle peel strength was measured at a pulling speed of 300 mm / min using a Tensilon type tensile tester. And the adhesive strength (N / 25 mm) between the pressure-sensitive adhesive layers were determined and evaluated in the following three stages.
A: “The interface between the foam and the adhesive layer cannot be peeled off, shows a good anchoring property (adhesion), and has no problem in practical use”
Δ: “The interface between the foam and the adhesive layer can be peeled off, but the adhesive strength is 5 N / 25 mm or more, and there is no practical problem”
X: “The interface between the foam and the adhesive layer can be peeled off, but the adhesive strength is 5 N / 25 mm or less, which is a practical problem”

<< Evaluation method of high temperature holding power >>
A test sample having a width of 25 mm was cut out from the vibration damping material (laminate) having the configuration of “peelable film / adhesive layer / foam sheet” obtained in each Example and each Comparative Example, and the bonded portion was 25 mm × 25 mm. After being affixed to a stainless steel plate and left in an environment of 80 ° C. for 20 minutes, a load of 500 g was applied in that environment, and the time until dropping was evaluated in the following three stages.
○: “For 10 hours or more, the displacement is less than 10 mm and does not fall, and there is no practical problem at all”.
Δ: “10 hours or more, it does not fall, but a displacement of 10 mm or more occurs, which is a practical problem”
×: “Fall in less than 10 hours, impractical”

As mentioned above, it turns out that the pressure sensitive adhesive composition of this invention is excellent in adhesive force, high temperature holding power, and anchoring property.
On the other hand, in Comparative Examples 1-6, coexistence of high temperature holding power and anchoring property cannot be performed, and it is unsuitable for a foam base material use (damping material use).

The pressure-sensitive adhesive composition of the present invention can form a polymer having an aromatic ring structure in the main chain skeleton while maintaining a cohesive force peculiar to a polyester structure, and further a silane compound having a specific functional group. Since it contains, the adhesive physical property which was not obtained with acrylic resin can be expressed. Examples thereof include heat resistance, adhesive strength characteristics, and anchoring properties in a laminate as in the present invention. In particular, weather resistance, durability, heat resistance, cold resistance, water resistance, etc. have been emphasized in the application of composite vibration damping materials. In recent years, applications for building materials, home appliances, automotive cushioning materials, gap tapes, etc., and their requirements Performance is becoming increasingly severe. Therefore, the pressure-sensitive adhesive composition of the present invention is considered to be more useful because it can exhibit properties that have been difficult so far as described above.
The pressure-sensitive adhesive composition of the present invention is suitable for use as a composite vibration damping material, and in addition to general labels and seals, paints, elastic wall materials, waterproof coating materials, flooring materials, tackifiers, adhesives Agents, adhesives for laminated structures, sealing agents, molding materials, coating agents for surface modification, binders (magnetic recording media, ink binders, casting binders, fired brick binders, graft materials, microcapsules, glass fiber sizing, etc.) , Urethane foam (rigid, semi-rigid, soft), urethane RIM, UV / EB cured resin, high solid paint, thermosetting elastomer, microcellular, textile processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant , Gel coating agent, resin for artificial marble, impact resistance agent for artificial marble, resin for ink, film (laminate adhesive, protective agent) Film), laminated glass resin, reactive diluent, various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather, can also very effectively used as various resin additives and a raw material thereof or the like.

Claims (10)

A polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain, a glass transition temperature in the range of −80 to 0 ° C., an amino group, a vinyl group, a glycidyl group, a mercapto group, and the following general formula (1 A reactive compound (F) capable of reacting with a hydroxyl group and / or a carboxyl group in the resin (D) and a silane compound (E) having a functional group selected from a β-ketoester group represented by A pressure-sensitive adhesive composition comprising:

(In the general formula (1), R ¹ represents an alkyl group.) The pressure-sensitive adhesive composition according to claim 1, wherein the silane compound (E) is a compound represented by the following general formula (2).

(In the above general formula (2), R ¹ , R ² and R ⁵ each independently represents an alkyl group, m represents an integer of 0 or more, a and b each independently represent 1 to 3, a + b + c = 4) The pressure-sensitive adhesive composition according to claim 2, wherein the silane compound (E) is a compound represented by the following general formula (3) or (4).

(In the general formulas (3) and (4), R ^{1 to} R ⁵ each independently represents an alkyl group, and m represents an integer of 0 or more.) Silane compound (E) 0.01-10 weight part and reactive compound (F) 0.001-20 weight part with respect to 100 weight part of polyester-type resin (D) which has a hydroxyl group and / or a carboxyl group in a side chain. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is contained. A polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain,
A dibasic acid component (A) having no hydroxyl group;
A diol (B) having no carboxyl group;
A trihydric or higher polyhydric alcohol (c1), a trihydric or higher polyhydric carboxylic acid (c2), a compound having two cyclic ether groups in the molecule (c3), two hydroxyl groups and one carboxyl group in one molecule At least one side-chain functional group-introducing component selected from the group consisting of dioxycarboxylic acid (c4) having the above and oxydicarboxylic acid (c5) having two carboxyl groups and one or more hydroxyl groups in one molecule ( The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive composition is a polyester resin (D1) obtained by reacting C). A polyester resin (D) having a hydroxyl group and / or a carboxyl group in the side chain is added to the side chain functional group in the polyester resin (D1) having a hydroxyl group and / or a carboxyl group in the side chain, and a cyclic ester compound ( A polyester resin system (D2) having a ring-opening portion of the cyclic ester compound (G) formed by ring-opening addition of G) as a side chain and a hydroxyl group at the terminal of the ring-opening portion. Item 6. The pressure-sensitive adhesive composition according to Item 5. 7. The pressure-sensitive type according to claim 1, wherein the reactive compound (F) has two or more functional groups capable of reacting with the side chain functional group in the polyester resin (D) in one molecule. Adhesive composition. A single-sided pressure-sensitive adhesive sheet obtained by laminating a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 7 on one surface of a sheet-like substrate. A double-sided pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 7 is laminated on both surfaces of a sheet-like substrate. The pressure-sensitive adhesive sheet according to claim 8 or 9, wherein the sheet-like substrate is a foam.