JP2010270187A - Method for producing resin for pressure-sensitive adhesive, pressure-sensitive adhesive, and pressure-sensitive adhesive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin for a pressure-sensitive adhesive having an antistatic function, and to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive film using the resin for a pressure-sensitive adhesive, the adhesive or adhesive film having good rework property, transparency and moist heat resistance. <P>SOLUTION: The method for producing a resin for a pressure-sensitive adhesive includes steps of: obtaining a copolymer (C) by copolymerizing an active hydrogen group-containing α,β-unsaturated monomer (A) and an α,β-unsaturated monomer (B); and obtaining a copolymer (C-1) making the active hydrogen group in the copolymer (C) react with a cyclic ester (D) to produce a side chain (I). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a pressure-sensitive adhesive having an antistatic function and the resulting pressure-sensitive adhesive.

Due to dramatic advances in electronics in recent years, various flat panel displays (FPD) such as liquid crystal display (LCD), plasma display (PDP), rear projection display (RPJ), EL display, light emitting diode display, etc. It has come to be used as a display device in various fields. For example, these FPDs are not only used indoors, including personal computer displays and liquid crystal televisions, but are also used in vehicles such as car navigation displays.
For such display devices, various films such as an antireflection film for preventing reflection from an external light source and a protective film (protection film) for preventing scratches on the surface of the display device are usually used. For example, in a liquid crystal cell member constituting an LCD, a polarizing film or a retardation film is laminated.
Further, the FPD is not only used as a display device, but may be used as an input device by providing a touch panel function on the surface thereof. A protective film, an antireflection film, an ITO vapor deposition resin film, or the like is also used for the touch panel.
Such a film is attached to an adherend via a pressure-sensitive adhesive and used in a display device. Since the pressure-sensitive adhesive used in the display device is required to have excellent transparency, a pressure-sensitive adhesive mainly composed of an acrylic resin is generally used.

  Of the various films described above, a polarizing film generally has a three-layer structure in which both sides of a polyethenol polarizer are sandwiched between triacetylcellulose-based and cycloolefin-based protective films. For this reason, in a polarizing film, since the dimensional change characteristic of the material which comprises each layer differs, the warp by the dimensional change accompanying the change of temperature or humidity tends to arise.

On the other hand, for example, in an inspection process for a laminate in which a polarizing film is attached to a glass surface for a liquid crystal cell in an LCD manufacturing process, the polarizing film or the like is peeled off when there is air or dust entrainment during lamination. A new polarizing film or the like is reapplied. This re-pasting is also called “rework”.
However, since the laminated body after sticking is generally inspected after being stored at a high temperature for a certain period of time to improve adhesion, not only does the peel strength increase during that time, but it becomes difficult to peel off the polarizing film, After the releasability of the polarizing film is lowered and peeled off, contamination such as adhesive residue and cloudiness occurs on the glass surface.

In addition, since the polyvinyl alcohol film in the polarizing film undergoes a large dimensional change under high temperature or high temperature and high humidity conditions, for example, a laminate comprising a polarizing film / adhesive layer / glass is placed under high temperature or high temperature and high humidity conditions. If the dimensions of the polarizing film are changed, bubbles may be generated at the interface between the adhesive layer and the glass (foaming phenomenon), or the polarizing film may be lifted from the glass and peeled off (floating / peeling phenomenon).
Therefore, by adjusting the molecular weight of the pressure-sensitive adhesive and the degree of crosslinking of the pressure-sensitive adhesive and increasing the adhesive strength, the polarizing film does not foam, float, or peel even under harsh environments against dimensional changes. An attempt was made to do so.

  However, simply trying to resist the dimensional change of the polarizing film simply by increasing the adhesive force, the stress distribution due to the dimensional change of the polarizing film that occurs under high temperature or high temperature and high humidity conditions becomes non-uniform, and the stress is polarized. It concentrates on the four corners and the peripheral edge of the film. As a result, in the display device using the polarizing film, there is a problem that light leaks from the peripheral end portion of the display device, that is, so-called white spots occur.

In general, a pressure-sensitive adhesive sheet has a release liner attached to an adhesive layer for the purpose of protecting the adhesive layer. In use, the release liner is peeled off and attached to an adherend. However, peeling charging has been a problem, for example, the pressure-sensitive adhesive sheet is charged by static electricity when the release liner is peeled off, and dust and dirt are attached to cause appearance defects. Further, for example, in the LCD manufacturing process, rework is also performed as described above.
However, there are cases where troubles occur in liquid crystals and electronic circuits due to static electricity generated during rework. In addition, it has been pointed out that the same trouble occurs when the polarizing film is charged and attached to the glass surface for a liquid crystal cell due to static electricity generated when the release liner is peeled off as described above. Furthermore, the presence of static electricity has a problem of sucking dust and debris and causing defects due to foreign matters, and an early solution has been desired.

  On the other hand, various pressure-sensitive adhesives have been proposed. For example, in order to impart antistatic performance to the laminated members, the resin is often treated with an antistatic agent. Depending on how the antistatic agent is used, it is roughly divided into surface treatment and internal treatment.

  The surface treatment is a treatment of the antistatic agent on the surface of the resin molded product using a technique such as coating, dipping or spraying. A typical example is a water-soluble surfactant, but it has a drawback that its antistatic ability decreases with time.

  The internal treatment is a technique of adding an antistatic agent to the polymer during resin molding. Typical antistatic agents in this technique include conductive fine particles and surfactants.

  Examples of the conductive fine particles include metal powder, metal oxide fine particles such as ITO and ATO, and carbon (Patent Documents 1 to 3). To impart antistatic ability using these materials, A considerable amount must be added, and further advanced techniques are required to evenly distribute them. Further, due to the large amount of addition, the original physical properties are greatly affected, and transparency is lost.

  Surfactants include anionic, cationic, and nonionic surfactants that are inexpensive and are used for various purposes (Patent Document 4). However, they also have the problem of causing bleeding from the surface of the adhesive layer and contaminating others. In addition, the anionic system lacks compatibility with the resin, uniform dispersion is difficult and heat resistance is low, the cationic system has no problem with antistatic properties, but the thermal stability is low. There were problems such as low compatibility with polymers.

  As described above, the pressure-sensitive adhesive containing these surfactants is easily affected by humidity. Under high humidity and below, the cohesive force is reduced by the influence of moisture, and the adhesive layer tends to remain on the adherend. (So-called “glue residue” is likely to occur). Furthermore, these pressure-sensitive adhesives having surfactants and conductive fine particles have poor compatibility, so that the transparency of the coating film is impaired or coloring is observed. In addition, the surfactant or conductive fine particles may move to the interface between the adhesive layer and the adherend (so-called “bleed”), and the pressure-sensitive adhesive such as adhesive force There was also a problem of lowering the performance. Therefore, there is a demand for permanent antistatic performance with no compatibility and good compatibility.

  In addition, an antistatic pressure-sensitive adhesive containing an alkali metal salt as an antistatic agent in propenoic acid-based resin, which is used in electronic tape applications, protective film applications, and polarizing plate fixing applications, respectively, is disclosed. (Patent Documents 5 to 7). However, the use of antistatic pressure-sensitive adhesives containing metal ions in materials used for electrical products and electronic components has the potential for contamination associated with bleeding of metal ions, and further resistance to moisture and heat as an adhesive sheet Decreases.

  Also known is a pressure-sensitive adhesive comprising a propenoic acid-based pressure-sensitive adhesive containing a propenoic acid-based resin and a crosslinking agent and a polyether polyol (Patent Document 8) or a polycaprolactone polyol (Patent Document 9). ing.

However, the pressure-sensitive adhesive film using the pressure-sensitive adhesive described in Patent Documents 8 and 9 is contained when it is exposed to a high temperature or a high temperature and high humidity condition for a long time after being attached to an adherend. Since the polyol being used is easy to absorb moisture due to its high hydroxyl value, extremely small bubbles are generated in a streak-like state at the peripheral edge of the optical film. This phenomenon is called a “crack” because very small bubbles that appear as streaks look like a kind of crack.
In addition, about 10 bubbles of 10 μm or less, which cannot be confirmed unless using an electron microscope, are generated in the center part per 10 m ² .
Further, in a display device of 20 inches or more, the luminance of the light source must be set high from the viewpoint of easy viewing. In the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive described in Patent Document 8, white spots are not regarded as a problem in a display device of less than 20 inches. However, there has also been a problem that white spots are conspicuous in a display device using a high-intensity light source used at 20 inches or more.

On the other hand, in order to improve flexibility and impact resistance, a pressure-sensitive adhesive obtained by copolymerizing a propenoic acid monomer having a ring-opening addition of a lactone is known (Patent Documents 10 and 11).
However, when producing the pressure-sensitive adhesive described in Patent Documents 10 and 11, the radicals generated from the initiator used cause the ester bond to be decomposed and the polymerization is not stably performed. In order to prepare a copolymer, it is possible only with a very small introduction amount. Therefore, although providing effects of flexibility and impact resistance when providing a general molded product, the pressure-sensitive adhesive optical film using the pressure-sensitive adhesive described in Patent Documents 10 and 11 is applied. After sticking to the body, if it is exposed to a heat cycle from low to high temperature under high temperature or high temperature and high humidity conditions, the oxyacid oligomer produced by decomposition during the polymerization is also polycaprolactone polyol. As in the case of blending (Patent Document 9), extremely small bubbles are generated in a streak-like state at the peripheral edge of the optical film.
Furthermore, it is not possible to obtain an antistatic effect only by copolymerizing a propenoic acid monomer having a ring-opening addition of a lactone.

In view of such a situation, the pressure-sensitive adhesive physical properties and optical properties due to the presence of a permanent antistatic effect are suppressed, and it can be used for everything from film labels to electrical and optical applications. A pressure sensitive adhesive was desired.
Furthermore, pressure-sensitive adhesives that have not only antistatic ability but also transparency, solubility in resins and solvents (compatibility), and wet heat resistance have been desired.

Japanese Unexamined Patent Publication No. 01-222141 Japanese Patent Laid-Open No. 05-070760 JP 2005-330409 A JP 04-007350 A Japanese National Patent Publication No. 10-511726 JP 2004-113217 A JP 2006-199873 A Japanese Patent Laid-Open No. 06-128539 JP 2002-053835 A JP 07-258350 A Japanese Patent Laid-Open No. 08-003252

  The present invention relates to a method for producing a pressure-sensitive adhesive resin having an antistatic function, the pressure-sensitive adhesive using the pressure-sensitive adhesive resin and having good reworkability, transparency, and heat-and-moisture resistance. An object is to provide a pressure-sensitive adhesive film.

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, in the first invention, an active hydrogen group-containing α, β-unsaturated monomer (A) and an α, β-unsaturated monomer (B) are copolymerized to produce a copolymer (C ), And
Characterized by comprising a step of reacting an active hydrogen group in the copolymer (C) with a cyclic ester (D) to produce a side chain (I) to obtain a copolymer (C-1). The present invention relates to a method for producing a pressure-sensitive adhesive resin.

  Moreover, 2nd invention makes the terminal of side chain (I) and the sealing compound (E) react, produces | generates side chain (II), and obtains a copolymer (C-2). It is related with the manufacturing method of resin for pressure sensitive adhesives of the said invention characterized by including.

  Moreover, 3rd invention is related with the manufacturing method of resin for pressure sensitive adhesives of the said invention characterized by cyclic ester (D) being an oxyacid condensate (F).

  The fourth invention relates to the method for producing a pressure-sensitive adhesive resin according to the third invention, wherein the oxyacid condensate (F) is a lactone.

  In the fifth invention, the sealing compound (E) is one or more compounds selected from the group consisting of a silane compound, a silanol group-containing compound, an acid anhydride group-containing compound, a monoisocyanate compound, and an amine compound. The present invention relates to a method for producing a pressure-sensitive adhesive resin according to any one of the second to fourth inventions.

  Moreover, 6th invention is related with the pressure sensitive adhesive characterized by including the resin for pressure sensitive adhesives obtained by the manufacturing method in any one of the said invention, and a crosslinking agent (G).

  Moreover, 7th invention is related with the pressure sensitive adhesive film formed by forming the contact bonding layer which consists of a pressure sensitive adhesive of the said invention on a base material (H).

  Moreover, 8th invention is related with the optical adhesive film formed by forming the contact bonding layer which consists of a pressure sensitive adhesive of the said invention on an optical film.

  Moreover, 9th invention is related with the laminated body by which an optical film, the contact bonding layer formed from the pressure sensitive adhesive of the said invention, and glass are laminated | stacked sequentially.

  The pressure-sensitive adhesive containing the pressure-sensitive adhesive resin obtained by the method for producing a pressure-sensitive adhesive resin of the present invention has an excellent antistatic function, and also has good reworkability, transparency, and moisture and heat resistance. . Therefore, a pressure-sensitive adhesive and a pressure-sensitive adhesive film having the above characteristics can be provided.

The method for producing a resin for a pressure-sensitive adhesive according to the present invention comprises copolymerizing an active hydrogen group-containing α, β-unsaturated monomer (A) and an α, β-unsaturated monomer (B). The step of obtaining the copolymer (C), the active hydrogen group in the copolymer (C) and the cyclic ester (D) are reacted to produce the side chain (I), and the copolymer (C It is preferable that the process of obtaining -1) is included.
The copolymer (C) is obtained by copolymerizing a monomer containing an active hydrogen group-containing α, β-unsaturated monomer (A) and an α, β-unsaturated monomer (B). can get. Such copolymerization is performed by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization using a polymerization initiator. In the present invention, solution polymerization is particularly preferable.

The active hydrogen group of the active hydrogen group-containing α, β-unsaturated monomer (A) is preferably a hydroxyl group, a carboxyl group, an amino group, an amide group, a maleimide group, etc., among which a hydroxyl group and a carboxyl group are preferred. Among the active hydrogen group-containing α, β-unsaturated monomer (A), among propenoic acid, 2-methylpropenoic acid, propenoic acid derivatives, 2-methylpropenoic acid derivatives, and other alkenyl group-containing compounds, active The compound which has a hydrogen group can be mentioned.
The α, β-unsaturated monomer (B) is a compound having an α, β-unsaturated group other than the active hydrogen group-containing α, β-unsaturated monomer (A).

  It is preferable that 0.01 to 20% by weight of the active hydrogen group-containing α, β-unsaturated monomer (A) is contained in 100% by weight of the monomer used for copolymerization of the copolymer (C). Although it can be used outside the above numerical range, it may be difficult to solve the problems of the present invention such as antistatic properties, transparency, and heat and humidity resistance.

  The copolymer (C) preferably has a glass transition point (Tg) of −80 to 10 ° C. so that well-balanced adhesive properties (particularly, compatibility between tack and cohesive force) can be obtained, and −60 ˜0 ° C. is more preferable. When the glass transition point is lower than −80 ° C., the cohesive force of the adhesive layer obtained by using the copolymer (C) is lowered, and the floating peeling tends to occur. On the other hand, when the glass transition point exceeds 10 ° C., it is difficult to obtain an adhesive layer having sufficient tack. If the Tg of the homopolymer that can be formed from each monomer that is a constituent component of the copolymer (C) is known, the copolymer weight is determined based on the Tg of each homopolymer and the constituent ratio of each monomer. The Tg of the combined (C) can be theoretically determined.

  The weight average molecular weight (Mw) of the copolymer (C) is preferably 50,000 to 2,000,000, and more preferably 200,000 to 1,500,000. When Mw exceeds 2,000,000, the fluidity of the copolymer (C) is lowered, and the coating property of the pressure-sensitive adhesive may be deteriorated. On the other hand, when Mw is less than 50,000, the cohesive force of the adhesive layer may be insufficient.

  Examples of the propenoic acid derivative or 2-methylpropenoic acid derivative include, for example, methyl (2-methyl) propenoate [combination of methyl propenoate and methyl 2-methylpropenoate together with “methyl (2-methyl) propenoate” write. The same applies hereinafter. ], (2-methyl) propenoic acid ethyl, (2-methyl) propenoic acid 1-propyl, (2-methyl) propenoic acid 2-propyl, (2-methyl) propenoic acid n-butyl, (2-methyl) propene Sec-butyl acid, iso-butyl (2-methyl) propenoate, tert-butyl (2-methyl) propenoate, n-amyl (2-methyl) propenoate, iso-amyl (2-methyl) propenoate, 2-methyl) propenoic acid n-hexyl, (2-methyl) propenoic acid 2-ethylhexyl, (2-methyl) propenoic acid n-octyl, (2-methyl) propenoic acid iso-octyl, (2-methyl) propenoic acid n-nonyl, iso-nonyl (2-methyl) propenoate, decyl (2-methyl) propenoate, dodecyl (2-methyl) propenoate, (2-methyl) propyl (2-methyl) propenoic acid alkyl esters such as octadecyl penate, lauryl (2-methyl) propenoate, stearyl (2-methyl) propenoate; cyclohexyl (2-methyl) propenoate, (2-methyl) propenoic acid Benzyl, (2-methyl) propenoate iso-bonyl, (2-methyl) propenoate phenyl, (2-methyl) propenoate 2-phenoxyethyl, (2-methyl) propenoate 2-oxo-1,2-phenyl (2-methyl) propenoic acid cyclic esters such as ethyl, (2-methyl) propenoic acid 2-oxo-1,2-diphenylethyl; (2-methyl) propenoic acid allyl ester, (2-methyl) propenoic acid 1- Methyl allyl, 2-methylallyl (2-methyl) propenoate, 1-butenyl (2-methyl) propenoate, (2-methyl 2-butenyl propenoate, 3-butenyl (2-methyl) propenoate, 1,3-methyl-3-butenyl (2-methyl) propenoate, 2-chloroallyl (2-methyl) propenoate, (2-methyl) 3-chloroallyl propenoate, (2-methyl) propenoate-o-allylphenyl, 2- (allyloxy) ethyl (2-methyl) propenoate, allyl lactyl (2-methyl) propenoate, citronellyl (2-methyl) propenoate (2-methyl) further containing an unsaturated group such as geranyl (2-methyl) propenoate, rosinyl (2-methyl) propenoate, cinnamyl (2-methyl) propenoate, ethenyl (2-methyl) propenoate, etc. Propenoic acid esters;

(2-methyl) propenoic acid perfluoromethyl, (2-methyl) propenoic acid perfluoroethyl, (2-methyl) propenoic acid perfluoropropyl, (2-methyl) propenoic acid perfluorobutyl, (2-methyl) propene Perfluorooctyl acid, (2-methyl) propenoic acid trifluoromethylmethyl, (2-methyl) propenoic acid 2-trifluoromethylethyl, (2-methyl) propenoic acid diperfluoromethylmethyl, (2-methyl) propene Acid 2-perfluoroethylethyl, (2-methyl) propenoic acid 2-perfluoromethyl-2-perfluoroethylmethyl, (2-methyl) propenoic acid triperfluoromethylmethyl, (2-methyl) propenoic acid 2- Perfluoroethyl-2-perfluorobutylethyl, (2-methyl) propene 2-perfluorohexyl ethyl, (2-methyl) propenoic acid 2-perfluorodecyl ethyl, (2-methyl) such as propenoic acid 2-perfluoroalkyl-hexadecyl ethyl (2-methyl) propenoic acid perfluoroalkyl esters;

  For example, 2-hydroxyethyl (2-methyl) propenoate, 1-hydroxypropyl (2-methyl) propenoate, 2-hydroxypropyl (2-methyl) propenoate, 3-hydroxypropyl (2-methyl) propenoate, 2-hydroxybutyl (2-methyl) propenoate, 4-hydroxybutyl (2-methyl) propenoate, 6-hydroxyhexyl (2-methyl) propenoate, 8-hydroxyoctyl (2-methyl) propenoate, (2 10-hydroxydecyl (methyl) propenoate, 12-hydroxylauryl (2-methyl) propenoate, 18-hydroxystearyl (2-methyl) propenoate, 5-hydroxyamyl (2-methyl) propenoate, (2-methyl) ) 2-Hydroxy-3-phenoxypropyl propenoate, (2-methyl) prope Acid 1,4-cyclohexanedimethanol, (2-methyl) propenoic acid 3-chloroacetoxy-2-hydroxypropyl, 2-ethyl-2- (2-methyl) propenoyloxymethyl-3-methoxycarbonyloxypropanol, etc. Hydroxyl-containing (2-methyl) propenoic acid esters;

  For example, N-methylaminoethyl (2-methyl) propenoate, N-tributylaminoethyl (2-methyl) propenoate, N, N-dimethylaminoethyl (2-methyl) propenoate, (2-methyl) propenoic acid N, N-diethylaminoethyl, pentamethylpiperidinyl (2-methyl) propenoate, tetramethylpiperidinyl (2-methyl) propenoate, 2,4-diamino-6,2-methylpropenoyloxyethyl-s -Amino group-containing (2-methyl) propenoates such as triazine;

  For example, (2-methyl) propenoic acid glycidyl, (2-methyl) propenoic acid (3,4-glycidylcyclohexyl) methyl, (2-methyl) propenoic acid (3-methyl-3-oxetanyl) methyl, (2-methyl) ) Oxygen atom-containing heterocycle-containing (2-methyl) propenoates such as tetrahydrofurfuryl propenoate;

  For example, 3- (2-methylpropane-2-enoyloxypropyl) trimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) triethoxysilane, 3- (2-methylpropan-2- Enoyloxypropyl) triisopropoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) methyldimethoxysilane, 3- (2-methylpropane-2-enoyloxypropyl) methyldiethoxysilane, 3 -(2-methyl) propenoic acid esters containing alkoxysilyl groups such as (propane-2-enoyloxypropyl) trimethoxysilane;

  For example, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(2-methyl) Propane-2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5 '-(2-methyl) propan-2-enoyloxypropylphenyl) -2H-benzo Triazole, 2- (2′-hydroxy-5 ′-(2-methyl) propane-2-enoyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-tert) -Butyl-5 '-(2-methyl) propane-2-enoyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-3' Benzotriazole-based (2-methyl) propenoic acid derivatives such as -tert-butyl-5 '-(2-methyl) propane-2-enoyloxyethylphenyl) -5-chloro-2H-benzotriazole;

  For example, 2-hydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2-((2-methyl) propane-2-enoyloxy} butoxydiphenyl Methanone, 2,2′-dihydroxy-4- {2- (2-methyl) propane-2-enoyloxy} ethoxydiphenylmethanone, 2-hydroxy-4- {2- (2-methyl) propan-2-enoyloxy } Diphenylmethanone-based (2-methyl) propenoic acid derivatives such as ethoxy-4 ′-(2-hydroxyethoxy) diphenylmethanone;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methylphenyl) ) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [ 2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- (2- (2-Methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2-ethoxyphenyl) -6- [2-hydroxy-4- (2- (2- Methyl) propane-2-enoyloxy Ethoxy)]-S-triazine, 2,4-bis (2,4-dimethoxyphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]- S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine, 2,4 Triazine-based (2-(2,4-diethylphenyl) -6- [2-hydroxy-4- (2- (2-methyl) propane-2-enoyloxyethoxy)]-S-triazine Methyl) propenoic acid derivatives Kind;

  For example, ether group-containing (2-methyl) propenoates such as 2-methoxyethyl (2-methyl) propenoate and 2-ethoxyethyl (2-methyl) propenoate;

  For example, alkene oxide-containing (2-methyl) propenoic acid derivatives such as an oxirane adduct of (2-methyl) propenoic acid;

  For example, (2-methyl) propenoic acid phosphooxyethyl, (2-methyl) propenoic acid phosphooxypropyl, (2-methyl) propenoic acid 3-chloro-2-acid phosphooxypropyl, (2-methyl) propene Phosphonyl group-containing (2-methyl) propenoic acid derivatives such as acid acid phosphooxypolyoxyethene oxide, (2-methyl) propenoic acid phosphooxypolyoxypropene oxide and ammonium salts and amine salts thereof;

  For example, di (2-methyl) propenoic acid ethane 1,2-diol, di (2-methyl) propenoic acid, 2,2′-oxyethane-1-ol, di (2-methyl) propenoic acid 3,6-di Oxaoctane-1,8-diol, di (2-methyl) propenoic acid 3,6,9-trioxaundecane-1,11-diol, di (2-methyl) propenoic acid 3,6,9,12-tetra Oxatetradecane-1,14-diol, 2-ethyl-2- (hydroxymethyl) propane-1,3-diol tri (2-methyl) propenoate, 2,2-bis (hydroxy) tri (2-methyl) propenoate Methyl) propane-1,3-diol, 1,1,1-trishydroxymethylethane di (2-methyl) propenoate, 1,1,1-trishydroxy tri (2-methyl) propenoate Chiruetan, tri (2-methyl) polyfunctional (2-methyl) propenoic acid esters such as propenoic acid 1,1,1-tris hydroxymethyl propane.

  Examples of the alkenyl group-containing compound include ethenylbenzene, α-isopropenylbenzene, β-isopropenylbenzene, 1-methylethenylbenzene, 2-methylethenylbenzene, 3-methylethenylbenzene, 1-butylethenyl. Aromatic ethenyl monomers such as tenenylbenzene and 1-chloro-4-isopropenylbenzene;

  For example, 3-ethenylbenzenecarboxylic acid, 4-ethenylbenzenecarboxylic acid, 4-isopropenylbenzenecarboxylic acid, 4-ethenyl-2-hydroxybenzenecarboxylic acid, 4-ethenyl-2-methoxybenzenecarboxylic acid and its sodium Aromatic carboxylic acid monomers such as salts and potassium salts;

  For example, ethenyl phenyl pentyl ether, ethenyl phenyl hexyl ether, ethenyl phenyl heptyl ether, ethenyl phenyl octyl ether, ethenyl phenyl nonyl ether, ethenyl phenyl decyl ether, ethenyl phenyl undecyl ether, ethenyl phenyl dodecyl ether Ethenyl phenyl tridecyl ether, ethenyl phenyl tetradecyl ether, ethenyl phenyl pentadecyl ether, ethenyl phenyl hexadecyl ether, ethenyl phenyl heptadecyl ether, ethenyl phenyl octadecyl ether, ethenyl phenyl nonadecyl ether, Tenenylphenyl eicosyl ether, ethenylphenyl henecosyl ether, ethenylphenyl docosyl ether, ethenylphenyl Butyl butyl ether, ethenyl phenyl methyl pentyl ether, ethenyl phenyl methyl hexyl ether, ethenyl phenyl methyl heptyl ether, ethenyl phenyl methyl octyl ether, ethenyl phenyl methyl nonyl ether, ethenyl phenyl methyl decyl ether, ethenyl phenyl methyl ether Decyl ether, ethenyl phenyl methyl dodecyl ether, ethenyl phenyl methyl tridecyl ether, ethenyl phenyl methyl tetradecyl ether, ethenyl phenyl methyl pentadecyl ether, ethenyl phenyl methyl hexadecyl ether, ethenyl phenyl methyl heptadecyl ether, Ethenyl phenyl methyl octadecyl ether, ethenyl phenyl methyl nonadecyl ether, ethenyl phenyl methyl Lee waist ether, ethenyl phenylmethyl hen eicosyl ether, aromatic ethenyl ether monomer having a long-chain alkyl groups such as ethenyl phenylmethyl docosyl ether;

  For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether System monomers;

  Hexyl 4-ethenylbenzenecarboxylate, octyl 4-ethenylbenzenecarboxylate, nonyl 4-ethenylbenzenecarboxylate, decyl 4-ethenylbenzenecarboxylate, dodecyl 4-ethenylbenzenecarboxylate, 4-ethenylbenzene Tetradecyl carboxylate, hexadecyl 4-ethenylbenzenecarboxylate, octadecyl 4-ethenylbenzenecarboxylate, eicosyl 4-ethenylbenzenecarboxylate, docosyl 4-ethenylbenzenecarboxylate, hexyl 4-isopropenylbenzenecarboxylate, 4 -Octyl isopropenylbenzenecarboxylate, nonyl 4-isopropenylbenzenecarboxylate, decyl 4-isopropenylbenzenecarboxylate, dodecyl 4-isopropenylbenzenecarboxylate, 4-isopropenylbenzenecarboxyl Ethenylbenzene having a long-chain alkyl group such as tetradecyl acid, hexadecyl 4-isopropenylbenzenecarboxylate, octadecyl 4-isopropenylbenzenecarboxylate, eicosyl 4-isopropenylbenzenecarboxylate, docosyl 4-isopropenylbenzenecarboxylate Carboxylate ester or isopropenylbenzene carboxylate monomers;

  For example, tetra (ethene oxide) ethenylphenyl ether, methyltetra (etheneoxide) ethenylphenylether, ethyltetra (etheneoxide) ethenylphenylether, propyltetra (etheneoxide) ethenylphenylether, n-butyltetra (etheneoxide) ) Ethenyl phenyl ether, n-pentyltetra (ethene oxide) ethenyl phenyl ether, tetra (propene oxide) ethenyl phenyl ether, methyl tetra (propene oxide) ethenyl phenyl ether, ethyl tetra (propene oxide) ethenyl phenyl ether, Propoxytetra (propene oxide) ethenyl phenyl ether, n-butyltetra (propene oxide) ethenyl phenyl ether, n Pentaxytetra (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl phenyl ether, methyl poly (ethene oxide) ethenyl phenyl ether, ethyl poly (ethene oxide) ethenyl phenyl ether, poly (propene oxide) ethenyl phenyl Ether, methyl poly (propene oxide) ethenyl phenyl ether, ethyl poly (propene oxide) ethenyl phenyl ether, poly (ethene oxide) ethenyl benzyl ether, methyl poly (ethene oxide) ethenyl benzyl ether, ethyl poly (ethene oxide) ethenyl benzyl Ether, poly (propene oxide) ethenyl benzyl ether, methyl poly (propene oxide) ethenyl benzyl ether Ethyl poly (propene oxide) ethenyl benzyl ether, poly (ethene oxide) ethenyl phenyl ethyl ether, methyl poly (ethene oxide) ethenyl phenyl ethyl ether, ethyl poly (ethene oxide) ethenyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl An ethenylbenzene monomer having a long-chain polyalkene oxide moiety such as ethyl ether, methyl poly (propene oxide) ethenylphenyl ethyl ether, ethyl poly (propene oxide) ethenylphenyl ethyl ether;

  For example, poly (ethene oxide) isopropenyl phenyl ether, methyl poly (ethene oxide) isopropenyl phenyl ether, ethyl poly (ethene oxide) isopropenyl phenyl ether, poly (propene oxide) isopropenyl phenyl ether, methyl poly (propene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethene oxide) isopropenyl benzyl ether, methyl poly (ethene oxide) isopropenyl benzyl ether, ethyl poly (ethene oxide) isopropenyl benzyl ether, poly (propene oxide) isopropenyl benzyl ether Ether, methylpoly (propene oxide) isopropenylbenzyl Isopropenyl monomer having a polyalkene oxide moiety, such as ether;

  For example, mono long chain alkyl ester of dicarboxylic acid such as ethenylphenylnonyl butanedioate, ethenylphenylmethyldecyl hexahydrobenzene-1,2-dicarboxylate, ethenylphenylethyldodecyl benzene-1,4-dicarboxylate Monomer;

  For example, butanedioic acid ethenyl phenyl poly (ethene oxide), hexahydrobenzene-1,2-dicarboxylic acid ethenyl phenyl methyl poly (ethene oxide), benzene-1,4-dicarboxylic acid ethenyl phenyl ethyl poly (ethene oxide) ) Monocarboxylic acid esters of dicarboxylic acids such as 4-ethenylbenzenecarboxylate methyl poly (ethene oxide), 4-ethenylbenzenecarboxylate ethyl poly (ethene oxide), 4-isopropenylbenzenecarboxylate methyl poly (propene oxide), 4-Ethenylbenzenecarboxylic acid ester or polypropenebenzenecarboxylic acid ester having a polyalkene oxide moiety such as ethyl 4- (isopropenylbenzenecarboxylate) poly (propene oxide) Monomer;

  For example, fluorine-containing ethenyl monomers such as perfluoroethene, perfluoropropene, perfluoro (propyl ethenyl ether), ethenylidene fluoride;

  For example, triethyloxysilyl group-containing ethenyl monomers such as ethenyltrimethoxysilane and ethenyltriethoxysilane;

  For example, cis-butenedioic acid diallyl, 2-methylidenebutanedioic acid diallyl, (E) -but-2-enoic acid ethenyl, (Z) -octadeca-9-enoic acid ethenyl, (9Z, 12Z, 15Z) -octadeca- Ethenyl ester-based monomers further containing an unsaturated bond such as ethenyl 9,12,15-trienoate;

  For example, nitrile group-containing ethenyl monomers such as 2-propenenitrile, 2-methyl-2-propenenitrile, 2-cyanoethyl (2-methyl) propenoate;

  For example, 2-propenamide, 2-methyl-2-propenamide, N, N-dimethyl-2-propenamide, N, N-diethyl-2-propenamide, N-methoxymethyl-2-propenamide, N- Ethoxymethyl (2-methyl) propenamide, N- (n-, iso-) butoxymethyl (2-methyl) propenamide, N-methoxyethyl (2-methyl) propenamide, N-ethoxyethyl (2-methyl) Propenamide, N- (n-, iso-) butoxyethyl (2-methyl) propenamide, N- [3- (N ′, N′-dimethylamino) propyl] -2-propenamide, N-isopropyl-2 -Aliphatic amide group-containing ethenyl monomers such as propenamide, N-ethenylmethanamide, N-ethenylacetamide;

 For example, cyclic amide group-containing ethenyl monomers such as 4-propenoylmorpholine, N-ethenyl-2-pyrrolidone, N-ethenyl-2-azehan-2-one;

  For example, nitrogen atom content such as 2-ethenylpyridine, 4-ethenylpyridine, 2-ethenylpiperazine, N-ethenylimidazole, 4-ethenylpiperazine, 2,4-diamino-6-ethenyl-s-triazine Heterocyclic ethenyl monomers;

  For example, amino group-containing ethenyl monomers such as allylamine, p-ethenylamine, N-methyl-N-nitroso-ethenyl, oxetane-2-yl-ethenylamine, oxiranylethenylamine;

  For example, ethenyl esters such as ethenyl ethanoate, ethenyl propanoate, ethenyl pivalate, ethenyl benzenecarboxylate, ethenyl 3-phenyl-2-propenoate;

  For example, alkenyl group-containing sulfonic acid compounds such as ethenylbenzenesulfonic acid, ethenylsulfonic acid, allylsulfonic acid, allyloxybenzenesulfonic acid, 2-methylallylsulfonic acid, 2-methylallyloxybenzenesulfonic acid, ethenylsulfuric acid, etc. , Ammonium ethenylbenzenesulfonate, monomethylammonium ethenylbenzenesulfonate, dimethylammonium ethenylbenzenesulfonate, trimethylammonium ethenylbenzenesulfonate, tetramethylammonium ethenylbenzenesulfonate, ethylammonium ethenylbenzenesulfonate, Diethylammonium ethenylbenzenesulfonate, triethylammonium ethenylbenzenesulfonate, tetraethylammonium ethenylbenzenesulfonate, Such as propylammonium benzenesulfonate, dipropylammonium ethenylbenzenesulfonate, tripropylammonium ethenylbenzenesulfonate, butylammonium ethenylbenzenesulfonate, pentylammonium ethenylbenzenesulfonate or hexylammonium ethenylbenzenesulfonate Alkenyl salts of alkenyl group-containing ethenylbenzene sulfonate, sodium ethenylbenzenesulfonate, potassium ethenylbenzenesulfonate, lithium ethenylbenzenesulfonate, magnesium ethenylbenzenesulfonate, zinc ethenylbenzenesulfonate, ethenylbenzene Metal salts of ethenylbenzene sulfonic acid containing alkenyl group such as iron sulfonate, ammonium ethenyl sulfonate, ethenyls Metal salts and ammonium salts of alkenyl group-containing ethenyl sulfonic acid such as sodium fonate and potassium ethenyl sulfonate, ammonium ethenyl sulfonate, sodium ethenyl sulfonate, potassium alkenyl alkenyl group containing allyl sulfonic acid, sodium ethenyl Metal salts and ammonium salts such as alkylsulfosuccinates, ammonium salts of ethenyloxybenzenesulfonate, sodium ethenyloxybenzenesulfonate, potassium ethenyloxybenzenesulfonate, potassium alkenyl groups containing alkenyl groups and ammonium salts Alkenyl group-containing 2-methyl such as ammonium 2-methylallylsulfonate, sodium methallyl-2-methylallylsulfonate, potassium methallyl-2-methylallylsulfonate Metal salts and ammonium salts of ruallylsulfonic acid, ammonium 2-methylallyloxybenzenesulfonate, sodium 2-methylallyloxybenzenesulfonate, potassium alkenyl group of methallyl-2-methylallyloxybenzenesulfonate 2-methylallyloxybenzene Metal salts and ammonium salts of sulfonic acid, (2-methyl) 2-propenamide sulfonic acid [2-propenamide sulfonic acid and 2-methyl-2-propenamide sulfonic acid are combined to form “(2-methyl) 2- Propenamide sulfonic acid ". The same applies hereinafter. ], Tert-butyl- (2-methyl) 2-propenamidesulfonic acid, alkenyl group-containing sulfonic acids such as (2-methyl) 2-propenamide-2-methyl-1-propanesulfonic acid

  For example, (2-methyl) propenoic acid, 2-carboxyethyl propenoate, 3-phenylpropenoic acid, 2-methylidene succinic acid, cis-butenedioic acid, trans-butenedioic acid, penta-2-enedioic acid, 2- Unsaturated carboxylic acids such as methyl fumaric acid;

  For example, unsaturated carboxylic acid anhydrides such as 2,5-dihydrofuran-2,5-dione, 3-methylidenetetrahydrofuran-2,5-dione, 3-methyl-2,5-dihydrofuran-2,5-dione, etc. Things;

  For example, monoalkyl esters and dialkyl esters of the above unsaturated carboxylic acids;

  For example, glycidyl group-containing ethenyl esters such as glycidyl cinnamate, allyl glycidyl ether, ethenylcyclohexene monooxirane, 1,3-butadiene monooxirane;

  For example, hydroxyl-containing ethenyl esters such as 4-hydroxyethenylbenzene, 1-ethenyl-1-cyclohexanol, and allyl alcohol;

  Examples thereof include halogen-containing ethenyl esters such as chloroethene, 1,1-dichloroethene, and allyl chloride, but are not particularly limited thereto. These may be used alone or in combination.

  Moreover, in obtaining the copolymer (C) used for this invention, the compound which has (alpha), (beta)-unsaturated double bond other than these as needed can also be used, Examples include maleimide derivatives such as, for example, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

  For example, alkenes such as ethene, propene, 1-butene, 2-butene, 2-methylpropene;

Examples thereof include dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like.
In the present invention, as described above,
And those having an active hydrogen group and having a sulfonyl group and a phosphonyl group.

  For example, the above, hydroxyl group-containing compounds having various hydroxyl groups, carboxyl group-containing compounds such as carboxylic acid, sulfonyl group-containing compounds such as alkenyl group-containing amide sulfonic acids, phosphonyl group-containing phosphonyl group compounds, etc. , Sol, amino group-containing, or the like, primary or secondary amino group-containing compounds, amide group-containing compounds such as, and maleimide group-containing compounds such as cyclic esters (described later) In view of reactivity with D) and reactivity with the crosslinking agent (G), it is preferable to have at least one of carboxyl group-containing compounds or hydroxyl group-containing compounds.

In the method for producing a pressure-sensitive adhesive resin of the present invention, the active hydrogen group in the obtained copolymer (C) is reacted with the cyclic ester (D), and the ring-opening addition is performed, whereby the side chain (I). To obtain a copolymer (C-1).
The copolymer (C-1) has a side chain (I), so that when used in a pressure-sensitive adhesive, adhesion to the adherend is improved, and the terminal of the side chain (I) Since the reaction between the active hydrogen group and the cross-linking agent proceeds efficiently and the cohesion is improved by suppressing the plasticization by the side chain (I), there is an advantage that a tough cross-linked structure can be formed.

The ring-opening addition of the cyclic ester (D) may be a single addition of only one molecule, or the cyclic ester (D) is further subjected to ring-opening addition to the active hydrogen group generated at the end of the side chain (I). Multiple ring-opening additions may be performed. When the ring-opening addition is multiplexed in this way, the side chain (I) can be made longer. As a result, the side chain (I) can move more flexibly, so that the active hydrogen group at the end of the side chain (I) can react with the crosslinking agent more efficiently. Moreover, since side chain (I) will have two or more ester bonds, there exists an advantage that affinity with a to-be-adhered body becomes higher.

The cyclic ester (D) is preferably reacted in an amount of 0.2 to 100 mol, more preferably 0.5 to 80 mol, based on 1 mol of the active hydrogen group in the copolymer (C). It is more preferable to react 8 to 60 mol, and particularly preferable to react 1.5 to 40 mol. If it deviates from the above range, both tack and cohesion may not be satisfied when used in a pressure sensitive adhesive.
The copolymer (C) thus obtained preferably has an acid value or a hydroxyl value in the range of 50 to 150 mgKOH / g, more preferably in the range of 50 to 80 mgKOH / g.

  The cyclic ester (D) is preferably an oxyacid condensate (F) in which a hydroxyl group of a hydroxycarboxylic acid and a carboxylic acid are condensed by dehydration within a molecule or between molecules to form a ring structure. This oxyacid condensate (F) may be a dimer or a multimer of trimer or higher as long as it can form a ring by a dehydration reaction of hydroxycarboxylic acid. As the hydroxycarboxylic acid, aliphatic, alicyclic, aromatic and heterocyclic compounds can be used.

  Examples of the aliphatic hydroxycarboxylic acid include hydroxyethanoic acid, 2-hydroxypropanoic acid, hydroxypropenoic acid, α-oxybutanoic acid, α-hydroxyisobutanoic acid, hydroxypentanoic acid, α-hydroxyhexanoic acid, and δ-hydroxyhexanoic acid. 2,3-dihydroxypropanoic acid, 2-oxopropanoic acid, hydroxybutanedioic acid, 2-hydroxypropane-1,2,3-tricarboxylic acid, octanoic acid, hydroxydodecanoic acid, (9Z, 12Z) -octadeca-9 , 12-dienoic acid, α-hydroxytriacontanoic acid, α-hydroxytetratriacontanoic acid, α-hydroxyhexatriacontanoic acid, α-hydroxyoctatriacontanoic acid, α-hydroxytetraacontanoic acid, hydroxy-2, 2-dimethylpropanoic acid, hydride Xipropanoic acid, 6-hydroxypentanoic acid, α-hydroxyheptanoic acid, 10-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 3-hydroxytetradecanoic acid, 16-hydroxyhexadecanoic acid 15-hydroxypentadecanoic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid, α-hydroxyhexaeicosanoic acid, α-hydroxyoctaicosanoic acid, α-hydroxytriacontane Examples include acid, β-hydroxymitetradecanoic acid, 1,3-bis (hydroxymethyl) propanoic acid and the like.

  Examples of alicyclic, aromatic and heterocyclic hydroxycarboxylic acids include 2-hydroxybenzenecarboxylic acid, 3,5-di-tert-butyl-2-hydroxybenzenecarboxylic acid, 3-hydroxybenzenecarboxylic acid, 3 , 4-Dihydroxybenzenecarboxylic acid, 4-hydroxy-3-phenylbenzenecarboxylic acid, 4-hydroxy-3-methoxybenzenecarboxylic acid, 4-hydroxy-3,5-dimethoxybenzenecarboxylic acid, 4'-hydroxy-4- Examples thereof include carboxybiphenyl, 6-hydroxy-2-naphthalene carboxylic acid, 3-hydroxy-2-naphthalene carboxylic acid, and 5-hydroxy-1-naphthalene carboxylic acid.

  These hydroxycarboxylic acids may be organic compounds having a carboxylic acid and a hydroxyl group in one molecule, and are not limited to the above examples.

  Of the above oxyacid condensates, lactones are preferred. Specifically, for example, β-propiolactone, β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, δ-caprolactone, γ- Heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ-nonalactone, ε-caprolactone glycolide, pivalolactone, 7-heptanolide, 8-octonolide, 11-undecanolide, 12-dodecanolide, 15 -Pentadecanolide, 10-oxahexadecanolide, 2-nonene-4-olide, 16-hexadecanolide, 7-decene-4-olide, 9-decene-5-olide, 2-decene-5-olide, 7-decene-5-olide, 6-decene-4-olide, 8-decene-5-olide 8-undecene-5-olide, 4-methyl-cis-7-decene-4-olide, 2-butene-4-olide, 2-methyl-4-butanolide, 3-methyl-4-octanolide, 3-methyl -4-nonanolide, 4-methyl-4-decanolide, cyclopentadecalide, 2,4-decadiene-5-olide, 4-methyl-5-hexene-4-olide, pentano-4-lactone, 4-ethenyl- γ-valerolactone, glucuronolactone, jasmolactone, assy lactone, menthone lactone, mint lactone, masa lactone, wine lactone, panto lactone, homoserine lactone, mevalonolactone, glucono delta lactone, bergapten, umbrella, sclareolide, α-angelica Lactone, β-angelica lactone, 7-decene 1,4-lactone, 9-decene-5-olide, 2,3-dimethyl-2,4-nonadiene-4-olide, dihydroxyactinidiolide, 5-hydroxy-8-undenesenoic acid-δ-lactone 2-hydroxy-3,3-dimethyl-4-butanolide, 1,4-dioxacycloheptadecane-5,17-dione, α-acetyl-γ-butyrolactone α-methyl-β-propiolactone, β- Methyl-α-propiolactone, α, α-dimethyl-β-propiolactone, D-glucono-1,5-lactone, 4-hydroxy-4-methyltetrahydropyran-2-one, phenanthrene-1,10: 9,8-dicarbolactone, 3α-hydroxy-5α-cholano-24,17-lactone and the like.

  The cyclic dimers of hydroxycarboxylic acid that can be used as the cyclic ester (D) in the present invention include 3,6-dimethyl-1,4-dioxane-2,5-dione and hydroxyethane by 2-hydroxypropanoic acid. Examples include 1,4-dioxane-2,5-dione and the like due to an acid.

Among the lactones, those having 4 to 18 carbon atoms constituting the ester ring are preferable from the viewpoint of the length of the side chain (I) formed by ring opening and the reactivity with the active hydrogen group. Specifically, butyrolactone, valerolactone, and caprolactone are particularly preferable.

In the method for producing a pressure-sensitive adhesive resin of the present invention, the side chain (I) of the copolymer (C-1) is reacted with the sealing compound (E) to produce a side chain (II). And it is preferable to include the process of obtaining a copolymer (C-2). By the said process, the ratio of the side chain (I) which has an active hydrogen group from the whole side chain which a copolymer (C-2) has can be reduced. This is because the active hydrogen group at the end of the side chain (I) is necessary for the reaction with the cross-linking agent, but if it is excessive, when used as a pressure-sensitive adhesive, there is a possibility that the heat and humidity resistance may be lowered. . Specifically, when a hydroxyl group or a carboxyl group is present more than necessary at the end of the side chain (I), the above physical properties may be deteriorated.
Further, by using the sealing compound (E), it is possible to simultaneously seal a hydroxyl group and a carboxyl group other than the terminal of the side chain (I) of the copolymer (C-1). Therefore, it is preferable that the terminal of side chain (II) does not have an active hydrogen group. However, the end of the side chain (II) may have a functional group other than a hydroxyl group and a carboxyl group depending on the desired physical properties.

In this invention, 0.1-50 mgKOH / g is preferable and, as for the hydroxyl value of a copolymer (C-2), 0.5-30 mgKOH / g is more preferable. In the case where the copolymer (C-2) has a carboxyl group and a hydroxyl group, and a crosslinking agent (G) capable of reacting with the carboxyl group is used, 0.1 to 10 mgKOH / g is preferable. ˜8 mg KOH / g is more preferred.
On the other hand, the acid value of the copolymer (C-2) is preferably from 0.1 to 50 mgKOH / g, more preferably from 0.5 to 30 mgKOH / g. And when the crosslinking agent (G) which can react with a hydroxyl group is used, 0.5-10 mgKOH / g is preferable. When it is outside the above numerical ranges, there is a risk that the heat-and-moisture resistance when used as a pressure-sensitive adhesive decreases.

  When the hydroxyl value or acid value is lower than 0.1 mgKOH / g, the reactivity of the crosslinking agent (G) with respect to the hydroxyl group or carboxyl group is inferior and the cohesive force of the cured resin may be insufficient. Moreover, when a hydroxyl value or an acid value becomes higher than 50 mgKOH / g, there exists a possibility that the pot life of the pressure sensitive adhesive composition which mix | blended the crosslinking agent (G) may become short.

  The side chain branched from the main chain of the copolymer by the sealing reaction as described above has a side chain capable of crosslinking reaction having an active hydrogen group and a side chain not having an active hydrogen group (sealed). And exist. That is, the copolymer (C-2) of the present invention has a side chain having a crosslinkable functional group (side chain I) and a side not having an active hydrogen group such as a hydroxyl group or a carboxyl group (sealed). A plurality of side chains including the chain (side chain II) are branched from the main chain of the copolymer (C), and the structure of the end of the side chain differs depending on the type of the sealing compound (E). When used as an agent, various properties such as adhesion and durability can be imparted.

  The sealing compound (E) needs to have a functional group capable of reacting with the terminal active hydrogen group of the side chain (I). Specific examples include a silane compound (e1), an acid anhydride group-containing compound (e2), a monoisocyanate compound (e3), and an amine compound (e4). Moreover, sealing compound (E) may be used independently or may be used in combination of 2 or more type.

Examples of the silane compound (e1) used in the present invention include hydrosilanes, alkoxysilanes, chlorosilanes, silanols, silylamines, and cyclic compounds thereof.
Examples of hydrosilanes include trimethylsilane, triethylsilane, tripropylsilane, tributylsilane, trihexylsilane, diethylmethylsilane, butyldimethylsilane, dimethylphenylsilane, triphenylsilane, methylphenylethenylsilane, and pentamethyldisiloxane. , Allyldimethylsilane, tris (trimethylsiloxy) silane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,7,7,7-octamethyltetra Examples thereof include hydrosilanes having a monofunctional Si—H group such as siloxane and 1,3,5,7,9-octaphenylcyclotetrasiloxane.

  Examples of alkoxysilanes include methoxytrimethylsilane, methoxytriethylsilane, methoxydimethylethynylsilane, dimethylethoxyethynylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, allyloxytrimethylsilane, ethoxydimethylethenylsilane, trimethylpropoxysilane, and trimethyl. Isopropoxysilane, 1-methylpropoxytrimethylsilane, butoxytrimethylsilane, isobutoxytrimethylsilane, t-butoxytrimethylsilane, hexyloxytrimethylsilane, 3-aminopropyldimethylethoxysilane, tetrahydrofurfuryloxytrimethylsilane, phenoxytrimethylsilane, cyclohexyl Oxytrimethylsilane, 1-cyclohexenyloxytrime Alkoxysilanes having a monofunctional alkoxy group such as silane, dimethylethoxyphenylsilane, benzyloxytrimethylsilane, methoxytripropylsilane, benzyldimethylethoxysilane, 2-ethylhexyloxytrimethylsilane, octyloxytrimethylsilane, dodecyloxytrimethylsilane Is mentioned.

  Examples of chlorosilanes include trimethylchlorosilane, dimethylethenylchlorosilane, allyldimethylchlorosilane, dimethylpropylchlorosilane, dimethylisopropylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, dimethylphenylchlorosilane, methylphenylethenylchlorosilane, benzyldimethylchlorosilane, Examples thereof include chlorosilanes having a monofunctional chlorosilyl group, such as tripropylchlorosilane, dimethyloctylchlorosilane, tributylchlorosilane, diphenylmethylchlorosilane, diphenylethenylchlorosilane, triphenylchlorosilane, trihexylchlorosilane, dimethyloctadecylchlorosilane, and tribenzylchlorosilane.

  Examples of silanols include silanol compounds having a monofunctional silanol group such as trimethylsilanol, triethylsilanol, and triphenylsilanol.

  Examples of silylamines include trimethylsilyldimethylamine, trimethylsilyldiethylamine, dimethylaminotrimethylsilane, allylaminotrimethylsilane, N-methyl-N-trimethylsilylacetamide, anilinotrimethylsilane, 1-trimethylsilylpyrrole, 1-trimethylsilylpyrrolidone, 1- Silylamines having a monofunctional silylamino group such as trimethylsilylimidazole and 1-trimethylsilyl-1,2,4-triazole; 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3-divinyl Silylamines having a bifunctional silylamino group such as -1,1,3,3-tetramethyldisilazane, N, N′-bis (trimethylsilyl) -N-phenylurea; Examples thereof include silylamines having a trifunctional or higher cyclic silylamino group such as 5,5-hexamethylcyclotrisilazane and 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane.

  Examples of the acid anhydride-containing compound (e2) used in the present invention include those having a anhydride and derivative of a known dicarboxylic acid compound having a molecular weight of about 90 to 500 and an acid anhydride ring of a tri- or higher functional polycarboxylic acid. Any of an aliphatic compound, an aromatic compound, and an alicyclic compound may be included.

  Examples of the aliphatic dicarboxylic acid include ethanedioic acid, propanedioic acid, butanedioic acid, hexanedioic acid, decanedioic acid, nonanedioic acid, octanedioic acid, (Z) -but-2-enedioic acid, chloro (Z) -but-2-enedioic acid, (E) -but-2-enedioic acid, dodecanedioic acid, heptanedioic acid, 2-methyl- (Z) -but-2-enedioic acid, pentanedioic acid Acid, 2-methylidenebutanedioic acid, tetrahydrofuran-2,5-dione, 2,5-dihydrofuran-2,5-dione, and the like, and anhydrides of these aliphatic dicarboxylic acids can be used. Further, derivatives of tetrahydrofuran-2,5-dione (methyltetrahydrofuran-2,5-dione, 2,2-dimethyltetrahydrofuran-2,5-dione, butyltetrahydrofuran-2,5-dione, isobutyltetrahydrofuran-2,5- Dione, hexyl succinic anhydride, octyl succinic anhydride, dodecenyltetrahydrofuran-2,5-dione, phenyltetrahydrofuran-2,5-dione, etc.), tetrahydropyran-2,6-dione derivatives (tetrahydropyran-2) , 6-dione, 3-allyltetrahydropyran-2,6-dione, 2,4-dimethyltetrahydropyran-2,6-dione, 2,4-diethyltetrahydropyran-2,6-dione, butyltetrahydropyran-2 , 6-dione, hexyltetrahydropyran 2,6-dione etc.), derivatives of 2,5-dihydrofuran-2,5-dione (2-methyl 2,5-dihydrofuran-2,5-dione, 2,3-dimethyl 2,5-dihydrofuran) -2,5-dione, butyl 2,5-dihydrofuran-2,5-dione, pentyl 2,5-dihydrofuran-2,5-dione, hexyl 2,5-dihydrofuran-2,5-dione, octyl 2,5-dihydrofuran-2,5-dione, decyl 2,5-dihydrofuran-2,5-dione, dodecyl 2,5-dihydrofuran-2,5-dione, 2,3-dichloro 2,5- Anhydrous derivatives such as dihydrofuran-2,5-dione, phenyl 2,5-dihydrofuran-2,5-dione, 2,3-diphenyl 2,5-dihydrofuran-2,5-dione, etc.) can also be used. .

  Examples of the aromatic dicarboxylic acid include benzene-1,2-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, 2,5-dimethylbenzene-1,4-dicarboxylic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, bicyclo [2,2,1] hept-2-enedicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, Examples thereof include phenyl-2,3-dihydro-1H-indene dicarboxylic acid, and anhydrides of these aromatic dicarboxylic acids can be used. Further, 1,3-dihydroisobenzofuran-1,3-dione, 4-methyl-1,3-dihydroisobenzofuran-1,3-dione and the like can be mentioned, and hexahydro-1,3-dihydroisobenzofuran- 1,3-dione derivatives ((3-methyl-hexahydro-1,3-dihydroisobenzofuran-1,3-dione, 4-methyl-hexahydro-1,3-dihydroisobenzofuran-1,3-dione), Derivatives of tetrahydro-1,3-dihydroisobenzofuran-1,3-dione (1,2,3,6-tetrahydro-1,3-dihydroisobenzofuran-1,3-dione, 3-methyl-1,2, 3,6-tetrahydro-1,3-dihydroisobenzofuran-1,3-dione, 4-methyl-1,2,3,6-tetrahydro-1,3-dihydroiso 1,3-dihydroisobenzofuran-1,3-dione such as Nzofuran-1,3-dione, methylbutenyl-1,2,3,6-tetrahydro-1,3-dihydroisobenzofuran-1,3-dione) Derivatives can also be used.

  Examples of the alicyclic dicarboxylic acid include dimer acid, 1,4-cyclohexyl dicarboxylic acid, 1,3-cyclohexyl dicarboxylic acid, 1,2-cyclohexyl dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and the like. The anhydrides of these alicyclic dicarboxylic acids and the like can be used.

  Furthermore, 4,5,6,7,8,8-hexachloro-3a, 4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione, 1,4,5,6,7, 7-hexachloro-5-norbornene-2,3-dicarboxylic acid anhydride, biphenyldicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, endomethylene-1,2,3,6-tetrahydro-1 , 3-dihydroisobenzofuran-1,3-dione, methyl-3,6-endomethylene-1,2,3,6-tetrahydro-1,3-dihydroisobenzofuran-1,3-dione, 1,2- Cyclohexanedicarboxylic acid anhydride, 1-cyclopentene-1,2-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, o Tahidoro dioxo-4,5-isobenzofurandione carboxylic anhydride, and the like.

  As what has an anhydride ring of polycarboxylic acid more than trifunctional, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid is mentioned, for example. Examples of the trifunctional or higher polycarboxylic acids having two or more anhydride rings include 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic acid. Dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tri Carboxycyclopentyl ethane dianhydride, 2,3,5,6-tetracarboxycyclohexane dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, 3,5,6-tricarboxynorbornane-2- Ethanoic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohex 1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic anhydride, 1,2 , 4,5-benzenetetracarboxylic dianhydride, ethene oxide di-1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid ester, propene oxide di-1,3-dihydro-1,3 -Dioxo-5-isobenzofuran carboxylic acid ester, butene oxide di-1,3-dihydro-1,3-dioxo-5-isobenzofuran carboxylic acid ester, 3,3 ', 4,4'-benzophenone tetracarboxylic acid Anhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 2,2 ′, 3 , 3′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, naphthalene-1,8 : 4,5-tetracarboxylic dianhydride, 4,4 ′-(hexafluoropropylidene) diphthalic anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-Dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride Anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′- (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic Acid dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (tri Phenylbenzenedicarboxylic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylbenzenedicarboxylic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis [4- (3,4-dicarboxyl) Phenoxy) phenyl] fluorene anhydride, ethene oxide bis (anhydrotrimellitate), 3,4-dicarboxy-1,2,3,4 -Tetrahydro-1-naphthalenebutanedioic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalenebutanedioic dianhydride, 9,9-bis ( 3,4-dicarboxyphenyl) fluorene dianhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, methyl nadic anhydride, allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylic anhydride, methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, allylmethylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylic acid anhydride, methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, and the like.

  These acid anhydrides can be used alone or in combination of two or more as the acid anhydride-containing compound (e2). Use of a cyclic anhydride-containing compound having one anhydride ring is preferable because a pressure-sensitive adhesive excellent in adhesiveness, heat resistance, moist heat resistance and transparency can be obtained.

  Examples of the monoisocyanate compound (e3) used in the present invention include methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, octyl isocyanate, decyl isocyanate, octadecyl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, p. -Chlorophenyl isocyanate, p-nitrophenyl isocyanate, 2-chloroethyl isocyanate, 2,4-dichlorophenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, trichloroacetyl isocyanate, chlorosulfonyl isocyanate, (R)-(+)-α -Methylbenzyl isocyanate, (S)-(-)-α-methylben Diisocyanate, (R)-(−)-1- (1-naphthyl) ethyl isocyanate, (R)-(+)-1-phenylethyl isocyanate, (S)-(−)-1-phenylethyl isocyanate, p -Toluenesulfonyl isocyanate and the like.

  The monoisocyanate compound (e3) used in the present invention can be used alone or in combination of two or more.

  As the amine compound (e4) used in the present invention, a known compound containing a primary amino group can be used. For example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, t-butylamine, pentylamine, isopentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, diisobutylamine, nonylamine, decylamine, Undecylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine, amylamine, 2-methyl-3-pentylamine, 3-isobutoxypropylamine, 3-methoxypropylamine, 3- Propoxypropylamine, 3-butoxypropylamine, 3- (2-ethylhexyloxy) propylamine, 3-decyloxypropylamine, laurylamine Myristylamine, cetylamine, coconutamine, stearylamine, oleylamine, 3-lauryloxypropylamine, 3-myristyloxypropylamine, beef tallow amine, polyoxypropenamine, polyoxyetheneamine, 2-aminoethanol, 6-aminoca Aliphatic amines such as pronitrile and rosinamine;

  For example, cyclohexylamine, aniline, benzylamine, phenethylamine, p-methoxyphenethylamine, 1-phenylethylamine, 1- (4-methylphenyl) ethylamine, 1- (3-methoxyphenyl) ethylamine, 2- (phenylmethoxy) cyclopentane Amine, 1- (1-naphthyl) ethylamine, 1- (2-naphthyl) ethylamine, 5-aminoindane, 1-aminotetralin, 1-methyl-3-phenylpropylamine, 1-amino-3-phenoxy-2-propanol O-toluidine, 2-ethylaniline, 2-fluoroaniline, o-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 1-aminopiperidine, N-amino -4-pipecoli N-aminoethylpiperidine, N-aminoethyl-2-pipecoline, N-aminoethyl-4-pipecoline, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N -Aminobutylpiperidine, 4-aminomethyl-1-butylpiperidine, N-aminohexylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, N-aminobutylmorpholine, N-aminohexylmorpholine, 3-amino-1 -Benzylpyrrolidine, 1-benzyl-2-methyl-3-aminopyrrolidine, 1-amino-4-methylpiperazine, furfurylamine, aminopyrazine, 2-aminomethylpyrazine, 2-aminoethylpyrazine, pyrazineamide, 5-methyl Pyrazinamide, 2- Mino-3,5-dibromopyrazine, picolinamide, isonicotinamide, 2-aminonicotinic acid, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-methylpyridine, 2-aminomethyl Pyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 2-amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine, 2-amino-3-nitropyridine, 2-amino-5-nitropyridine, 3-amino-2-chloropyridine, 4-amino-2-chloropyridine, 2-amino-5-chloropyridine, 2-amino-3 , 5-dichloropyridine, 3-amino-2,6-dichloropyridine, 3-amino-2-chloro-4-picoline, 2 -Amino-3,5-dichloro-6-methylpyridine, 2-amino-5-chloro-3-methylpyridine, 3-amino-3,5-dichloro-4-methylpyridine, 4-amino-3,5- Examples thereof include amines possessing an alicyclic, aromatic or heterocyclic ring structure such as dichloro-4,6-dimethylpyridine and 3-aminoethyl-6-chloropyridine.

In the present invention, the side chain (II) is formed when the terminal active hydrogen group of the side chain (I) is a hydroxyl group, the sealing compound (E) is a silane compound or a monoisocyanate compound and is monofunctional. Is preferably used. Moreover, when the terminal active hydrogen group of side chain (I) is a carboxyl group, it is preferable to use an amine compound for sealing compound (E).

  In the present invention, by changing the structure of the side chain (II) of the copolymer (C-2) depending on the type of the sealing compound (E) used, various functions are imparted when used in a pressure-sensitive adhesive. be able to. For example, when a silane compound is used, the adhesion can be improved, for example, the adhesion to glass is improved. Moreover, when a monoisocyanate compound is used, heat resistance and heat-and-moisture resistance improve by the urethane bond to form. Further, when an amine compound is used, the antistatic function can be improved by the amide bond or acid-base bond that is formed.

  In the present invention, a catalyst may be appropriately used in the reaction for forming the side chain (I) and the reaction for forming the side chain (II). Catalysts include ammonia, amines, quaternary ammonium salts, quaternary phosphonium salts, alkali metal hydroxides, alkaline earth metal hydroxides, Lewis acids, tin, lead, titanium, iron, zinc, zirconium, Examples include organometallic compounds containing cobalt and the like, metal halides, and the like.

  Examples of amines include triethylamine, pyridine, phenylamine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, N-methylpiperidine, cyclohexylamine, n-butylamine, dimethyloxazoline, imidazole, N-methylimidazole, N, N. -Dimethylethanolamine, N, N-diethylethanolamine, N, N-dimethylisopropanolamine, N-methyldiethanolamine and the like can be mentioned.

  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-butenedininitrate-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 ethanoate, zirconium benzenecarboxylate, 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 ethanoate, lead (Z) -octadeca-9-enoate, lead 2-ethylhexanoate, lead benzenecarboxylate, lead naphthenate and the like.

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

  Examples of the organic cobalt compounds include cobalt ethanoate, cobalt benzenecarboxylate, and cobalt 2-ethylhexanoate.

  Examples of the organic zinc compounds include zinc ethanoate, zinc ethanedioate, 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 ethanoate, germanium oxide, antimony trioxide, aluminum trichloride, zinc chloride, titanium chloride and the like can be mentioned. These catalysts may be used alone or in combination of two or more. As a usage-amount of a catalyst, it is preferable to use 0.0001-10 weight part with respect to a total of 100 weight part of a copolymer (C-1) and a sealing compound (E), 0.0001-1 weight part is used. A range is more preferred. If the amount exceeds 10 parts by weight, the product may be colored, or the catalyst that has not been deactivated may adversely affect the adhesive properties.

  It is preferable that the pressure sensitive adhesive of this invention contains the resin for pressure sensitive adhesives obtained by the above-mentioned manufacturing method, and a crosslinking agent (G).

  The crosslinking agent (G) used in the present invention is a compound having a functional group capable of reacting with a hydroxyl group, a carboxyl group, an amino group, an amide group, a maleimide group, or the like, which the pressure-sensitive adhesive resin has. Examples of such compounds include polyisocyanate compounds, oxirane compounds, amine compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, melamine compounds, and metal chelate compounds. These compounds are required to have two or more functional groups in the molecule.

  When the functional group of the pressure-sensitive adhesive resin is a carboxyl group, examples of the crosslinking agent (G) include a polyisocyanate compound, an amino compound, an aziridine compound, an oxazoline compound, a melamine compound, and a metal chelate compound. When the active hydrogen group in the copolymers (C), (C-1) and (C-2) is a hydroxyl group, examples of the crosslinking agent (G) include polyisocyanate compounds. Among these, a polyisocyanate compound is particularly preferably used because it is 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-propene diisocyanate, 2,3-butene diisocyanate, 1,3-butene 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.

  Further, 2-methylpentane-2,4-diol adduct of the above polyisocyanate, trimer having an isocyanurate ring, and the like can be used in combination. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and these polyisocyanate modified products can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as a 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 using a polyisocyanate compound as a crosslinking agent (G), a well-known catalyst can be used as needed for reaction promotion. For example, a tertiary amine compound, an organometallic compound, etc. are mentioned, and it is possible to use alone or in combination.

  Examples of the tertiary amine compound include triethylamine, triethenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like. it can.

Examples of organometallic compounds include tin compounds and non-tin compounds.
Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate , Triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
Examples of the non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, (Z) -octadeca-9-leadate, 2-ethylhexanoate, lead benzenecarboxylate, naphthene. Lead type such as lead acid, iron type such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt type such as cobalt benzenecarboxylate and cobalt 2-ethylhexate, zinc naphthenate, zinc 2-ethylhexanoate, etc. Examples thereof include zinc-based and zirconium naphthenate.
Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.

  Among the crosslinking agents (G), examples of oxirane compounds include 2,2-bis (hydroxyphenyl) propane / 2-chloromethyloxirane type oxirane resins, 2,2-bis (hydroxyphenyl) methane type, 2 , 2-bis (4-hydroxyphenyl) ethane type, 2,2-bis (4-hydroxyphenyl) butane type, 4,4′-sulfonyldiphenol type, 1,1-dichloro-2,2-bis (4 -Hydroxyphenyl) ethene type, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene type, 2,2-bis (4-hydroxy-3-methylphenyl) propane type, 2,2 -Bis (4-hydroxy-3-methylphenyl) methane type, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane type, 2,2-biphenyl (4-hydroxy-3,5-dimethylphenyl) propane type, 2,2-bis (4-hydroxycyclohexyl) propane type, 2,2-bis (2-hydroxy-5-biphenylyl) propane type and these Copolymer-type oxirane resin, phenol novolak type, orthocresol novolak type, para-tertiary butylphenol novolak type, paraoctylphenol novolak type, nonylphenol novolak type and co-condensation type oxirane resins, ethene oxide diglycidyl ether, polyethene Oxide diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, 2-methylpentane-2,4-diol triglycidyl ether, Examples thereof include diglycidylphenylamine, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, and the like.

Among the crosslinking agents (G), examples of amine compounds are preferably polyamines having two or more primary amino groups, and from the viewpoint of excellent curing speed, primary amino groups that are not directly bonded to the aromatic ring. An aliphatic polyamine (which may contain an aromatic ring in its skeleton) which is a polyamine having two or more is preferable.
Aliphatic polyamines include 2,5-dimethyl-2,5-hexamethylenediamine, mensendiamine, 1,4-bis (2-amino-2-methylpropyl) piperazine, and propylene branched carbon at both ends of the molecule. Polypropene oxide (propene oxide skeleton diamine, such as “Jeffamine D230” and “Jephamine D400” manufactured by Sun Techno Chemical Co., Ltd., etc.), propene skeleton triamine, such as “Jeffamine T403”, etc. Ethenediamine, propenediamine, butenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethenehexamine, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine, 1,2-diamino Propane, iminobispropylamine, methyl _{iminobispropylamine, H 2 N (CH 2 CH} 2 O) 2 (CH 2) 2 NH 2 [ Sun Techno Chemical Co., Ltd. "Jeffamine EDR148" (ethene oxide skeleton diamine)] or the like Polyether skeleton diamine, 1,5-diamino-2-methylpentane (“MPMD” manufactured by DuPont Japan), metaxylylenediamine (MXDA), polyamidoamine (Sanwa Chemical) “X2000”), isophoronediamine, 1,3-bisaminomethylcyclohexane (“1,3BAC” manufactured by Mitsubishi Gas Chemical Company), 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3, 5-Trimethyl-cyclohexylamine, dimethyleneamine with norbornane skeleton Manufactured by Mitsui Chemicals, Inc. "NBDA"), and the like.
Among these, since the curing rate is particularly high, 1,3-bisaminomethylcyclohexane, dimethyleneamine having a norbornane skeleton, metaxylylenediamine, H ₂ N (CH ₂ CH ₂ O) ₂ (CH ₂ ) ₂ NH ₂ (Ethene oxide skeleton diamine), propene oxide skeleton diamine, propene oxide skeleton triamine, and polyamidoamine (trade name: X2000) are useful.

  Ketimines, which are the reaction products of these polyamines and ketones, are also included in the amino compounds, and 1-phenylethanone or 1-phenylethane-1-one is used from the viewpoints of stability, adjustment of reactivity, and overcoatability. 1-phenylethanone or 1-phenylethanone or 1-phenylethan-1-one and norbornane skeleton dimethyleneamine (NBDA); 1-phenylethanone Or obtained from 1-phenylethane-1-one and metaxylylenediamine; 1-phenylethanone or 1-phenylethane-1-one and Jeffamine EDR148, which is a diamine having an ethene oxide or propene oxide skeleton , Jeffermin D230, Jeffermin D400 etc. or B pen oxide triamines such as those obtained from JEFFAMINE T403 like a skeleton may be used.

  Among the crosslinking agents (G), examples of the aziridine compound 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) 2-methylpentane-2,4-diol-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) ) -1,3,5-triazine, 2-methylpentane-2,4-diol tris [3- (1-aziridinyl) propionate], 2-methylpentane- , 4-diol tris [3- (1-aziridinyl) butyrate], 2-methylpentane-2,4-diol tris [3- (1- (2-methyl) aziridinyl) propionate], 2-methylpentane-2, 4-diol 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 and the like. That.

  Among the crosslinking agents (G), as the carbodiimide compound, 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.

  Among the crosslinking agents (G), as the oxazoline compound, a compound having two or more oxazoline groups in the molecule is preferably used. Specifically, 2′-methylenebis (2-oxazoline), 2,2′-ethenebis is used. (2-oxazoline), 2,2'-ethenebis (4-methyl-2-oxazoline), 2,2'-propenebis (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-phenylenebis ( -Phenyl-2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylene Bis (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 ' -Bis (4-ethyl-2-oxazoline), 2,2'-bis (4-phenyl-2-oxazoline) and the like can be mentioned. Alternatively, ethenyl monomers such as 2-isopropenyl-2-oxazoline and 2-isopropenyl-4,4-dimethyl-2-oxazoline, and other monomers that can be copolymerized with these ethenyl monomers. It may be a copolymer with a monomer.

  Among the crosslinking agents (G), the melamine compound is a compound having a triazine ring in the molecule, such as melamine, benzoguanamine, cyclohexanecarboguanamine, methylguanamine, ethenylguanamine, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine and the like. Can be mentioned. These low-condensates, alkyl etherified formaldehyde resins and aminoplast resins may also be used.

  Among the crosslinking agents (G), examples of the metal chelate compounds include aluminum, iron, copper, zinc, tin, titanium, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium and other polyvalent metals such as acetylacetone and acetoethane. Examples thereof include compounds coordinated to ethyl acid. These crosslinking agents (G) can be used alone or in combination.

  Further, the crosslinking agent (G) is preferably used in an amount of 0.001 to 50 parts by weight, more preferably 0.01 to 30 parts by weight, based on 100 parts by weight of the pressure-sensitive adhesive resin. When the usage-amount of a crosslinking agent (G) exceeds 50 weight part, there exists a possibility that the adhesiveness of a pressure sensitive adhesive may fall. On the other hand, if the amount is less than 0.001 part by weight, a sufficient cross-linked structure cannot be obtained, so that the cohesive force of the pressure-sensitive adhesive is lowered, and the heat resistance and moist heat resistance may be lowered.

  The pressure-sensitive adhesive of the present invention preferably contains an organic solvent. In addition, various resins, softeners, dyes, pigments, antioxidants, tackifiers, silane coupling agents, plasticizers, fillers, antistatic agents, antiaging agents, etc., as long as the effects of the present invention are not impaired. May be blended.

  In the pressure-sensitive adhesive of the present invention, since the side chain (I) and the side chain (II) have many ester bonds, they exhibit a pendant state in which many unpaired electrons of this ester bond exist, Since the liquid crystal cell is oriented near the glass interface, the distance between unpaired electrons is shortened, and a network is formed through the unpaired electrons to form a conductive path. On this conductive path formed by side chain (I) and side chain (II), ion conduction is likely to occur due to moisture in the absorbed air and ionization of the catalyst used in step (2) and step (3). Therefore, the antistatic performance is improved. Therefore, it functions as a permanent antistatic performance without having a normal antistatic agent. Moreover, since the heat resistance and heat-and-moisture resistance under conditions severer than before can be improved, it can be preferably used for an optical member.

The copolymer (C-23) used in the present invention is conventionally preferably produced by the following method.
Step (1): copolymerization using an active hydrogen group-containing α, β-unsaturated monomer (A), α, β-unsaturated monomer (B), an organic solvent, and a polymerization initiator. A copolymer (C) is produced. The polymerization temperature is preferably 50 to 150 ° C, more preferably 60 to 100 ° C, and further preferably 70 to 90 ° C. When polymerized within the above range, the weight average molecular weight can be easily controlled.
Step (2): The copolymer (C) is subjected to a ring-opening addition reaction for forming a side chain (I) using a cyclic ester compound (D) and, if necessary, an organic solvent and a catalyst. A coalescence (C-1) is produced. The reaction temperature is preferably 50 to 180 ° C, more preferably 80 to 120 ° C.
Step (3): The copolymer (C-1) is subjected to a sealing reaction to form a side chain (II) using a sealing compound (E) and, if necessary, an organic solvent and a catalyst. A coalescence (C-2) is produced. The reaction temperature is preferably 50 to 180 ° C, more preferably 80 to 120 ° C.
In addition, when the reaction temperature of a process (2) and a process (3) is less than a lower limit, progress of reaction is slow. On the other hand, if the upper limit is exceeded, side reactions such as decomposition and coloring may occur.

  The pressure-sensitive adhesive film of the present invention is obtained by forming an adhesive layer made of the above-mentioned pressure-sensitive adhesive on the substrate (H). As a method for producing a pressure-sensitive adhesive film, for example, specifically, a pressure-sensitive adhesive is applied to the release-treated surface of a release liner, dried, and a base material (H) is bonded, or a base material ( H) is a method in which a pressure-sensitive adhesive is applied and dried, and the release treatment surface of the release liner is bonded to the surface of the adhesive layer.

  Examples of the substrate (H) include cellophane, various plastic sheets, and sheet-like substrates such as paper. Moreover, a base material can also be used independently, The thing in the multilayer state formed by laminating | stacking a several base material can also be used. Further, a sheet-like base material whose surface is peeled can also be used.

  Various plastic sheets are also referred to as various plastic films, such as polyethenol film (also referred to as PEA film), triacetyl cellulose film (also referred to as TAC film), polypropene (also referred to as PP film), polyethene (also referred to as PE film), poly Polyolefin resin films such as cycloolefin (also referred to as COP film), ethene-ethanoic acid ethenyl copolymer (also referred to as EVA film), polyethene terephthalate (also referred to as PET film), polybutene terephthalate (also referred to as PBT film), etc. Polyester resin film, polycarbonate resin film (also called PC film), polynorbornene resin film, polyarylate resin film , Propenoic acid resin film, polyphenylene sulfide resin film (also referred to as PPS film), polyethenylbenzene resin film (also referred to as PST film), ethenyl resin film, polyamide resin film (also referred to as PA film) ), A polyimide resin film (also referred to as a PI film), an oxirane resin film, and the like. Among these substrates, it is particularly preferable to use a sheet-like substrate such as a PEA film, a TAC film, a polyolefin resin film, a polyester resin film, or a PC film as an optical film.

  Moreover, in this invention, it is also preferable to set it as the optical adhesive film which used the optical film for the base material (H) and the adhesive layer which consists of a pressure sensitive adhesive was formed on the said optical film. The optical adhesive film can also be used for display applications such as laminating on a liquid crystal cell or the like.

Examples of the optical film used in the present invention include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film.
A polarizing film, also called a polarizing plate, is a multilayer structure film in which both sides of a polyethenol polarizer are sandwiched between two triacetylcellulose-based protective films (hereinafter referred to as “TAC film”) and two cycloolefin-based films. It is.

After applying a pressure sensitive adhesive to a release liner or optical film by an appropriate method according to a conventional method, if the pressure sensitive adhesive composition contains a liquid medium such as an organic solvent or water, a method such as heating If the liquid medium is removed or the pressure-sensitive adhesive does not contain a liquid medium that should be volatilized, the molten resin layer is cooled and solidified to form an adhesive layer on the release liner or optical film. Can be formed.
The thickness of the pressure sensitive adhesive layer is preferably 0.1 μm to 200 μm, and more preferably 0.1 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 peelable sheet or the like is not particularly limited, and may be a Meyer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, A knife coater, reverse coater, spin coater or the like is preferably used.

The laminate of the present invention is obtained by sequentially laminating a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention and glass using an optical film as a substrate. Here, the optical film is preferably a polarizing film. The glass may be the glass surface of a liquid crystal cell.
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 resin composition, the film thickness, and the selected solvent, heating with hot air of about 60 to 180 ° C. is usually sufficient.
Film film

  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 copolymer (C) (step 1)>
(Synthesis Example 1)
A polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, a polymerization reactor equipped with a nitrogen introduction tube, and a dropping device, the following monomers (active hydrogen group-containing α, β-unsaturated monomer) (A), and α, β-unsaturated monomer (B)), catalyst, and solvent were respectively charged in the following ratios.

[Polymerization tank]
N-butyl propenoate (B) 29.5 parts methyl propenoate (B) 15 parts propenoic acid (A) 5 parts 2-hydroxyethyl 2-methylpropenoate (A) 0.5 part methyl ethanoate 30 parts 2, 0.05 parts of 2'-azobisisobutyronitrile [Drip device]
N-butyl propenoate (B) 40 parts propenoic acid (A) 10 parts ethyl ethanoate 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 reflux temperature in a nitrogen atmosphere with stirring. When the polymerization conversion reached about 70%, the dropping of the mixture of the α, β-unsaturated compound, 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 added with 197 parts of methyl ethanoate and cooled to room temperature to obtain a pressure-sensitive adhesive resin solution containing the copolymer (C).
This solution is colorless and transparent, has a nonvolatile content of 30.1% by weight and a viscosity of 9,000 mPa · s. The copolymer (C) has an acid value of 194.0 mgKOH / g, a hydroxyl value of 2.0 mgKOH / g, The glass transition temperature was −25 ° C. and the weight average molecular weight was 1,425,000.

<Production of Copolymer (C-1) (Step 2)>
A polymerization reaction device having a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube attached to the polymerization tank was prepared, and the copolymer (C) solution obtained in step (1) was added to the polymerization tank and the dropping device, The cyclic ester (D), the catalyst and the organic solvent were charged in the following ratios.

[Polymerization tank]
Copolymer (C) solution 200 parts [Drip device]
ε-caprolactone (D) 57 parts tetrabutylammonium tetrahydroborate (catalyst) 0.5 part ethyl ethanoate 30 parts

After the air in the polymerization tank was replaced with nitrogen gas, the resin solution was stirred, and the temperature was raised to 100 ° C. over 1 hour while removing the solvent from the system. At this time, the amount of the desorbed solvent was 36 parts.
Subsequently, the cyclic ester (D) mixture was dropped at a constant rate over 1 hour from the dropping device. Further, after reacting and aging for 12 hours with stirring, 171 parts of ethyl ethanoate was added and cooled to room temperature to complete the reaction, and the reaction containing the copolymer (C-1) having a side chain (I) was observed. A resin solution for pressure adhesive was obtained.
This solution is colorless and transparent, has a non-volatile content of 40.2% by weight and a viscosity of 8,800 mPa · s. The pressure-sensitive adhesive resin has an acid value of 58.2 mgKOH / g, a hydroxyl value of 0.6 mgKOH / g, glass The resin had a transition temperature of -36 ° C and a weight average molecular weight of 1,350,000.

<Production of copolymer (C-2) (step 3)>
A polymerization reaction apparatus in which a stirrer, a thermometer, a reflux condenser, a dropping apparatus, and a nitrogen introducing pipe are attached to the polymerization tank is prepared, and the copolymer (C-1) obtained in step (2) is prepared in the polymerization tank and the dropping apparatus. A pressure-sensitive adhesive resin solution, an amine compound (e4), a catalyst, and an organic solvent were charged at the following ratios.

[Polymerization tank]
200 parts of resin solution for pressure-sensitive adhesive containing copolymer (C-1) [Drip device]
Triethylamine (e4) 3 parts tetrabutylammonium tetrahydroborate (catalyst) 0.5 parts ethyl ethanoate 10 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 90 ° C. while stirring the solution. Next, the amine compound (e4) mixture was added dropwise to the stirring solution at a constant speed from a dropping device over 1 hour. After completion of the dropping, the mixture was further aged for 6 hours with stirring, and then 63 parts of ethyl ethanoate was added and cooled to room temperature to obtain a pressure-sensitive adhesive resin solution containing a copolymer (C-2).
This solution is colorless and transparent, has a non-volatile content of 30.5% by weight, and a viscosity of 5,000 mPa · s. This pressure-sensitive adhesive resin has an acid value of 5.2 mgKOH / g, a hydroxyl value of 0.2 mgKOH / g, The glass transition temperature was -36 ° C and the weight average molecular weight was 1,300,000. Moreover, it was confirmed from the C13 nuclear magnetic resonance spectrum (C13-NMR) that about 96% of the amine compound (e4) reacted with the side chain (I) to form the side chain (II) in the pressure-sensitive adhesive resin. did it.

(Synthesis Example 2)
The composition of the monomer used in the step (1) of Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. A transparent solution of the pressure-sensitive adhesive resin containing (C) was obtained.

[Polymerization tank]
N-butyl propenoate (B) 34.6 parts methyl propenoate (B) 15 parts propenoic acid (A) 0.3 part 2-hydroxyethyl 2-methylpropenoate (A) 0.1 part methyl ethanoate 30 parts 2,2'-Azobisisobutyronitrile 0.05 part [Drip device]
N-butyl propenoate (B) 49.8 parts propenoic acid (A) 0.2 parts ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. with stirring and reacted for 8 hours, and the copolymer (C) was contained in the same manner as in Step (1) of Synthesis Example 1. A resin solution for pressure-sensitive adhesive was obtained.
This solution is colorless and transparent, has a non-volatile content of 30.3% by weight and a viscosity of 7,600 mPa · s. The pressure-sensitive adhesive resin has an acid value of 4.9 mgKOH / g, a hydroxyl value of 0.3 mgKOH / g, and a glass transition. The temperature was -34 ° C and the weight average molecular weight was 1,100,000.

(Synthesis Example 3)
The cyclic ester (D) used in Step (2) of Synthesis Example 1 was changed to 50 parts of δ-valerolactone, and the resulting copolymer (C-1) solution was methyl ethanoate with a nonvolatile content of about 30% by weight. Preparation was performed in the same manner as in Synthesis Example 1 except that 200 parts of the solution prepared in Step (3) was used, and the non-volatile content was adjusted to about 30% by weight with ethyl ethanoate. A resin solution for pressure-sensitive adhesive containing 30.2% copolymer (C-2) having a viscosity of 4,000 mPa · s was obtained. The pressure-sensitive adhesive resin had an acid value of 5.8 mg KOH / g, a hydroxyl value of 0.3 mg KOH / g, a glass transition temperature of −37 ° C., and a weight average molecular weight of 127,000. In the above resin, the side chain (II) -derived copolymer (C-2) had a content of about 95%.

(Synthesis Example 4)
The cyclic ester (D) used in the step (2) of Synthesis Example 1 was changed to 43 parts of γ-butyrolactone, and the resulting copolymer (C-1) solution was reduced to a nonvolatile content of about 30% by weight with methyl ethanoate. Preparation was performed in the same manner as in Synthesis Example 1 except that 200 parts of the adjusted solution was used in step (3), and the nonvolatile content was adjusted to about 30% by weight with ethyl ethanoate. A solution of a resin for pressure-sensitive adhesive containing a copolymer (C-2) having a viscosity of 3.3% and a viscosity of 3,800 mPa · s was obtained. The pressure-sensitive adhesive resin had an acid value of 6.1 mgKOH / g, a hydroxyl value of 0.2 mgKOH / g, a glass transition temperature of −38 ° C., and a weight average molecular weight of 1130,000. In the resin, the content of the copolymer (C-2) derived from the side chain (II) was about 97%.

(Synthesis Example 5)
The composition of the monomer used in the step (1) of Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. A transparent solution of the pressure-sensitive adhesive resin containing (C) was obtained.

[Polymerization tank]
2-ethylhexyl propenoate (B) 37 parts n-butyl propenoate (B) 5 parts methyl propenoate (B) 5 parts 4-hydroxybutyl propenoate (A) 3 parts methyl ethanoate 30 parts 2,2'-azo Bisisobutyronitrile 0.05 parts [Drip device]
2-ethylhexyl propenoate (B) 47 parts 4-hydroxybutyl propenoate (A) 3 parts ethyl ethanoate 36 parts 2,2′-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. with stirring and reacted for 8 hours, and the copolymer (C) was contained in the same manner as in Step (1) of Synthesis Example 1. A solution of a pressure sensitive adhesive resin was obtained.
This solution is light yellow and transparent, has a non-volatile content of 30.2% by weight and a viscosity of 5,000 mPa · s. The pressure-sensitive adhesive resin has a hydroxyl value of 23.4 mgKOH / g, a glass transition temperature of −40 ° C., and a weight. The average molecular weight was 600,000.

  A pressure-sensitive adhesive resin solution containing the copolymer (1) obtained in the step (1) of Synthesis Example 5, a cyclic ester (D), a catalyst, and an organic solvent are charged in the following ratios, and the others are synthesis examples. Reaction was carried out in the same manner as in Example 1, and the non-volatile content was adjusted to about 30% by weight with ethyl ethanoate to obtain a transparent solution of the pressure sensitive adhesive resin containing the copolymer (C-1).

[Polymerization tank]
200 parts of resin solution for pressure-sensitive adhesive containing copolymer (C) [Drip device]
ε-caprolactone (D) 114 parts tetrabutylammonium tetrahydroborate (catalyst) 0.5 parts ethyl ethanoate 30 parts

This solution is colorless and transparent, has a non-volatile content of 40.1% by weight and a viscosity of 3,800 mPa · s. The pressure-sensitive adhesive resin has a hydroxyl value of 8.5 mgKOH / g, a glass transition temperature of −42 ° C., and a weight average. It was a resin having a molecular weight of 650,000.
Next, it was prepared in the same manner as in Step (3) of Synthesis Example 1 except that triethylamine, which is the amine compound (e4) used in Step (3) of Synthesis Example 1, was changed to 2 g of trimethylsilanol of silane compound (e1). For pressure-sensitive adhesive containing a copolymer (2) that is colorless and transparent and has a non-volatile content of 30.3% and a viscosity of 3,200 mPa · s. A resin solution was obtained. The pressure-sensitive adhesive resin had a hydroxyl value of 1.5 mgKOH / g, a glass transition temperature of −39 ° C., and a weight average molecular weight of 580,000. In the resin, the content of the side chain (II) -derived copolymer (C-2) was about 94%.

(Synthesis Example 6)
The composition of the monomer used in the step (1) of Synthesis Example 5 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. A transparent solution of the pressure-sensitive adhesive resin containing (C) was obtained.

[Polymerization tank]
2-ethylhexyl propenoate (B) 39.8 parts n-butyl propenoate (B) 5 parts methyl propenoate (B) 5 parts 4-hydroxybutyl propenoate (A) 0.2 part methyl ethanoate 30 parts 2, 0.05 parts of 2'-azobisisobutyronitrile [Drip device]
2-ethylhexyl propenoate (B) 49.9 parts 4-hydroxybutyl propenoate (A) 0.1 part ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. while stirring and reacted for 8 hours, and the copolymer (C) was contained in the same manner as in Step (1) of Synthesis Example 5. A resin solution for pressure-sensitive adhesive was obtained.
This solution was colorless and transparent, had a non-volatile content of 30.4% and a viscosity of 3,000 mPa · s. The pressure-sensitive adhesive resin had a hydroxyl value of 1.2 mgKOH / g, a glass transition temperature of −35 ° C., and a weight average molecular weight of 620,000.

(Synthesis Example 7)
The cyclic ester (D) used in the step (2) of Synthesis Example 5 was changed to 100 parts of δ-valerolactone, and the resulting resin solution for pressure-sensitive adhesive containing the copolymer (C-1) was treated with ethanoic acid. Preparation was performed in the same manner as in Synthesis Example 5 except that 200 parts of a solution adjusted to a nonvolatile content of about 30% by weight with ethyl was used in step (3), and the nonvolatile content was adjusted to about 30% by weight with ethyl ethanoate. Thus, a pressure-sensitive adhesive resin solution containing a copolymer (3) which was colorless and transparent and had a nonvolatile content of 30.3% and a viscosity of 3,200 mPa · s was obtained. The pressure-sensitive adhesive resin had a hydroxyl value of 1.7 mgKOH / g, a glass transition temperature of −38 ° C., and a weight average molecular weight of 550,000. In the resin, the content of the copolymer (C-2) derived from the side chain (II) was about 98%.

(Synthesis Example 8)
The cyclic ester (D) used in the step (2) of Synthesis Example 5 was changed to 86 parts of γ-butyrolactone, and the resulting resin solution for pressure-sensitive adhesive containing the copolymer (C-1) was treated with ethyl ethanoate. Prepared in the same manner as in Synthesis Example 5 except that 200 parts of the solution adjusted to a non-volatile content of about 30% by weight was used in step (3), and the non-volatile content was adjusted to about 30% by weight with ethyl ethanoate. A pressure-sensitive adhesive resin solution containing a copolymer (3) which was colorless and transparent and had a non-volatile content of 30.0% and a viscosity of 3,300 mPa · s was obtained. The pressure-sensitive adhesive resin had a hydroxyl value of 1.9 mgKOH / g, a glass transition temperature of −32 ° C., and a weight average molecular weight of 520,000. In the resin, the content of the copolymer (C-2) derived from the side chain (II) was about 97%.

(Synthesis Example 9)
Preparation was performed in the same manner as in Synthesis Example 5 except that the silane compound (e1) used in Step (3) of Synthesis Example 5 was changed to 2 parts of phenyl isocyanate as the monoisocyanate compound (e3). The non-volatile content was adjusted to about 30% by weight to obtain a pressure-sensitive adhesive resin solution containing a copolymer (3) that was colorless and transparent and had a non-volatile content of 30.5% and a viscosity of 4,000 mPa · s. The pressure-sensitive adhesive resin had a hydroxyl value of 1.4 mg KOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 560,000. In the resin, the content of the copolymer (C-2) derived from the side chain (II) was about 98%.

(Synthesis Example 10)
Synthesis except that the silane compound (e1) used in Step (3) of Synthesis Example 5 was changed to 2.5 parts of 1,3-dihydroisobenzofuran-1,3-dione as the acid anhydride-containing compound (e2). Preparation was carried out in the same manner as in Example 5, the non-volatile content was adjusted to about 30% by weight with ethyl ethanoate, a colorless and transparent copolymer having a non-volatile content of 30.2% and a viscosity of 4,200 mPa · s (3) A pressure-sensitive adhesive resin solution was obtained. The pressure-sensitive adhesive resin had an acid value of 8.6 mg KOH / g, a hydroxyl value of 0.1 mg KOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 580,000. In the resin, the content of the copolymer (C-2) derived from the side chain (II) was about 98%.

(Synthesis Example 11)
The composition of the monomer used in Synthesis Example 1 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. Otherwise, the polymerization was performed in the same manner as in Synthesis Example 1, and the copolymer (C) was contained. A transparent solution of a pressure sensitive adhesive resin was obtained.

[Polymerization tank]
2-methylpropenoic acid lauryl 18 parts ethyl propenoate 20 parts ethanylpyrrolidone 5 parts propenoic acid 2-hydroxyethyl 7 parts ethyl ethanoate 30 parts 2,2′-azobisisobutyronitrile 0.05 part [drip apparatus]
2 parts lauryl 2-methylpropenoate 5 parts ethyl propenoate 40 parts 2-hydroxyethyl propenoate 5 parts ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. with stirring and reacted for 8 hours, and the copolymer (C) was contained in the same manner as in Step (1) of Synthesis Example 1. A resin solution for pressure-sensitive adhesive was obtained.
This solution was colorless and transparent, had a non-volatile content of 30.1% and a viscosity of 8,500 mPa · s. The pressure-sensitive adhesive resin has a hydroxyl value of 56. It was mgKOH / g, glass transition temperature -28 degreeC, and the weight average molecular weight 1,650,000.

  A pressure-sensitive adhesive resin solution containing the copolymer (C) obtained in the step (1) of Synthesis Example 11, a cyclic ester (D), a catalyst and an organic solvent are charged in the following ratios, respectively, otherwise the synthesis example The reaction was conducted in the same manner as in No. 11, and the non-volatile content was adjusted to about 30% by weight with ethyl ethanoate to obtain a transparent solution of the pressure-sensitive adhesive resin containing the copolymer (C-1).

[Polymerization tank]
200 parts of resin solution for pressure-sensitive adhesive containing copolymer (C) [Drip device]
γ-Nonalactone (D) 156 parts Tetrabutylphosphonium hexafluorophosphate (catalyst)
0.5 part ethyl ethanoate 30 parts

This solution is colorless and transparent, has a non-volatile content of 40.3% by weight and a viscosity of 8,800 mPa · s. The pressure-sensitive adhesive resin has a hydroxyl value of 15.6 mgKOH / g, a glass transition temperature of −31 ° C., and a weight average. The resin had a molecular weight of 1,480,000.
Next, in the same manner as in Step (3) of Synthesis Example 1, except that triethylamine, which is the amine compound (e4) used in Step (3) of Synthesis Example 1, was changed to 2 g of phenyl isocyanate of the monoisocyanate compound (e2). The pressure-sensitive adhesive was prepared and adjusted with ethyl ethanoate to a non-volatile content of about 30% by weight, was colorless and transparent, and contained a copolymer (C) having a non-volatile content of 30.4% and a viscosity of 7,200 mPa · s. A resin solution was obtained. The pressure-sensitive adhesive resin had a hydroxyl value of 0.9 mgKOH / g, a glass transition temperature of −29 ° C., and a weight average molecular weight of 1,500,000. In the resin, the content of the copolymer (C-2) derived from the side chain (II) was about 98%.

(Synthesis Example 12)
The composition of the monomer used in Synthesis Example 11 was changed, and charged into the polymerization tank and the dropping device at the following ratios respectively. Otherwise, polymerization was performed in the same manner as in Synthesis Example 1, and the copolymer (C) was contained. A transparent solution of a pressure sensitive adhesive resin was obtained.

[Polymerization tank]
2-Methylpropenoate lauryl 24.9 parts Ethyl propenoate 20 parts Ethanylpyrrolidone 5 parts 2-Hydroxyethyl propenoate 0.1 parts Ethyl ethanoate 30 parts 2,2'-azobisisobutyronitrile 0.05 part [Drip device]
Lauryl 2-methylpropenoate 9.9 parts ethyl propenoate 40 parts 2-hydroxyethyl propenoate 0.1 part ethyl ethanoate 36 parts 2,2'-azobisisobutyronitrile 0.05 part

After the air in the polymerization tank was replaced with nitrogen gas, the mixture was heated to 100 ° C. while stirring and reacted for 8 hours, and in the same manner as in Step (1) of Synthesis Example 1, the feeling of containing the copolymer (C). A resin solution for pressure adhesive was obtained.
This solution was colorless and transparent, had a non-volatile content of 30.2% and a viscosity of 8,500 mPa · s. The pressure-sensitive adhesive resin had a hydroxyl value of 0.8 mgKOH / g, a glass transition temperature of −30 ° C., and a weight average molecular weight of 1,350,000.

  The resin solutions for pressure-sensitive adhesives obtained in Synthesis Examples 1 to 12 are the solution appearance, nonvolatile content (NV), viscosity (Vis), weight average molecular weight (Mw), glass transition temperature (Tg), acid value (AV). The hydroxyl group value (OHV) and the side chain (II) formation rate were evaluated as follows. The results are shown in Table 1.

The symbols in Table 1 are as follows.
PAEH: 2-ethylhexyl propenoate, PAB: n-butyl propenoate, PAM: methyl propenoate, PAE: ethyl propenoate, PA: propenoic acid, PAHE: 2-hydroxyethyl propenoate, PAHB: 4-hydroxybutyl propenoate , MPAHE: 2-hydroxyethyl 2-methylpropenoate, MPAL: lauryl 2-methylpropenoate, EP: ethanylpyrrolidone, EAc: ethyl ethanoate, MeAc: methyl ethanoate, εCL: ε-caprolactone, γBL: γ- Butyrolactone, δVL: δ-valerolactone, γNL: γ-nonalactone, TEA: triethylamine, TMSiOH: trimethylsilanol, PhAnh: 1,3-dihydroisobenzofuran-1,3-dione, PhNCO: phenyl isocyanate, TBAB Tetrabutylammonium tetrahydroborate, TBPHFP: tetrabutyl phosphonium hexafluorophosphate.

<Appearance of solution>
The appearance of the pressure-sensitive adhesive resin solution was visually evaluated.

<Measurement of nonvolatile content concentration (NV)>
About 1 g of a resin solution for pressure-sensitive adhesive was weighed in a metal container, dried in an oven at 150 ° C. for 20 minutes, and the residue was weighed to calculate the residual ratio, thereby obtaining a non-volatile concentration (%). .

<Measurement of solution viscosity (Vis)>
The temperature of the pressure-sensitive adhesive resin solution was maintained at 25 ° C., and the viscosity (mPa · s) was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 12 rpm for 1 minute.

<Measurement of weight average molecular weight (Mw)>
The pressure sensitive adhesive resin is dissolved in tetrahydrofuran and separated and quantified by the difference in molecular size by liquid chromatography using GPC (gel permeation chromatograph) “HPC-8020” manufactured by Tosoh Corporation. The weight average molecular weight (Mw) of the coalescence was determined in terms of polyethenylbenzene.

<Measurement of glass transition temperature (Tg)>
An “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) was connected to a robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) and used for measurement.
Apply and dry the resin solution for pressure sensitive adhesive on the peeled polyester film, scrape about 10 mg of the dried copolymer, put it in an aluminum pan as a sample, weigh it and set it in a differential scanning calorimeter, The aluminum pan of the same type without a sample was used as a reference, heated at a temperature of 100 ° C. for 5 minutes, and then rapidly cooled to −120 ° C. using liquid nitrogen. Thereafter, the temperature was increased at 10 ° C./min, and the glass transition temperature (Tg) (° C.) was determined from the DSC chart obtained during the temperature increase.

<Measurement of acid value (AV)>
In a stoppered Erlenmeyer flask, weigh accurately each sample (about 1.5 g of the pressure-sensitive adhesive resin with a non-volatile content of about 30% and about 1.3 g with a non-volatile content of about 40%). 100 ml of a mixed solution of ethanol (volume ratio: toluene / ethanol = 2/1) was added and dissolved. To this was added a phenolphthalein test solution as an indicator, which was held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned light red.
The acid value (mgKOH / g) was determined by the following equation as the value of the resin in the dry state.
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)>
In a stoppered Erlenmeyer flask, weigh accurately each sample (about 1.5 g of the pressure-sensitive adhesive resin with a non-volatile content of about 30% and about 1.3 g with a non-volatile content of about 40%). 100 ml of ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. Further, 5 ml of an acetylating agent (a solution in which 25 g of ethane acid 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] / (Non-volatile 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)

<Production rate of side chain (II)>
The production rate of the side chain (II) was determined using a C13 nuclear magnetic resonance spectrum (C13-NMR).
Apply and dry the pressure-sensitive adhesive resin solution on the release liner, scrape about 10g of the dried pressure-sensitive adhesive resin into a 10φ measuring tube (height: about 5cm), and add about 0.2ml of heavy chlorobenzene. After adding about 5 ml of chlorobenzene, the sample was capped and dissolved in an oven at 120 ° C. for 1 hour to obtain a measurement sample. This measurement sample was measured using a nuclear magnetic resonance absorber (manufactured by JEOL Ltd .: JMN-LA400) under the conditions of a measurement temperature of 120 ° C. and a spin intensity of 17 rpm.
Nuclear magnetic resonance absorption shows various patterns due to chemical structure. Since signals appear with different chemical shifts depending on the surrounding structure even with the same C—H bond or C—O bond, pay attention to the characteristic bonds in the copolymer structure in advance, and use the intensity of the chemical shift signal to It can also be used for quantification of polymers. The rate of formation of the copolymer (C-2) having a side chain (II) in the pressure-sensitive adhesive resin is determined by the chemical shift of the carbon atom directly linked to the active hydrogen group that is expressed by the ring-opening reaction of the cyclic ester compound. The production rate was determined by the identification.

Example 1
Ethanolate is added to 100 parts of the resin solution for pressure-sensitive adhesive containing the copolymer (C-2) obtained in Synthesis Example 1, and TDI / MPD (tolylene diene) is further added as a crosslinking agent (G). 10 parts of 2-methylpentane-2,4-diol adduct of isocyanate) was added to a non-volatile content of about 20% and stirred well to obtain a pressure sensitive adhesive.
This was coated on the release liner so that the thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to form an adhesive layer.
After drying, a single-sided polarizing film (also referred to as a polarizing plate) having a multilayer structure in which both sides of a polyethenol (PEA) polarizer are sandwiched between triacetylcellulose-based protective films (hereinafter referred to as “TAC film”) in the adhesive layer. Were laminated to form a release liner / adhesive layer / TAC film / PEA / TAC film, and further aged at a temperature of 23 ° C. and a relative humidity of 50% for 1 week to obtain a pressure-sensitive adhesive film.

(Comparative Example 1)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (C-2) obtained in Synthesis Example 1, a pressure-sensitive type containing the copolymer (C) obtained in Step (1) of Synthesis Example 1 An attempt was made to prepare a pressure-sensitive adhesive film in the same manner as in Example 1 except that the adhesive resin solution was used. However, the increase in viscosity of the pressure-sensitive adhesive suddenly increased and could not be applied.

(Comparative Example 2)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (C-2) obtained in Synthesis Example 1, the pressure-sensitive adhesive resin solution containing the copolymer (C) obtained in Synthesis Example 2 A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that was used.

(Examples 2 and 3)
Pressure-sensitive adhesive containing the copolymer (C-2) obtained in Synthesis Examples 3 and 4 instead of the resin solution for pressure-sensitive adhesive containing the copolymer (C-2) obtained in Synthesis Example 1 A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the resin solution for the agent was used.

(Examples 4 to 7)
The resin solution for pressure-sensitive adhesives containing the copolymer (C-2) used in Synthesis Example 1 was replaced with 10 parts of TDI / MPD as a crosslinking (G), and in Example 4, HBAP (2,2′-bis 1 part of hydroxymethylbutanol tris [3- (1-aziridinyl) propionate]), in Example 5, 5 parts of TGMXDA (N, N, N ′, N′-tetraglycidyl-m-xylylenediamine), in Example 6 V-05 (“Carbodilite V-05” which is a carbodiimide compound: Nisshinbo Co., Ltd.) 5 parts, except that 1 part of Al chelate (aluminum tris (acetylacetonate)) in Example 7 was added. Produced a pressure-sensitive adhesive film in the same manner as in Example 1. In Example 7, a pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the solvent was changed from ethyl ethanoate (EAc) to isopropyl alcohol (IPA).

(Example 8)
For the pressure-sensitive adhesive containing the copolymer (C-2) obtained in Synthesis Example 11 instead of the resin solution for the pressure-sensitive adhesive containing the copolymer (C-2) obtained in Synthesis Example 1. A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the resin solution was used and the number of parts of TDI / MPD used as the cross-linking (G) was changed to 1 part.

(Comparative Example 3)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (C-2) obtained in Synthesis Example 11, a pressure-sensitive type containing the copolymer (C) obtained in Step (1) of Synthesis Example 11 An attempt was made to create a pressure-sensitive adhesive film in the same manner as in Example 1 except that the adhesive resin solution was used. However, the viscosity increase of the pressure-sensitive adhesive suddenly progressed and could not be applied. .

(Comparative Example 4)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (C-2) obtained in Synthesis Example 11, a pressure-sensitive type containing the copolymer (C) obtained in Step (1) of Synthesis Example 12 A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the adhesive resin solution was used.

Example 9
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (C-2) obtained in Synthesis Example 11, the copolymer (C-1) obtained in Step (2) of Synthesis Example 11 is included. A pressure-sensitive adhesive film was produced in the same manner as in Example 1 except that the resin solution for pressure-sensitive adhesive was used.

(Examples 10 and 11)
The resin solution for pressure-sensitive adhesives containing the copolymer (C-2) used in Synthesis Example 11 was replaced with XDI / MPD (Xylylene Diisocyanate) in Example 10 instead of TDI / MPD as the crosslinking (G). Nate 2-methylpentane-2,4-diol adduct), and in Example 11, HMDI / burette (hexamethylene diisocyanate burette adduct) was added in the same manner as in Example 1, except that 1 part each was added. Thus, a pressure-sensitive adhesive film was produced.

(Example 12)
Ethanolate is added to 100 parts of the resin solution for pressure-sensitive adhesive containing the copolymer (C-2) obtained in Synthesis Example 5, and TDI / MPD (tolrange is used as a crosslinking agent (G). 1 part of 2-methylpentane-2,4-diol adduct of isocyanate) was added to adjust the non-volatile content to about 20% and stirred well to obtain a pressure-sensitive adhesive.
This was coated on a release liner so that the thickness after drying was 20 μm, and dried at 100 ° C. for 2 minutes to form an adhesive layer.
After drying, a 38 μm thick PET film is bonded to the adhesive layer to form a laminate structure of “release liner / adhesive layer / PET film”, and further aged for one week at a temperature of 23 ° C. and a relative humidity of 50%. A pressure-sensitive adhesive film was obtained.

(Comparative Example 5)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (C-2) obtained in Synthesis Example 5, the pressure-sensitive type containing the copolymer (C) obtained in Step (1) of Synthesis Example 5 A pressure-sensitive adhesive film was produced in the same manner as in Example 12 except that the adhesive resin solution was used.

(Comparative Example 6)
For the pressure-sensitive adhesive containing the copolymer (C-1) obtained in Synthesis Example 6 instead of the resin solution for the pressure-sensitive adhesive containing the copolymer (C-2) obtained in Synthesis Example 5. A pressure-sensitive adhesive film was produced in the same manner as in Example 12 except that the resin solution was used.

(Example 13)
Instead of the pressure-sensitive adhesive resin solution containing the copolymer (C-2) obtained in Synthesis Example 5, the copolymer (C-1) obtained in Step (2) of Synthesis Example 5 is included. A pressure-sensitive adhesive film was produced in the same manner as in Example 12 except that the resin solution for pressure-sensitive adhesive was used.

(Examples 14 and 15)
Instead of TDI / MPD as the crosslinking (G), the resin solution for pressure-sensitive adhesive containing the copolymer (C-2) used in Synthesis Example 5 was replaced with XDI / MPD (Xylylene Diisocyanate) in Example 14. Example 2 except that 1 part of 2-methylpentane-2,4-diol adduct of nate) and 1 part of HMDI / burette (hexamethylene diisocyanate burette adduct) were added in Example 15. Thus, a pressure-sensitive adhesive film was produced.

  The pot life and coating processability of the obtained pressure-sensitive adhesive were evaluated by the following methods. The results are shown in Table 2. Moreover, the following items were evaluated about the obtained pressure sensitive adhesive film. The evaluation results are shown in Table 3.

<Evaluation method of pot life>
About the obtained pressure-sensitive adhesive, after adding a crosslinking agent (G), the viscosity at 25 ° C. is changed every 12 hours using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 12 rpm for 1 minute. Measurement was performed under conditions, and pot life was evaluated in three stages.
○: “There is no change in viscosity. The rate of increase in viscosity up to 8 hours is less than 2 times.”
Δ: “Slight increase in viscosity is observed and the rate of increase in viscosity up to 5 hours is less than 2 times.”
X: “A sudden increase in viscosity was observed and gelled in less than 5 hours.

<Evaluation method of coatability>
The obtained pressure-sensitive adhesive was applied to a release liner with a comma coater at a speed of 2 m / min, dried in a 100 ° C. oven to form an adhesive layer with a thickness of 25 μm, and a thickness on the surface of the adhesive layer. A 50 μm polyester film was laminated to prepare a pressure-sensitive adhesive film. The state of the adhesive layer surface (coating surface) after peeling the release liner was visually observed and evaluated in three stages.
○: “A smooth coated surface was obtained.”
Δ: “Slight repellency and foaming are recognized at the end of the coated surface, but there is no practical problem.”
×: “Repelling, foaming and streaking are recognized on the coated surface, and there are practical problems.”

<Antistatic evaluation method (surface resistance value)>
The release liner of the pressure-sensitive adhesive film was peeled off, and the surface resistance value of the exposed adhesive layer surface was measured under the conditions of 23 ° C.-35, 45, 55% RH (manufactured by Mitsubishi Chemical Corporation). MCT-HT450) was used (unit: Ω / □) to evaluate the antistatic performance.

<Evaluation method of optical characteristics>
The pressure-sensitive adhesives obtained in the examples and comparative examples were coated and dried on the release liner in the same manner as described above to form an adhesive layer with a thickness of 25 μm, and the release liner was bonded to the surface of the pressure-sensitive adhesive. An agent film was obtained. After aging for one week at a temperature of 23 ° C. and a relative humidity of 50%, both release liners were removed, and the appearance of the adhesive layer was visually determined. HAZE was determined to be “NDH-300A” [Nippon Denshoku Industries ( Made by Co., Ltd.].
○: Good appearance. HAZE: less than 1.
(Triangle | delta): Cloudiness etc. are not recognized and it is 1 or more and less than 3.
X: Some cloudiness is recognized or HAZE: 3 or more. There are practical problems.

<Evaluation method of removability (reworkability)>
The resulting pressure-sensitive adhesive film is cut into a size of 25 mm × 150 mm, the release liner is peeled off, and is attached to a float glass plate with a thickness of 1.1 mm using a laminator, and an autoclave at 50 ° C. and 5 atmospheres. It was held for 20 minutes to obtain a laminate of a pressure-sensitive adhesive film and a glass plate. The laminate was allowed to stand at 23 ° C. and 50% relative humidity for 1 week, and then peeled off at a speed of 300 mm / min in the direction of 180 °. The haze on the glass surface after peeling was visually observed and evaluated in three stages.
○: “No cloudiness and good appearance”
Δ: “Slightly cloudy, but practically no problem”
×: “Transfer of the adhesive layer is recognized over the entire surface, and is not practical”

<Method for evaluating heat resistance and heat and humidity resistance>
The obtained pressure-sensitive adhesive film is cut into a size of 150 mm × 80 mm, the release liner is peeled off, and a laminator is formed so that the absorption axes of the respective polarizing plates are orthogonal to both surfaces of a 1.1 mm thick float glass plate. It stuck using. Subsequently, the glass plate with the polarizing plate attached thereto was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to obtain a laminate of the pressure-sensitive adhesive sheet and the glass plate.
The laminate was left to stand at 80 ° C. for 1000 hours and at 100 ° C. for 1000 hours, and the floating peeling, deviation, and light leakage when white light was transmitted through the laminate were visually observed. The heat resistance was evaluated.
In addition, when the laminate was left to stand at 60 ° C. and a relative humidity of 90% for 1000 hours, and at 80 ° C. and a relative humidity of 90% for 1000 hours, Light leakage (white spots) was visually observed to evaluate wet heat resistance.
Here, “displacement” is the displacement of the sticking position observed around the polarizing plate attached to the glass due to contraction of the polarizing plate.
The heat resistance and moist heat resistance were evaluated based on the following four criteria. In Examples 12 to 15 and Comparative Examples 5 and 6, since the base material was a PET film, only “floating peeling” was evaluated.
A: “Floating peeling, whitening, and displacement were not recognized at all, and it was good.”
○: “No floating peeling or whitening is observed, the displacement is less than 0.2 mm, and there is no problem in practical use.”
Δ: “Slightly floating peeling or whitening is observed, but the deviation is less than 0.2 to 0.5 mm, and there is no practical problem.”
×: “There are floating floats and white spots that are not practical.”

From the results of Table 3, since Comparative Examples 1 and 3 had an acid value or a hydroxyl value of 50 mgKOH / g or more, they could not be applied. Moreover, since Comparative Examples 2, 4-6 do not have a cyclic ester compound (D), it turns out that sufficient antistatic performance cannot be obtained. Moreover, since Comparative Examples 2 and 4 do not have a sealing compound (E), after sticking to a glass plate, if left under a further severe high temperature or high temperature and high humidity for a long time, foaming or floating It can be seen that peeling occurs and the durability is inferior.
On the other hand, the pressure-sensitive adhesive and pressure-sensitive visual adhesive film using the pressure-sensitive adhesive resin obtained by the method for producing the pressure-sensitive adhesive resin of the present invention are coatability, heat resistance, It turns out that it is excellent in heat-and-moisture resistance, an optical characteristic, antistatic property, and the rework property of an optical film.

  The pressure-sensitive adhesive of the present invention is suitable for use as an optical member, and in addition to general labels and seals, paints, elastic wall materials, waterproof coating materials, flooring materials, tackifiers, adhesives, adhesion for laminated structures Agent, sealing agent, molding material, coating agent for surface modification, binder (magnetic recording medium, ink binder, casting binder, fired brick binder, graft material, microcapsule, glass fiber sizing, etc.), urethane foam (hard, semi-solid (Hard, soft), urethane RIM, UV / EB cured resin, high solid paint, thermosetting elastomer, microcellular, textile processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, for artificial marble Resin, impact modifier for artificial marble, ink resin, film (laminate adhesive, protective film, etc.), synthetic resin It was 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 (9)

A step of copolymerizing the active hydrogen group-containing α, β-unsaturated monomer (A) and the α, β-unsaturated monomer (B) to obtain a copolymer (C); and
Characterized by comprising a step of reacting an active hydrogen group in the copolymer (C) with a cyclic ester (D) to produce a side chain (I) to obtain a copolymer (C-1). A method for producing a pressure-sensitive adhesive resin. It comprises a step of reacting the end of the side chain (I) with the sealing compound (E) to produce a side chain (II) to obtain a copolymer (C-2). Item 2. A process for producing a pressure-sensitive adhesive resin according to Item 1. The method for producing a pressure-sensitive adhesive resin according to claim 1 or 2, wherein the cyclic ester (D) is an oxyacid condensate (F). The method for producing a pressure-sensitive adhesive resin according to claim 3, wherein the oxyacid condensate (F) is a lactone. The sealing compound (E) is one or more compounds selected from the group consisting of a silane compound, a silanol group-containing compound, an acid anhydride group-containing compound, a monoisocyanate compound, and an amine compound. The manufacturing method of resin for pressure sensitive adhesives in any one of 2-4. A pressure-sensitive adhesive comprising a pressure-sensitive adhesive resin obtained by the production method according to claim 1 and a crosslinking agent (G). A pressure-sensitive adhesive film formed by forming an adhesive layer comprising the pressure-sensitive adhesive according to claim 6 on the substrate (H). An optical adhesive film obtained by forming an adhesive layer comprising the pressure-sensitive adhesive according to claim 6 on an optical film. A laminate in which an optical film, an adhesive layer formed from the pressure-sensitive adhesive according to claim 6 and glass are sequentially laminated.