JP2017210511A - Pressure-sensitive adhesive, adhesive film and optical laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive which shows excellent removability when used for an adhesive film and which less likely causes floating or peeling from an adherend after exposed to a high temperature environment or a high temperature and high humidity environment, and an adhesive film using the above adhesive.SOLUTION: The pressure-sensitive adhesive comprises a polyurethane resin (A) and a reactive compound (B) having a functional group that can react with a hydroxyl group, and contains, as a monomer unit constituting the polyurethane resin (A), a polyol (a1) unit and a polyisocyanate (a2) unit. The polyurethane resin (A) has an aromatic ring in the main chain, has an alkyl group having 4 to 22 carbon atoms and a hydroxyl group in a side chain, and has a weight average molecular weight of 10,000 to 500,000. The pressure-sensitive adhesive contains the reactive compound (B) having a functional group that can react with a hydroxyl group by 0.1 to 50 parts by weight with respect to 100 parts by weight of the polyurethane resin (A).SELECTED DRAWING: None

Description

  The present invention relates to a pressure-sensitive adhesive, an adhesive film using the same, and an optical laminate.

  Display devices such as liquid crystal displays used in various devices such as home and commercial appliances such as electronic calculators, electronic watches, mobile phones, and televisions are becoming larger, especially liquid crystal televisions and plasma televisions. The increase in size is remarkable. In recent years, touch panel type liquid crystal displays such as smartphones and tablets are rapidly spreading, and a large market expansion is expected in the future. On the other hand, liquid crystal displays are also used in in-vehicle devices such as car navigation systems, and are required to have durability that can be used in harsh interior environments such as high-temperature and high-humidity atmospheres.

Conventionally, a surface protective film is generally attached to an exposed surface side of an optical member such as a liquid crystal display in order to prevent surface contamination and scratches during processing, assembly, inspection, transportation, and the like. In particular, since the surface protection film for optical members may be repeatedly applied and peeled off during the manufacturing process, the surface of the optical member is contaminated during ease of sticking (wetting and spreading to the adherend) and peeling. Re-peelability (also called reworkability) is not required. In addition, as the optical member becomes thinner, the optical member itself becomes easier to break, and the surface protection film needs to have an adhesive property but can be peeled with a weaker force (light release property). It is coming. Furthermore, the surface protection film is required to have high durability that does not foam or peel off from the adherend even when exposed to heat and wet heat.
The laminated body such as an optical member to which this surface protective film is attached not only can be easily peeled off, but also prevents foaming, floating and peeling even under harsh environments such as high temperature or high temperature and high humidity conditions. Therefore, pressure sensitive adhesives containing acrylic resins and pressure sensitive adhesives containing silicone resins have been used.
However, pressure-sensitive adhesives containing acrylic resins may have a significant increase in adhesive strength over time after application due to insufficient cohesive strength of the adhesive layer itself, or adhesive residue may occur during peeling. There is a problem in using it as a surface protective film for a member that dislikes mixing of foreign matters such as an optical member and an electronic member.
In addition, the adhesive layer of the silicone resin tends to contaminate the adherend after peeling, and there is a problem in using it as a surface protective film for members that require particularly low contamination such as optical members and electronic members. It was.

  Then, the pressure sensitive adhesive containing the polyurethane resin which uses the polyether polyol as a polyol unit is disclosed as a pressure sensitive adhesive which does not use an acrylic resin or a silicone resin (patent document 1 or 2). However, since the conventional pressure-sensitive adhesive of Patent Document 1 or 2 uses a polyurethane resin, flexibility is obtained and the adhesive force is improved, but the cohesive force is reduced and the adhesive remains easily. was there.

  In addition, a pressure-sensitive adhesive containing a polyurethane resin in which polyether polyol and polyester polyol are used in combination as a polyol unit is disclosed (Patent Document 3). However, an adhesive film using a polyurethane resin using a polyester polyol as a polyol unit has high cohesive force and can suppress adhesive residue, but the elastic modulus of the adhesive layer itself is also high and adhesion to the substrate is increased. There was a problem that it was lowered and sufficient adhesive strength could not be maintained.

For this improvement, a pressure-sensitive adhesive containing a carboxylic acid ester (Patent Document 4) or a polyether polyol or polyester polyol as a polyol unit is used for a polyurethane resin in which polyether polyol and polyester polyol are used in combination as a polyol unit. A pressure-sensitive adhesive (Patent Document 5) is disclosed in which the polyurethane resin contains a plastic resin such as a polyalkylene glycol compound, an epoxy compound, or a phosphate ester compound.
However, the pressure-sensitive adhesive of Patent Document 4 or 5 can increase the flexibility by containing a plastic resin in the polyurethane resin, but the cohesive force becomes poor. In addition to the deterioration of workability such as the sticking out and stickiness of the pressure adhesive, there was a problem that the removability was poor.

  Moreover, in order to provide removability, a polyurethane resin using a polyester polyol or a polyether polyol having an aromatic ring in a polyol unit is disclosed (Patent Document 6). However, it is possible to increase the glass transition point (Tg) only by introducing an aromatic ring into the polyol unit. However, since it has crystallinity, the workability is reduced due to the increase in viscosity of the resin solution and the transparency. Sex is a problem. Moreover, since the pressure-sensitive adhesive layer becomes too hard, the adhesion to the adherend, the low-temperature characteristics, etc. were not satisfactory.

  In view of such a situation, durability such as heat resistance and moist heat resistance, wet spreadability, and removability are good, and it can be used from film label applications to electrical and optical applications, and is highly versatile. A pressure-sensitive adhesive that can also be used for a surface protective film has been desired.

JP 2006-18295 A JP 2014-028876 A Japanese Patent Laid-Open No. 2002-501954 JP, 2015-151429, A Japanese Patent Laying-Open No. 2015-007226 JP 2003-221570 A

  The problem to be solved by the present invention is to solve the above-mentioned problems, when used in an adhesive film, it has excellent removability and is exposed to a high temperature environment or a high temperature and high humidity environment. An object of the present invention is to provide a pressure-sensitive adhesive that hardly causes floating or peeling from the surface and an adhesive film using the pressure-sensitive adhesive. Furthermore, when used as a surface protection film, it has good wettability, maintains high transparency even when exposed to high-temperature and high-humidity environments, and has good adhesive force even in a slightly viscous region. An object of the present invention is to provide a pressure-sensitive adhesive that does not contaminate an adherend such as a glass plate during peeling, and an adhesive film using the pressure-sensitive adhesive.

  As a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved by the pressure-sensitive adhesive shown below, and have completed the present invention.

  That is, an embodiment of the present invention is a pressure-sensitive adhesive containing a polyurethane resin (A) and a reactive compound (B) having a functional group capable of reacting with a hydroxyl group, and constitutes the polyurethane resin (A). The monomer unit contains a polyol (a1) unit and a polyisocyanate (a2) unit, and the polyurethane resin (A) has an aromatic ring in the main chain and an alkyl group having 4 to 22 carbon atoms in the side chain. Reactive compound (B) 0.1 having a hydroxyl group, a weight average molecular weight of 10,000 to 500,000, and having a functional group capable of reacting with a hydroxyl group with respect to 100 parts by weight of polyurethane resin (A). It is a pressure-sensitive adhesive containing -50 parts by weight.

In the embodiment of the present invention, the polyol (a1) unit is 70 to 99% by weight and the polyisocyanate (a2) unit is 1 to 30% in the total of 100% by weight of the monomer units constituting the polyurethane resin (A). It is the said pressure sensitive adhesive which is weight%.

  An embodiment of the present invention is the pressure-sensitive adhesive, wherein the polyol (a1) contains a diol having an aromatic ring.

  An embodiment of the present invention is the pressure-sensitive adhesive described above, wherein the polyol (a1) contains a polyol having 3 or more hydroxyl groups.

  Moreover, the embodiment of this invention is the said pressure sensitive adhesive whose aromatic ring content rate in a polyurethane resin (A) is 2 to 30 weight%.

  An embodiment of the present invention is the pressure-sensitive adhesive according to any one of claims 1 to 5, wherein the polyisocyanate (a2) contains a diisocyanate.

  Moreover, the embodiment of this invention is the said pressure sensitive adhesive in which a reactive compound (B) contains polyisocyanate (b1).

  Moreover, the embodiment of this invention is the said pressure sensitive adhesive which contains ester compound (C) further.

  Furthermore, an embodiment of the present invention is the pressure-sensitive adhesive further including an ionic compound (D).

  An embodiment of the present invention is a pressure-sensitive adhesive film in which an adhesive layer formed from the pressure-sensitive adhesive is laminated on at least one surface of the base material (G).

  Moreover, the embodiment of this invention is the said pressure sensitive adhesive film whose base material (G) is a transparent film (H).

  Moreover, the embodiment of this invention is the said pressure sensitive adhesive film whose transparent film (H) is an optical film (I).

  An embodiment of the present invention is an optical laminate in which the optical film (I), an adhesive layer formed from the pressure-sensitive adhesive, and glass are sequentially laminated.

  By using the pressure-sensitive adhesive of the present invention, it is suitable for bonding for optical members that can form a pressure-sensitive adhesive layer excellent in adhesion to the substrate, removability, heat resistance, moist heat resistance and transparency. A pressure-sensitive adhesive that can be used in the present invention is provided. Furthermore, the use of the pressure-sensitive adhesive does not cause foaming or peeling even at high temperatures or high humidity, and it also provides excellent prevention of dirt and scratches on the surface of optical members during processing, assembly, inspection, transportation, etc. Thus, a surface protective film that does not contaminate the adherend during peeling can be provided.

Hereinafter, embodiments of the present invention will be described.
The pressure-sensitive adhesive of the present invention is a pressure-sensitive adhesive containing 0.1 to 50 parts by weight of the reactive compound (B) having a functional group capable of reacting with the hydroxyl group with respect to 100 parts by weight of the polyurethane resin (A). It is characterized by being an agent. The pressure-sensitive adhesive of the present invention is preferably used as an adhesive film in which an adhesive layer formed by coating on a substrate is laminated.
Hereinafter, the components of the pressure-sensitive adhesive will be specifically described.

<Polyurethane resin (A)>
The polyurethane resin (A) is a resin containing a polyol (a1) unit and a polyisocyanate (a2) unit as monomer units constituting it, and is a resin produced by polymerizing these monomer mixtures.

<< Polyol (a1) >>
First, the polyol (a1) unit, which is a monomer unit constituting the polyurethane resin (A), will be described.
As used herein, the polyol (a1) preferably contains a diol having an aromatic ring. Moreover, it is preferable that the diol which has a C4-C22 alkyl group is included. Furthermore, it is preferable to contain a trifunctional or higher functional polyol having 3 or more hydroxyl groups.

  By including a diol having an aromatic ring in the main chain, the polyol (a1) can maintain durability without foaming, floating and peeling even under severe conditions such as high temperature or high temperature and high humidity. The tack (adhesiveness) can be reduced, and the adhesive force of the pressure-sensitive adhesive to the glass plate can be reduced to a re-peelable region (for example, an adhesive force of less than 10.0 mN / 25 mm). . In addition, by including a diol having an alkyl group having 4 to 22 carbon atoms in the side chain, the density of the polyurethane resin (A) is partially reduced, so that flexibility from room temperature to low temperature is maintained and stable wetting is achieved. It becomes possible to obtain spreadability. Further, by containing a trifunctional or higher functional polyol having 3 or more hydroxyl groups, it is possible to introduce a hydroxyl group that can be a crosslinking point with the reactive compound (B) described later into the polyurethane resin (A). Therefore, it is possible to control the balance between the removability and the adhesiveness and wettability of the slightly viscous region.

  Examples of such polyol (a1) include low molecular weight polyols (a1-1), polyether polyols (a1-2), polyester polyols (a1-3), polyamide polyols (a1-4), and polycarbonate polyols. And other polyols (a-6) not similar to (a1-5) and (a1-1) to (a1-5).

The low molecular weight polyols (a1-1) are compounds that can be monomers that serve as the minimum units constituting the polyols (a1-2) to (a1-6) having a repeating unit having a polymerization degree of 2 or more described later. It is.
Examples of the low molecular weight polyols (a1-1) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, and 2-methyl-1,3-propane. Diol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-butyl-3-ethyl-1,5- Pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 3 , 3′-dimethylolheptane, 1,8-octanediol, 2-methyl-1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,12-octadecanediol, 1,4-tetracosanediol, 1,6-tetracosanediol, Chain aliphatic diols such as 1,4-hexacosanediol and 1,6-octacosanediol;

  For example, o-, m-, and p-dihydroxybenzene, 1,2-indanediol, benzene-1,2-dimethanol (also known as phthalyl alcohol), benzene-1,3-dimethanol (also known as isophthalyl) Alcohol), benzene-1,4-dimethanol (also known as terephthalyl alcohol), 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, (3,4-dihydroxyphenyl) methanol (alias: protocatechuyl alcohol), (4-hydroxy-3-methoxyphenyl) methanol (alias: vanillyl alcohol), 2- (4- Hydroxy-3-methoxyphenyl) ethane-1-ol (also known as homovanillyl alcohol), 3 (4-hydroxy-3-methoxyphenyl) prop-2-en-1-ol (also known as coniferyl alcohol), 3- (4-hydroxy-3,5-dimethoxyphenyl) prop-2-en-1-ol (Alternative name: Synapyl alcohol), 1,2-diphenylethane-1,2-diol (Alternative name: hydrobenzoin), hydroquinone, resorcin, 4-chlororesorcin, 4-methylresorcin, 5-methylbenzene-1,3- Diol (alias: orcinol), 2-methylbenzene-1,4-diol (alias: tolhydroquinone), 2,3-dimethylbenzene-1,4-diol (alias: o-xylohydroquinone), 2,6-dimethyl Benzene-1,4-diol (also known as m-xylohydroquinone), 2,5-dimethylbenzene-1,4-di (Aka p-xylohydroquinone), 2,3,5-trimethylbenzene-1,4-diol (aka pseudo spider hydroquinone), 2-isopropyl-5-methylbenzene-1,4-diol (alias) : Thymohydroquinone), 2,3,5,6-tetramethylbenzene-1,4-diol (alias: jurohydroquinone), 5-pentylbenzene-1,3-diol (alias: olivetol), 4,4′- Methylene diphenol (alias: pp-bisphenol F), 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxymethylbiphenyl, 4,4′-biphenyldiol, 2,3-dihydroxybutenyl, Tetranitrobiphenyldiol, 5,5′-dipropyl-biphenyl-2,2′-diol, 3,3′-diamy Nobiphenyl-4,4′-diol, 5,5′-tetramethylbiphenyl-4,4′-diol, diphenylsilanediol, (E) -4,4 ′-(hex-3-ene-3,4- Diyl) diphenol (also known as diethylstilbestrol), 2,2-bis (4-hydroxyphenyl) sulfone (also known as bisphenol S), 4,4'-isopropylidenephenol, 4,4'-dihydroxydiphenyl ether : 4,4'-oxydiphenol), 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 1,3-naphthalenediol, 1,5-naphthalenediol, 1,7-naphthalenediol 1,7-dihydroxymethylnaphthalene, ammonium 1,4-dihydroxy-2-naphthalenesulfonate, 9 Aromatic diols such as 9,9'-bis (4-hydroxyphenyl) fluorene, 9,9'-bis (3-methyl-4-hydroxyphenyl) fluorene 1,4-dihydro-9,10-anthracenediol;

  For example, glycerin, 1,1,1-trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane, 1,1,1-trimethylolhexane, 1,1,1- Trimethylol heptane, 1,1,1-trimethylol octane, 1,1,1-trimethylol nonane, 1,1,1-trimethylol decane, 1,1,1-trimethylol undecane, 1,1,1- Trimethylol dodecane, 1,1,1-trimethylol tridecane, 1,1,1-trimethylol tetradecane, 1,1,1-trimethylol pentadecane, 1,1,1-trimethylol hexadecane, 1,1,1 -Trimethylol heptadecane, 1,1,1-trimethylol octadecane, 1,1,1-trimethylol nonadecane, 1,1,1-to Methylol-sec-butane, 1,1,1-trimethylol-tert-pentane, 1,1,1-trimethylol-tert-nonane, 1,1,1-trimethylol-tert-tridecane, 1,1,1 -Trimethylol-tert-heptadecane, 1,1,1-trimethylol-2-methyl-hexane, 1,1,1-trimethylol-3-methyl-hexane, 1,1,1-trimethylol-2-ethyl -Hexane, 1,1,1-trimethylol-3-ethyl-hexane, 1,1,1-trimethylolisoheptadecane, trimethylolbutene, trimethylolheptene, trimethylolpentene, trimethylolhexene, trimethylolhept Ten, trimethylol octene, trimethylol decene, trimethylol dodecene, trimethyl Tridecene, trimethylolpentadecene, trimethylolhexadecene, trimethylolheptadecene, trimethyloloctadecene, 1,2,3-butanetriol, 1,2,6-butanetriol, 1,2,4-butanetriol, 1, 2,3-octanetriol, 1,3,7-octanetriol, 3,7-dimethyl-1,2,3-octanetriol, erytriol, 1,2,3,4-butanetetraol, 1,2, 10-dencantriol, pentaerythritol, dipentaerythritol, tripentaerythritol, diglycerin, triglycerin, polyglycerin, ditrimethylolethane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, benzene-1,3 5-triol Also known as: phloroglicinol), benzene-1,2,3-triol (also known as pyrogallol), stilbene-3,4 ', 5-triol (also known as resveratrol), inositol, sorbitan, sorbitol, mannitol, saccharose, cellulose, etc. And polyols having 3 or more hydroxyl groups.

Here, the dimer diol is a carboxylic acid having 18 carbon atoms such as an unsaturated fatty acid such as linoleic acid, oleic acid or linolenic acid, a dry oil fatty acid or a semi-dry oil fatty acid obtained from tall oil, cottonseed oil, soybean oil or the like. Is an aliphatic diol having 36 carbon atoms obtained by further complete hydrogenation of the dimer acid obtained by thermal polymerization of the dimer acid, and is obtained as a mixture of dimer diol geometric isomers having a branched structure and a cyclohexane ring. Compound. Examples of commercially available products include PRIPOL-2030 and 2033 (manufactured by CRODA Coating & Polymers) and Sovermol-908 (manufactured by BASF).
The term “chain aliphatic” as used herein means an acyclic chain carbon compound, and the cyclic carbon compound is defined as alicyclic.

  Moreover, 50-800 are preferable and, as for the formula weight (Mn, also called a number average molecular weight) of low molecular weight polyol (a1-1), 60-600 are more preferable. When the formula amount (Mn) is within this range, a pseudo crystal of a polyether polyol (a1-2), a polyester polyol (a1-3), a polyamide polyol (a1-4), or a polycarbonate polyol (a1-5) described later. Therefore, the viscosity of the polyurethane resin can be reduced and the coating processability is improved. Moreover, since flexibility becomes higher, it becomes easy to express adhesiveness. For the formula weight (Mn), literature values described in Chemical Handbook, Basic Edition, Rev. 5 (2004, The Chemical Society of Japan) etc. were used.

  Among these, in order to reduce the tack (tackiness) of the pressure-sensitive adhesive and to control the adhesiveness in the microviscous region, it is preferable to use the above aromatic diols. It is particularly preferable to use it together with a cyclic polyol. Among them, considering that tack (adhesiveness) is reduced in the polyurethane resin (A), benzene-1,3-dimethanol (also known as isophthalyl alcohol), 1,4-bis (2-hydroxyethoxy) benzene Is particularly preferred. In addition, in view of the point that the flexibility accompanying density reduction can be given, among the aliphatic diols and alicyclic diols, aliphatic diols and alicyclics having an alkyl group having 4 to 22 carbon atoms in the side chain. Diols are preferably used in combination, and diols having an alkyl group such as 2-butyl-2-ethyl-1,3-propanediol, 1,12-dodecanediol and dimer diol are particularly preferable. In addition, glycerin, 1,1,1-trimethylolpropane, 1,2,3-octanetriol, pentaerythritol, dipentaerythritol, benzene-1,2, in terms of forming a crosslinking point with a reactive compound described later. It is preferable to use polyols having three or more hydroxyl groups such as 3-triol, sorbitan and sorbitol.

  Known polyether polyols can be used as the polyether polyols (a1-2). The polyether polyols (a1-2) are polyoxyalkylene polyols obtained by ring-opening addition polymerization of alkylene oxide to an initiator having 2 to 4 active hydrogen atoms. Examples of the initiator include the low molecular weight polyols (a1-1) and aliphatic amines (for example, alkylene diamines such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, and neopentyl diamine, monoethanol amine, Alkanolamines such as diethanolamine), etc., but considering the wetting and spreading properties of the pressure-sensitive adhesive to the base material, the above-described low molecular weight polyols (a1-1) are used as initiators, and polyether polyols and It is particularly preferable to do this. These may be used alone or in combination of two or more.

Examples of the alkylene oxide include those having a polyoxyalkylene skeleton by ring-opening addition polymerization of ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, oxetane, tetrahydrofuran and the like.
Examples of the polyether polyol having an alkylene oxide skeleton include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol (ethylene oxide / propylene oxide copolymer), polytrimethylene glycol, polytetramethylene glycol, polypentamethylene glycol, poly Hexamethylene glycol, polyoctamethylene glycol, polyethylene tetramethylene glycol (ethylene oxide / tetramethylene oxide copolymer), ring-opening polymerization of alkylene oxide using the diols described in the above low molecular weight polyol (a1-1) as an initiator Alkyl polyalkylene glycol, cycloalkyl polyalkylene glycol, or bisphenol A or bisphenol Polyether diols such as polyalkylene diol having an ethylene oxide to bisphenol, an aromatic ring comprising by adding an alkylene oxide such as propylene oxide and the like;

  For example, polyoxyethylene glycerin, polyethylene triols such as polyoxyethylene trimethylol propane, polyoxypropylene glycerin, polypropylene triols such as polyoxypropylene trimethylol propane, polyoxyalkylene triols such as polyoxyethylene polyoxypropylene trimethylol propane, Polyethylene tetraols such as polyoxyethylene pentaerythritol, polypropylene tetraols such as polyoxypropylene pentaerythritol, ethylene oxide (EO) such as polyoxyethylene polyols such as polyoxyethylene sorbitol and polyoxypropylene sorbitol, or propylene oxide Number of moles of (PO) added: Polyols having 3 or more hydroxyl groups of 2 to 45 are listed. It is.

  Among these, when a polyarylalkylene glycol having an aromatic ring and an alkylene oxide skeleton is used, when used as a pressure-sensitive adhesive, durability such as good heat resistance and moist heat resistance is improved. (Adhesiveness) can be reduced. For example, polyoxyethylene bisphenol A ester (EO addition mole number: 2 to 12), polyoxypropylene bisphenol A ester (PO addition mole number: 2 to 2) in terms of both adhesiveness and wet spreadability in the microviscous region. 12) is particularly preferred. In addition, it is preferable to use a polyol having three or more hydroxyl groups that can introduce a hydroxyl group that can be a cross-linking point with the reactive compound (B) described later and that can further control the cohesive force. Polyethylene triols such as glycerin and polyoxyethylene trimethylolpropane, polypropylene triols such as polyoxypropylene glycerin and polyoxypropylene trimethylolpropane, and polyoxyalkylene triols such as polyoxyethylene polyoxypropylene trimethylolpropane can be used in combination preferable. By using polyols having 3 or more hydroxyl groups in combination, it is possible to control the adhesiveness of the microviscous region, re-peelability and wettability at a high level, and can be used for surface protection films, etc. Become.

  As the polyether polyol (a1-2), a commercially available product can be used. For example, PEG400 (Mn = 400, hydroxyl value = 275, acid value <0.5, linear liquid type), PEG600 (Mn = 600, Hydroxyl value = 180, acid value <0.5, linear liquid type), PEG1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear waxy type), PEG2000 (Mn = 2,000) , Hydroxyl value = 56, acid value <0.5, linear waxy type), PEG4000N (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear waxy type), PEG10000 (Mn = 10) , 000, hydroxyl value = 11, acid value <0.5, linear solid type), Newpol PP-400 (Mn = 400, hydroxyl value = 275, acid value <0.5, linear liquid type) ), New Pole PP-1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), New Pole PP-2000 (Mn = 2,000, hydroxyl value = 56, acid) Value <0.5, linear liquid type), New Pole PP-4000 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), New Pole GP-1000 (Mn = 1, 000, hydroxyl value = 112, acid value <0.5, linear liquid trifunctional type), Newpol GP-4000 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid trifunctional type) ), Primepole FF-3550 (Mn = 5,000, hydroxyl value = 34, acid value <0.5, linear liquid trifunctional type), Primepole FF-3320 (Mn = 3,000, hydroxyl value = 56, Acid value < .5, linear liquid trifunctional type), Primepole FH-2200 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Primepole PX-1000 (Mn = 1,000) , Hydroxyl value = 115, acid value <0.5, linear liquid type)

  ADEKA polyether P-1000 (Mn = 1,000, hydroxyl value = 110, acid value <0.1, linear liquid type), ADEKA polyether P-2000 (Mn = 2,000, hydroxyl value = 56, acid value) <0.1, linear liquid type), ADEKA polyether G-1500 (Mn = 1,500, hydroxyl value = 110, acid value <0.1, linear liquid trifunctional type), ADEKA polyether G-3000B (Mn = 3,000, hydroxyl value = 56, acid value <0.1, linear liquid trifunctional type), ADEKA polyether AM-302 (Mn = 3,000, hydroxyl value = 56, acid value <0.1, linear) Liquid trifunctional type), ADEKA polyether AM-502 (Mn = 4,600, hydroxyl value = 36, acid value <0.1, linear liquid trifunctional type) [above, manufactured by ADEKA Corporation];

  EXCENOL 420 (Mn = 400, hydroxyl value = 280, acid value <0.03, linear liquid type), EXCENOL 1020 (Mn = 1,000, hydroxyl value = 112, acid value <0.05, linear liquid type), EXCENOL 2020 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type), EXCENOL 3020 (Mn = 3,000, hydroxyl value = 35, acid value <0.03, linear liquid type) ), EXCENOL 510 (Mn = 4,000, hydroxyl value = 28, acid value <0.05, linear liquid type), EXCENOL 1030 (Mn = 1,000, hydroxyl value = 160, acid value <0.05, linear) Liquid trifunctional type), EXCENOL 240 (Mn = 3,000, hydroxyl value = 56, acid value <0.05, linear liquid trifunctional type), EXCEN OL 820 (Mn = 4,900, hydroxyl value = 34, acid value <0.05, linear liquid trifunctional type), EXCENOL 823 (Mn = 5,100, hydroxyl value = 33, acid value <0.05, linear Liquid trifunctional type) [above, manufactured by Asahi Glass Co., Ltd.];

  PTG 1000 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear wax type), PTG 2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear wax) ), PTG 3000 (Mn = 3,000, hydroxyl value = 36, acid value <0.05, linear wax type) [above, manufactured by Hodogaya Chemical Co., Ltd.];

  PTMG1000 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear wax type), PTMG 2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear wax type) Type) [Mitsubishi Chemical Corporation];

  BLAUNON GL-9 (Mn = 650, hydroxyl value = 259, acid value <0.05, linear liquid trifunctional type), BLAUNON GL-20 (Mn = 1,300, hydroxyl value = 127, acid value <0.05) , Linear liquid trifunctional type), BLAUNON GL-26 (Mn = 1,700, hydroxyl value = 100, acid value <0.05, linear liquid trifunctional type) [above, manufactured by Aoki Yushi Kogyo Co., Ltd.];

  UNIOX G-450 (Mn = 450, hydroxyl value = 374, acid value <0.05, linear liquid trifunctional type), UNIOX G-750 (Mn = 750, hydroxyl value = 224, acid value <0.05) , Linear liquid trifunctional type), Uniol TG1000 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid trifunctional type), Uniol TG2000 (Mn = 2,000, hydroxyl value = 84, Acid value <0.05, linear liquid trifunctional type), Uniol TG3000 (Mn = 3,000, hydroxyl value = 56, acid value <0.05, linear liquid trifunctional type), TG4000 (Mn = 4,000, Hydroxyl value = 42, acid value <0.05, linear liquid trifunctional type) [above, manufactured by NOF Corporation];

    HQ-20 (Mn = 200, hydroxyl value = 565, acid value <0.1, aromatic solid containing linear solid type), BA-4 glycol (Mn = 400, hydroxyl value = 280, acid value <0.1, Aromatic ring-containing linear liquid type), BA-6 glycol (Mn = 500, hydroxyl value = 225, acid value <0.1, aromatic ring-containing linear liquid type), BA-10 glycol (Mn = 660, hydroxyl value = 170). , Acid value <0.1, aromatic ring-containing linear liquid type), BA-17 glycol (Mn = 950, hydroxyl value = 170, acid value <0.1, aromatic ring-containing linear liquid type), BA-P4 glycol ( Mn = 450, hydroxyl value = 250, acid value <0.1, aromatic ring-containing linear liquid type), BA-P8 glycol (Mn = 660, hydroxyl value = 170, acid value <0.5, aromatic ring-containing linear liquid) Type), BPF4 Mn = 380, hydroxyl value = 300, acid number <0.1, the aromatic ring-containing linear liquid type) [above, Nippon Emulsifier Co. Ltd.] and the like can be given.

The polyester polyols (a1-3) can be obtained by the condensation reaction of the low molecular weight polyols (a1-1) and the polycarboxylic acids.
Known polycarboxylic acids used for obtaining the polyester polyol (a1-3) include, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, and chloromaleic acid. Aliphatic dicarboxylic acids such as fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride and the like;

  Examples thereof include alicyclic dicarboxylic acids such as dimer acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydrophthalic acid and tetrahydrophthalic acid, and anhydrides thereof.

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

  For example, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 4-methylcyclohexane-1,2,3-tricarboxylic acid, (1a, 2a, 4a) -1,2,4-cyclohexanetricarboxylic acid Acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, cyclopentanetetracarboxylic acid, ethylenetetracarboxylic acid, 4-methylcyclohexene-1,2,3- Tricarboxylic acid, trimesic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, cyclopentanetetra Carboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, ethylene A tri- or higher functional polycarboxylic acid such as glycol bistrimellitate carboxylic acid, 2,2 ′, 3,3′-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, and the like; Its anhydrides, etc .;

  In addition, polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone can also be used. In addition to improving durability such as heat resistance and heat-and-moisture resistance, it is preferable to use an aromatic polyester polyol using an aromatic dicarboxylic acid and its anhydride, which can reduce tack (adhesiveness), The above bifunctional dicarboxylic acid and its anhydride are preferable. In consideration of wettability to the base material, it is also possible to use the above aliphatic or alicyclic dicarboxylic acid and an aliphatic or alicyclic polyester polyol using the anhydride thereof in combination. These may be used alone or in combination of two or more.

  As the polyester polyols (a1-3), commercially available products may be used. For example, Kuraray polyol P510 (Mn = 500, hydroxyl value = 224, acid value <0.5, linear liquid type), Kuraray polyol P1010 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Kuraray polyol P2010 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray Polyol P3010 (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear liquid type), Kuraray polyol P4010 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid) Type), Kuraray polyol P5010 (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type), Kuraray polyol P6010 (M = 6,000, hydroxyl value = 19, acid value <0.5, linear liquid type), Kuraray polyol P2050 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray Polyol P3050 (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear liquid type), Kuraray polyol P4050 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid) Type), Kuraray polyol N2010 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray polyol N4010 (Mn = 4,000, hydroxyl value = 28, acid value <0. 5, linear liquid type), Kuraray polyol PNOA1010 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Kuraray polyol PNOA201 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray polyol P1012 (Mn = 1,000, hydroxyl value = 112, acid value <1, aromatic ring-containing linear liquid type) ), Kuraray polyol P2012 (Mn = 2,000, hydroxyl value = 56, acid value <1, aromatic ring-containing linear liquid type), Kuraray polyol P1013 (Mn = 1,000, hydroxyl value = 112, acid value <1, Aromatic ring-containing linear liquid type), Kuraray polyol P2013 (Mn = 2,000, hydroxyl value = 56, acid value <1, aromatic ring-containing linear liquid type), Kuraray polyol P1020 (Mn = 1,000, hydroxyl value = 112) Acid value <1, aromatic ring-containing linear liquid type), Kuraray polyol P2020 (Mn = 2,000, hydroxyl value = 56, acid value <1, aromatic ring-containing linear liquid type) ), Kuraray polyol P530 (Mn = 500, hydroxyl value = 224, acid value <0.5, aromatic ring-containing linear liquid type), Kuraray polyol P1030 (Mn = 1,000, hydroxyl value = 112, acid value <0) .5, aromatic ring-containing linear liquid type), Kuraray polyol P2030 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, aromatic ring-containing linear liquid type), Kuraray polyol F1010 (Mn = 1,000) , Hydroxyl value = 168, acid value <0.5, linear liquid trifunctional type), Kuraray polyol F2010 (Mn = 2,000, hydroxyl value = 84, acid value <0.5, linear liquid trifunctional type), Kuraray Polyol F3010 (Mn = 3,000, hydroxyl value = 56, acid value <0.5, linear liquid trifunctional type) [above, manufactured by Kuraray Co., Ltd.];

  For example, URIC H-62 (Mn = 430, hydroxyl value = 260, acid value <4.0, linear liquid type), URIC Y-202 (Mn = 980, hydroxyl value = 115, acid value <1.0, linear) Liquid type), URIC Y-332 (Mn = 910, hydroxyl value = 123, acid value <1.0, linear liquid type), URIC SE-3506 (Mn = 3,500, hydroxyl value = 32, acid value <1) 0.0, white solid type), URIC H-52 (Mn = 840, hydroxyl value = 200, acid value <3.0, white solid trifunctional type), URIC AC-005 (Mn = 550, hydroxyl value = 205, acid value <4.0, aromatic ring-containing linear liquid type), URIC AC-006 (Mn = 650, hydroxyl value = 178, acid value <5.0, aromatic ring-containing linear liquid type) Made by company];

  For example, PLACEL 205 (Mn = 530, hydroxyl value = 212, acid value <1.0, linear liquid type), PLACEL 208 (Mn = 830, hydroxyl value = 135, acid value <1.0, linear wax type) PLACEL 210 (Mn = 1,000, hydroxyl value = 114, acid value <1.0, linear wax type), PLACEL 220 (Mn = 2,000, hydroxyl value = 56, acid value <1.0, linear) Wax type), PLACEL 230 (Mn = 3,000, hydroxyl value = 37, acid value <1.0, linear waxy type), PLACEL 240 (Mn = 4,000, hydroxyl value = 28, acid value <1. 0, linear waxy type), PLACEL 303 (Mn = 300, hydroxyl value = 540, acid value <1.5, linear liquid trifunctional type), PLAC CEL 305 (Mn = 550, hydroxyl value = 305, acid value <1.0, linear liquid trifunctional type), PLACEL 308 (Mn = 850, hydroxyl value = 195, acid value <1.5, linear liquid trifunctional type) ), PLACEL 309 (Mn = 950, hydroxyl value = 187, acid value <1.0, linear liquid trifunctional type), PLACEL 312 (Mn = 1,250, hydroxyl value = 135, acid value <1.0, white) Solid trifunctional type), PLACEL 320 (Mn = 2,000, hydroxyl value = 84, acid value <1.0, white solid trifunctional type), PLACEL 420 (Mn = 1,000, hydroxyl value = 224) Acid value <1.0, linear liquid tetrafunctional type) [above, manufactured by Daicel Corporation];

  For example, Kyowapol 2000BA (Mn = 2,000, hydroxyl value = 58, acid value <0.5, linear liquid type), Kyowapol 5000PA (Mn = 5,000, hydroxyl value = 22, acid value <0.5) , Linear liquid type) [above, manufactured by Kyowa Hakko Chemical Co., Ltd.];

  For example, polylite OD-X-221 (Mn = 2,000, hydroxyl value = 56, acid value <0.3, linear liquid type), polylite OD-X-2586 (Mn = 850, hydroxyl value = 200, acid value) = 0.4, linear liquid type), polylite OD-X-2420 (Mn = 2,000, hydroxyl value = 56, acid value = 0.4, linear liquid type), polylite OD-X-2523 (Mn = 3). , 500, hydroxyl value = 32, acid value = 0.5, linear solid type), polylite OD-X-2547 (Mn = 4,500, hydroxyl value = 25, acid value = 0.3, linear solid type), Polylite OD-X-102 (Mn = 2,000, hydroxyl value = 56, acid value = 1.3, linear solid type), Polylite OD-X-2420 (Mn = 2,000, hydroxyl value = 56, acid value) = 0.3, linear liquid Polylite OD-X-2155 (Mn = 1,000, hydroxyl value = 115, acid value = 0.2, linear solid type), Polylite OD-X-2722 (Mn = 2,000, hydroxyl value = 58) , Acid value = 0.3, linear liquid type) [above, manufactured by DIC Corporation];

  For example, NIPPOLAN 4002 (Mn = 1,000, hydroxyl value = 110, acid value <2, linear solid type), NIPPOLAN 4040 (Mn = 2,000, hydroxyl value = 56, acid value <2, linear solid type), NIPPOLAN 4009 (Mn = 1,000, hydroxyl value = 110, acid value <2, linear solid type), NIPPOLAN 4010 (Mn = 2,000, hydroxyl value = 56, acid value <2, linear solid type), NIPPOLAN 164 (Mn = 1,000, hydroxyl value = 110, acid value <1, linear solid type), NIPPOLAN 4073 (Mn = 2,000, hydroxyl value = 56, acid value <1, linear solid type), NIPPOLAN 152 (Mn = 1,000, hydroxyl value = 110, acid value <1, linear liquid type), NIPPOLAN 1004 (Mn = 2,600, hydroxyl value = 42, acid value <2, linear liquid type) Nippolan 5018 (Mn = 2,000, hydroxyl value = 56, acid number <1, the linear solid type) [above, Tosoh - made Company]

  For example, MAXMOL RDK-133 (Mn = 360, hydroxyl value = 315, acid value = 0.5, linear liquid type), MAXMOL RDK-142 (Mn = 280, hydroxyl value = 400, acid value = 0.5, linear) Liquid type) [above, manufactured by Kawasaki Kasei Kogyo Co., Ltd.];

  For example, Adeka New Ace NS2400 (Mn = 2,000, hydroxyl value = 56, acid value <0.3, linear liquid type), Adeka New Ace YT-101 (Mn = 680, hydroxyl value = 165, acid value <0) .3, linear liquid type), Adeka New Ace F′-67 (Mn = 2,000, hydroxyl value = 56, acid value <0.3, linear liquid type), Adeka New Ace YG-108 (Mn = 1, 000, hydroxyl value = 120, acid value <0.3, linear solid type), Adeka New Ace V14-90 (Mn = 2,000, hydroxyl value = 56, acid value <0.3, linear solid type) Manufactured by Adeka Corporation];

For example, HS2H-200S (Mn = 2,000, hydroxyl value = 56, acid value <0.3, linear liquid type), HS2H-350S (Mn = 3,500, hydroxyl value = 32, acid value <0.3). , Linear liquid type), HS2H-500S (Mn = 5,000, hydroxyl value = 22, acid value <0.3, linear liquid type), HS2H-179A (Mn = 1,750, hydroxyl value = 64, acid value). <0.3, aromatic liquid-containing linear liquid type), HS2H-458T (Mn = 4,500, hydroxyl value = 25, acid value <0.3, aromatic ring-containing linear solid type), HS2F-237P (Mn = 2) , 000, hydroxyl value = 56, acid value <0.3, aromatic solid containing linear solid type)
[Above, Toyokuni Oil Co., Ltd.] and the like.

The polyamide polyol (a1-4) can be obtained by subjecting the low molecular weight polyol (a1-1) to a condensation reaction at the molecular ends of the polyamide formed by the condensation reaction with the polycarboxylic acid and polyamine.
As the polyamine, any polyamine having two or more amino groups can be used without any particular limitation. For example, ethylenediamine, propylenediamine, butylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1, 3-bis- (3-aminopropoxy) -2,2-dimethylpropane, α, ω-bis- (3-aminopropyl) polyethylene glycol ether, neopentyldiamine, 1,2-diaminobutane, 1,4-diamino Aliphatic diamines such as butane, hexamethylenediamine, trimethylhexamethylenediamine;

  For example, fats such as mensendiamine, isophoronediamine, 1,3- (bisaminomethyl) cyclohexane, 1,4- (bisaminopropyl) cyclohexane, 4,4′-methylenebis (2-methylcyclohexylamine), norbornanediamine Cyclic diamines;

  Examples thereof include polyamines having 3 or more amino groups such as methanetriamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, butane-1,1,4,4-tetraamine.

  Ketimines, which are the reaction products of these polyamines and ketones, are also included in the polyamines.

Of these, aliphatic diamines and alicyclic diamines are preferred as the polyamine, considering the solubility of the pressure-sensitive adhesive in the organic solvent described later and the wettability of the adherend.
Polyamines can be used alone or in combination of two or more. Polyamide polyol (a1-4) is preferably used in combination with other polyols from the viewpoint of solubility in organic solvents.

  As the polyamide polyol (a1-4), for example, TPAE617 (Mn = 15,000, Tg = 90 ° C., hydroxyl value = 16, acid value = 1, linear solid type) [Fuji Kasei Kogyo Co., Ltd.] Etc.].

  The polycarbonate polyol (a1-5) is a known polycarbonate polyol having in its molecule the structure represented by the following general formula [1].

General formula [1]
− [— O—R ¹ —O—CO—] _m —
(In the formula, R ¹ represents a divalent organic residue, and m represents an integer of 1 or more.)

The polycarbonate polyol (a1-5) acts on phosgene in the presence of alkali on (I) the reaction of a low molecular weight polyol (a1-1) and a carbonate ester, or (II) the low molecular weight polyol (a1-1). Can be obtained by the reaction. .
Examples of the carbonate ester include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

  Since the polycarbonate polyol (a1-5) has a carbonate structure as a linking group, the cohesive strength of the polyurethane resin (A) is increased, and it has excellent heat resistance, hydrolysis resistance, or weather resistance. When used as an agent, it is excellent in re-peelability particularly in a harsh environment. Among these, polycarbonate diols having a substituent having 4 to 22 carbon atoms in the side chain are preferable from the viewpoint of the viscosity and coating properties of the pressure-sensitive adhesive, or the processability of the adhesive film, and alkyl groups having 4 to 22 carbon atoms. Particularly preferred are polycarbonate diols having

  As the polycarbonate polyols (a1-5), commercially available products can be used. For example, oximer N112 (Mn = 1,000, Tg = 60 ° C., hydroxyl value = 112, acid value <0.5, linear type) [ Perstorp]];

  Duranol T5651 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), Duranol T5652 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear liquid type) ), Duranol T4671 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), Duranol T4672 (Mn = 2,000, hydroxyl value = 52, acid value <0.05, linear) Liquid type) [above, manufactured by Asahi Kasei Chemicals Corporation];

  ETERNACOLL UH-100 (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear liquid type), ETERNACOLLUH-200 (Mn = 2,000, hydroxyl value = 56, acid value <0.05, Linear liquid type) [above, manufactured by Ube Industries, Ltd.];

  BENEBiOL NL1010DB (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear solid type), BENEBiOL NL2010DB (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear solid type) ), BENEBiOLNL1010B (Mn = 1,000, hydroxyl value = 110, acid value <0.05, linear solid type), BENEBiOLNL2010B (Mn = 2,000, hydroxyl value = 56, acid value <0.05, linear solid type) [The above, manufactured by Mitsubishi Chemical Corporation];

  PLACEL CD205 (Mn = 500, hydroxyl value = 225, acid value <0.1, linear liquid type), PLACEL CD210 (Mn = 1,000, hydroxyl value = 116, acid value <0.1, linear wax type) PLACEL CD220 (Mn = 2,000, hydroxyl value = 56, acid value <0.1, linear wax type) [above, manufactured by Daicel Corporation];

Kuraray polyol C-1065N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear wax type), Kuraray polyol C-2065N (Mn = 2,000, hydroxyl value = 56, acid value < 0.5, linear wax type), Kuraray polyol C-1090 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Kuraray polyol C-2090 (Mn = 2,000) , Hydroxyl value = 56, acid value <0.5, linear liquid type), Kuraray polyol C-3090 (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear liquid type), Kuraray polyol C -4090 (Mn = 4,000, hydroxyl value = 28, acid value <0.5, linear liquid type), Kuraray polyol C-5090 (Mn = 5,000, hydroxyl value = 22, acid value < 0.5, linear liquid type), Kuraray polyol C-1015N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type), Kuraray polyol C-2015N (Mn = 2,000, Hydroxyl value = 56, acid value <0.5, linear liquid type) [above, manufactured by Kuraray Co., Ltd.];
Etc.

  The other polyol (a1-6) is a polyol that does not belong to the above polyols (a1-1) to (a1-5), a polyol containing at least one ionic functional group, and a siloxane such as dimethylsiloxanediol. Examples thereof include polyols having a skeleton and polyols having a diene skeleton such as polybutadiene diol and polyisoprene diol. The diene skeleton also includes a hydrogenated diene in which the diene skeleton is saturated with a hydrogen atom.

  Of the polyols containing at least one ionic functional group, the ionic functional group is a quaternary ammonium group, a tertiary amino group, a carboxylate group, a carboxyl group, a sulfonate group, a sulfonic acid group, or a phosphonium group. , Ionic groups such as phosphinic acid groups and sulfate ester groups, and precursor groups thereof. Carboxyl groups, tertiary amino groups, etc. are not ionic groups, but can be easily converted to ionic groups by neutralization or quaternization with ammonia, tertiary amines, acetic acid, etc. Including.

  Examples of the polyol containing at least one ionic functional group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, and 2,2-bis (hydroxymethyl) Carboxylic acid-containing polyol compounds such as herbic acid and 2,2-bis (hydroxymethyl) butanoic acid, and hydrogen groups of ammonia such as N, N-bis (2-hydroxypropyl) aniline and N-methyldiethanolamine as hydrocarbon groups And the like.

  Commercially available polyols having a siloxane skeleton include, for example, KF6001 (Mn = 1,800, hydroxyl value = 62, acid value <0.5, linear liquid type), KF6002 (Mn = 3,000, hydroxyl value = 35). Acid value <0.5, linear liquid type), KF6003 (Mn = 5,000, hydroxyl value = 22, acid value <0.5, linear liquid type) [above, manufactured by Shin-Etsu Chemical Co., Ltd.];

  XF42-B0970 (Mn = 1,850, hydroxyl value = 60, acid value <0.5, linear liquid type) [above, manufactured by Momentive Performance Materials, Inc.];

  SF8427 (Mn = 2,400, hydroxyl value = 46.8, acid value <0.1, linear liquid type), SF8428 (Mn = 3,200, hydroxyl value = 35, acid value <0.1, linear liquid type) [The above is made by Toray Dow Corning Co., Ltd.].

  Examples of commercially available polyols having a diene skeleton include GI-1000 (Mn = 1,500, hydroxyl value = 67, acid value <0.5, linear liquid type), GI-2000 (Mn = 2,100, Hydroxyl value = 47, acid value <0.5, linear liquid type), GI-3000 (Mn = 3,100, hydroxyl value = 26, acid value <0.5, linear liquid type) [above, manufactured by Nippon Soda Co., Ltd. ];

  Epol (Mn = 2500, hydroxyl value = 45, acid value <0.1, linear liquid type), PolybdR45HT (Mn = 1,200, hydroxyl value = 93.5, acid value <0.1, linear liquid type) ) [Idemitsu Kosan Co., Ltd.] and the like. The diene skeleton includes an olefin skeleton obtained by hydrogenating the diene skeleton.

  The polyol (a1) is a polyether polyol (a1-2), a polyester polyol (a1-3), a polyamide polyol (a1-4), a polycarbonate polyol (a1-5), or another polyol (a-6). As described above, a combination of a diol having two hydroxyl groups and a polyol having three or more hydroxyl groups is preferably used. / 1 to 40/60 (weight ratio) is preferable, and 98/2 to 50/50 (weight ratio) is more preferable. When the composition ratio is in the above range, it is possible to use the surface protective film or the like because it is possible to control the adhesiveness of the fine-viscous region, the removability and the wet spreadability at a high level.

The polyol (a1) preferably has a number average molecular weight (Mn) of 200 to 50,000, more preferably 400 to 30,000, and still more preferably 600 to 10,000. When the number average molecular weight (Mn) is in the above range, the viscosity suitable for coating can be maintained, and the handling during coating is excellent. Moreover, it becomes possible to give a moderate cohesive force and sufficient softness | flexibility to a polyurethane resin (A), and it becomes possible to express sufficient adhesiveness in a microviscous area | region. In addition, the adhesive film produced from the pressure-sensitive adhesive does not float or peel off even under a severe environment such as high temperature and high humidity. When such a polyol (a1) is used, a pressure-sensitive adhesive having excellent adhesion and wettability can be obtained. Moreover, application to a surface protection film is possible.
In addition, the said weight average molecular weight (Mw) and number average molecular weight (Mn) are the values of polystyrene conversion measured by the gel permeation chromatography (GPC) method. Details of the GPC measurement method are described in the Examples.

Of the polyol (a1), polyether polyol (a1-2), polyester polyol (a1-3), polyamide polyol (a1-4), polycarbonate polyol (a1-5), or other polyol (a1-6) The hydroxyl value is preferably in the range of 2 to 560 mg KOH / g, more preferably in the range of 4 to 280 mg KOH / g, and most preferably in the range of 4 to 200 mg KOH / g. When the hydroxyl value is in the above range, a pressure-sensitive adhesive having excellent adhesion and wettability is obtained in the same manner as the number average molecular weight (Mn), and application to a surface protective film becomes possible. Generally, if the hydroxyl value of a polyol is determined, the number average molecular weight is also determined, and it is known that the hydroxyl value and the number average molecular weight are linked.
The hydroxyl value (OHV) is a value measured according to JIS K1557-1: 2007, and the acid value (AV) is a value measured according to JIS K0070: 1992. Details of the measurement method are described in the examples. .

  In the said polyol (a1), when it has a glass transition temperature (Tg), it is although it does not specifically limit, Preferably it is -80-80 degreeC, More preferably, it is -70-40 degreeC. When the glass transition temperature (Tg) is in the above range, the pressure-sensitive adhesive containing the polyurethane resin (A) has sufficient tackiness and cohesive strength, so that cohesive failure of the adhesive layer is maintained while maintaining adhesiveness. Suppresses and prevents floating and peeling. The glass transition temperature (Tg) can be adjusted by appropriately selecting the type of polyol (a1) that is a constituent component. Moreover, it can also adjust to a suitable glass transition temperature using 2 or more types of polyol (a1) from which glass transition temperature differs. Details of the measurement method are described in the examples.

  Transparency of adhesive layer using pressure-sensitive adhesive, maintenance of durability such as heat resistance and heat-and-moisture resistance, expression of adhesive force in micro-viscous area due to reduction of tack (stickiness), adhesion to adherends such as glass plates It is preferable to use a diol having an aromatic ring in terms of removability after wearing, and in addition, it is preferable to use a diol having no aromatic ring in view of wettability with respect to the adherend. In particular, low molecular weight polyols (a1-1), polyether polyols (a1-2) or polyester polyols (a1-3) having an aromatic ring have an alkyl group having 4 to 22 carbon atoms in the side chain. It is preferable to use polyols in combination. The amount of low molecular weight polyols having an alkyl group having 4 to 22 carbon atoms is preferably from 0.1 to 30% by weight, more preferably from 0.5 to 20% by weight, based on the total amount of the polyol (a1). When the low molecular weight polyols having an alkyl group having 4 to 22 carbon atoms are in the above range, in addition to appropriate cohesive force, sufficient flexibility can be imparted, and pressure sensitive adhesive having excellent wettability. Is obtained.

In addition, it is preferable to use a polyol having three or more hydroxyl groups in combination with these diols in terms of forming a crosslinking point with a reactive compound described later and controlling the cohesive force.
The amount of polyols having 3 or more hydroxyl groups is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, based on the total amount of polyol (a1). When the polyols having 3 or more hydroxyl groups are within the above range, the adhesive film produced from the pressure-sensitive adhesive does not float or peel off even under a severe environment such as high temperature and high humidity, and after the peeling Good removability can be obtained without contaminating the adherend.

  The aromatic ring contained in the polyurethane resin (A) is also derived from the component polyol (a1), and the content of the aromatic ring is preferably 1 to 50% by weight in the total amount of the polyol (a1). More preferred is 40% by weight. When the aromatic ring content is in the above range, when used as a pressure-sensitive adhesive, tack (adhesiveness) can be reduced, so that not only the removability is good but also good. Durability such as heat resistance and moist heat resistance can be obtained. In addition, the content rate of an aromatic ring shows the content rate of the formula weight (Mn) 76g / mol of the phenylene group in a polyurethane resin (A).

<< Polyisocyanate (a2) >>
Next, the polyisocyanate (a2) unit, which is a monomer unit constituting the polyurethane urea resin (A), will be described.
A conventionally well-known thing can be used as polyisocyanate (a2), and aliphatic polyisocyanate, alicyclic polyisocyanate, or aromatic polyisocyanate is mentioned.
Examples of the polyisocyanate (a2) include aliphatic polyisocyanates or alicyclic polyisocyanates. In addition, aliphatic means an acyclic carbon compound, and a cyclic carbon compound is defined as an alicyclic.
Moreover, although polyisocyanate (a2) can also have 3 or more isocyanate groups, the diisocyanate which has two isocyanate groups is preferable at the point of the softness | flexibility provision accompanying the reduction of the density of a polyurethane urea resin.

  Examples of the polyisocyanate (a2) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. Aliphatic diisocyanates such as diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate;

  For example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4- Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, norbornene diisocyanate, dimer acid diisocyanate, octahydro-4,7-methano-1H -Alicyclic diisocyanates such as indenedimethyl diisocyanate;

  For example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (also known as 2,4-TDI), 2,6-tolylene diisocyanate (also known as : 2,6-TDI), 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenyl Methane triisocyanate, 1,3-phenylene bismethylene diisocyanate (alias: m-XDI), 1,4-phenylene bismethylene diisocyanate (alias: p-XDI), 2,2′-diphenylmethane diisocyanate (alias: 2,2-MDI), 4,4'-diphenyl Tan diisocyanate (alias: 4,4-MDI), 1,3-naphthalenediyl diisocyanate (alias: 1,3-NDI), 1,5-naphthalenediyl diisocyanate (alias: 1,5-NDI), ω, ω ′ Diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3 -Aromatic diisocyanates such as tetramethylxylylene diisocyanate;

  Examples thereof include polyisocyanates having three or more isocyanate groups such as lysine triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, and methylsilanetriyltrisisocyanate.

The polyisocyanate (a2) can have three or more isocyanate groups as described above, but diisocyanates having two isocyanate groups can impart flexibility with a decrease in the density of the polyurethane resin (A). This is preferable.
Among these, 2,4-tolylene diisocyanate (alias: 2,4-TDI), 2,6-tolylene diisocyanate (alias: 2,6-TDI), 1,4-phenylene bismethylene diisocyanate (alias: p-XDI), 2,2′-diphenylmethane diisocyanate (alias: 2,2-MDI), 4,4′-diphenylmethane diisocyanate (alias: 4,4-MDI) and the like are preferably used. Are aliphatic polyisocyanates such as hexamethylene diisocyanate (also known as HDI), alicyclic polyisocyanates such as isophorone diisocyanate (also known as IPDI) and 4,4′-methylenebis (cyclohexyl isocyanate) (also known as hydrogenated MDI). It is also possible to use diisocyanate that does not have an aromatic ring It is.

The polyurethane resin (A) is a resin obtained by polymerizing the polyol (a1) and the polyisocyanate (a2).
The weight-average molecular weight (Mw) of the polyurethane resin (A) is 10,000 to 500,000 in order to achieve both the coating suitability of the pressure-sensitive adhesive and the cohesive strength of the adhesive layer and the adhesive layer at a high level. Is preferable, and it is more preferable that it is 30,000-400,000. When Mw is in the above range, the cohesive force and the like are further improved, so that floating / peeling can be further suppressed, and wetting and spreading properties are further improved. In addition, the said weight average molecular weight and number average molecular weight are the values of polystyrene conversion measured by the gel permeation chromatography (GPC) method. Details of the GPC measurement method are described in the Examples.

  0.1-50 mgKOH / g is preferable and, as for the hydroxyl value (OHV) of a polyurethane resin (A), 0.5-30 mgKOH / g is more preferable. When the hydroxyl value (OHV) is in the above range, the crosslinking reaction with the reactive compound (B) having a functional group capable of reacting with a hydroxyl group becomes more efficient. It becomes easy to express the adhesive force in the slightly viscous region while maintaining the above. Moreover, after sticking time, it is easy to maintain durability, such as heat resistance and heat-and-moisture resistance, even under severe conditions such as high temperature and high humidity. In the case of further peeling, contamination such as cloudiness and adhesive residue is suppressed on the adherend.

  The solution viscosity of the polyurethane resin (A) is not particularly limited and can be appropriately selected depending on the application of the pressure-sensitive adhesive. The solution viscosity is preferably 3,000 to 10,000 mPa · s (25 ° C.) at a nonvolatile content concentration of 60% by weight. When the solution viscosity is within this range, it is preferable because the coating processability is improved while maintaining a sufficient cohesive force.

  The polyurethane resin (A) preferably contains 70 to 99% by weight of the polyol (a1) and 1 to 30% by weight of the polyisocyanate (a2) in all the constituent monomers, and the polyol (a1) 80 to 80%. More preferably, it is contained in an amount of 98% by weight and in the range of 2 to 20% by weight of polyisocyanate (a2). When the polyol (a1) and the polyisocyanate (a2) are in the above range, the viscosity suitable for coating is maintained, so that the polyurethane resin (A) is excellent in handling during coating. When this polyurethane resin (A) is used as a pressure sensitive adhesive, moderate cohesive force and sufficient flexibility can be obtained. In addition to being excellent in removability and removability, it is difficult to lift and peel off even under severe conditions such as high temperature and high humidity after pasting, and can be applied to a surface protective film.

  In addition, the aromatic ring contained in the polyurethane resin (A) is derived from the polyol (a1) or polyisocyanate (a2) as the monomer component, and the content of the aromatic ring is based on the total amount of the polyurethane resin (A). 1 to 30 weight% is preferable and 1.5 to 25 weight% is more preferable. When the aromatic ring content is in the above range, when used as a pressure-sensitive adhesive, tack (adhesiveness) can be reduced, so that not only the removability is good but also good. Durability such as heat resistance and moist heat resistance can be obtained.

<Reactive compound (B) having a functional group capable of reacting with a hydroxyl group>
Next, the reactive compound (B) having a functional group capable of reacting with a hydroxyl group will be described.
In this specification, the reactive compound (B) having a functional group capable of reacting with a hydroxyl group (hereinafter referred to as the reactive compound (B)) is 0.1 to 50 with respect to 100 parts by weight of the polyurethane resin (A). It is necessary to contain 1 part by weight, more preferably 1 to 30 parts by weight. When the reactive compound (B) is in this range, not only the heat resistance and moist heat resistance are improved by the crosslinking reaction with the hydroxyl group contained in the polyurethane resin (A), but also the adhesive layer in a harsh environment. Floating, peeling, or foaming can be suppressed, and application to a surface protective film becomes possible.

Moreover, since the polyurethane resin (A) has a hydroxyl group, examples of the functional group capable of reacting with the hydroxyl group in the reactive compound (B) include an isocyanate group, an alkoxysilyl group, and a methylol group.
Examples of the reactive compound (B) include polyisocyanate (b1), silane compound (b2), and methylolmelamine compound (b3). Among these, the reactive compound (B) is preferably a compound having two or more functional groups capable of reacting with the hydroxyl group of the polyurethane resin (A) in order to impart crosslinkability.
In particular, polyisocyanate (b1) is preferably used because it is excellent in adhesiveness after the crosslinking reaction and adhesion to the substrate (G) described later.

  The polyisocyanate (b1) is a compound having a plurality of isocyanate groups in the molecule. Polyisocyanate (b1) can be classified into aliphatic polyisocyanates, alicyclic polyisocyanates, or aromatic polyisocyanates. In addition, about aliphatic polyisocyanate, alicyclic polyisocyanate, or aromatic polyisocyanate, the polyisocyanate demonstrated by the said polyisocyanate (a2) can be used.

  The polyisocyanate (b1) is preferably a compound having 3 or more isocyanate groups. Such polyisocyanate (b1) is a polyisocyanate having three or more isocyanate groups as described above, and various polyisocyanates such as 2-methylpentane-2,4-diol and trimethylolpropane polyols. Adducts, trimers having an isocyanurate ring, and the like can be preferably used. Polyphenylmethane polyisocyanate (also known as PAPI) and these polyisocyanate-modified products are also preferred. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretonimine 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. The reaction product of a polyol and a diisocyanate can also be used as a compound having at least two isocyanate groups. In addition, as the polyisocyanate (b1), a blocked isocyanate in which an isocyanate group is blocked using a blocking agent can also be used.

  In the case of using the polyisocyanate (b1), a known catalyst can be used as necessary for promoting the reaction between the hydroxyl group of the polyurethane urea resin (A) and the isocyanate group. Examples of the catalyst include tertiary amine compounds and organometallic compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (also known as DBU), and the like.

Examples of the organometallic compound include a tin compound and a non-tin compound.
Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, Examples include tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.
Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. -Iron compounds such as iron ethylhexanoate and iron 2,4-pentadionate, cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate And zirconium naphthenate.
Among these, diazabicycloundecene (alias: DBU), dibutyltin dilaurate (alias: DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.
The catalyst can be used alone or in combination of two or more.

  In particular, polyisocyanate (b1) is an adduct of diisocyanate such as HDI, TDI, MDI, and IPDI with trimethylolpropane, a burette reacted with water, and an isocyanurate ring in terms of crosslinking reactivity. The body is preferably used, but from the standpoint of maintaining the adhesive strength in the microviscous region and reducing the density, adducts of HDI and IPDI with trimethylolpropane having no aromatic ring, burettes reacted with water, isocyanurate Ring trimers are particularly preferred.

  Examples of the silane compound (b2) include alkyl alkoxysilanes, aryl alkoxysilanes, carbamate alkoxysilanes, vinyl alkoxysilanes, halogen alkoxysilanes, (meth) acryloyl alkoxysilanes, mercapto alkoxysilanes, and imidazole alkoxys. Examples include alkoxysilanes having an alkoxyl group such as silane, isocyanate-based alkoxysilane, epoxy-based alkoxysilane, and amino-based alkoxysilane.

  For example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, methyltris (methoxyethoxy) silane, methyltris (methoxypropoxy) silane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxy Silane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, silane Chlorotrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxysilane, dimethylbis (methoxyethoxy) silane, dimethylbis (methoxypropoxy) silane, diethyldimethoxysilane , Diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methylethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxy Alkyl alkoxysilanes such as silane, methylpropyldiisopropoxysilane, methylpropyldiacetoxysilane, etc.

  For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi Aryl-based alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, methylphenyldiacetoxysilane;

  For example, (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, (3-carbamateethyl) propyltripropoxysilane, (3-carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl ) Propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamatebutyl) propyltrimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, (3-carbamatepentyl) propyltriethoxysilane (3-carbamatehexyl) propyltriethoxysilane, (3-carbamateoctyl) pentyl riboxysilane, (3-carbamateethyl) propylsilyltrichloride, (3-carbamateethyl) propyltrimethylsilane, (3-carbamateethyl) Carbamate alkoxysilanes such as) propyldimethylsilane, 3-carbamateethyl) propyltributylsilane, (3-carbamateethyl) ethyl-p-xylenetriethoxysilane, (3-carbamateethyl) -p-phenylenetriethoxysilane;

  For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltris (methoxypropoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, divinyldimethoxysilane , Divinyldiethoxysilane, divinyldiisopropoxysilane, divinyldiacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldiisopropoxysilane, methylvinyldiacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, Diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxy Orchids, vinyl and allylic alkoxysilanes such as methyl allyl diacetoxy silane;

  For example, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropyltrimethoxy Halogen-based alkoxysilanes such as silane, 3,3,3-trifluoropropyltriethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane ;

  For example, 3-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- (Meth) acryloyl-based alkoxysilanes such as acryloxypropylmethyldimethoxysilane;

  For example, mercapto alkoxysilanes such as 3-mercaptopropyltrimethoxylane, 3-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxysilane;

  For example, imidazole alkoxysilanes such as 3- (2-imidazolin-1-yl) propyltrimethoxysilane and 3- (2-imidazolin-1-yl) propyltriethoxysilane;

  For example, isocyanate-based alkoxysilanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltripropoxysilane;

  For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- ( Epoxy-based alkoxysilanes such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane;

  For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxy Silane, N- (2-aminomethyl) 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3- (2-aminoethylaminopropyl) trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane, methyltris (2-aminoethoxy) ) Silane Butylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) trimethylsilane, 2- (2-aminoethylthioethyl) methyldiethoxysilane, 3-allylaminopropyltrimethoxysilane, 3-cyclohexylaminopropyltri Methoxysilane, 2-cyclohexylaminoethylthiomethyltrimethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3 -Aminopropyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-piperazinopropylmethyldimethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane Amino-based alkoxysilanes such like.

Moreover, the silane compound (b2) can also use an oligomeric silane obtained by oligomerizing a mixture of two or more silanes by hydrolysis and condensation.
Among these, a silane compound having no aromatic ring is preferable in terms of wettability with respect to an adherend.
The silane compound (b2) is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl in terms of condensation reaction with the hydroxyl group of the polyurethane resin (A) and improvement in adhesion to the substrate surface. Alkyl alkoxysilanes such as triethoxysilane, 3-mercaptopropyltrimethoxylane, mercaptoalkoxysilanes such as 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silanes, epoxy alkoxysilanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, imidazole alkoxysilanes such as 3- (2-imidazolin-1-yl) propyltriethoxysilane, 3-aminopropyltri Methoxysila 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 2-cyclohexylaminoethylthiomethyl Amino alkoxysilanes such as trimethoxysilane and trimethylsilyldimethylamine, and isocyanate alkoxysilanes such as 3-isocyanatopropyltriethoxysilane are preferred. The silane compound (b2) can be used alone or in combination of two or more.

Examples of the methylol melamine compound (b3) include methylol melamine derivatives obtained by condensing melamine and formaldehyde, and compounds obtained by reacting these with a lower alcohol such as methyl alcohol, ethyl alcohol, or isopropyl alcohol. . Examples of the methylol melamine compound (b3) include monomethylol melamine, dimethylol melamine, trimethylol melamine (also known as cearicin), tetramethylol melamine, pentamethylol melamine, pentamethoxymethylol melamine, hexamethylol melamine, hexamethoxymethylol melamine, Hexaethoxymethylmelamine, hexakis- (methoxymethyl) melamine, N, N ′, N ″ -trimethyl-N, N ′, N ″ -trimethylolmelamine, N, N ′, N ″ -trimethylolmelamine, N, N Examples include ', N ″ -tributyl-N, N ′, N ″ -trimethylol melamine, (hydroxymethyl) pentakis (methoxymethyl) melamine, hexamethylol melamine pentamethyl ether and the like.
Among these, pentamethoxymethylol melamine and hexamethoxymethyl melamine are preferable from the viewpoint of condensation reaction with the hydroxyl group of the polyurethane resin (A) and improvement in adhesion to the substrate surface.
A methylol melamine type compound (b3) can be used individually or in combination of 2 or more types.

  In addition to the polyisocyanate (b1), the silane compound (b2), and the methylolmelamine compound (b3), the reactive compound (B) is excellent in adhesiveness after crosslinking reaction and adhesion to a substrate. Polyisocyanate (b1) is preferable in terms of achieving a high level of flexibility and wettability by controlling the crosslinking density.

<Ester compound (C)>
Next, the ester compound (C) will be described.
The pressure-sensitive adhesive of the present invention can further contain an ester compound (C).
The ester compound (C) can impart a plastic effect to the adhesive layer after coating, and can further improve the wetting and spreading properties of the adhesive film to an adherend such as a glass plate. Moreover, since it becomes possible to lighten peeling at the time of peeling after sticking an adhesive film to a to-be-adhered body, workability | operativity improves. Further, contamination such as adhesive residue on the adherend can be suppressed. In addition, components other than a polyurethane resin (A) and the reactive compound (B) which has a functional group which can react with a hydroxyl group are called arbitrary components.

  The ester compound (C) includes an esterified product of a fatty acid such as aliphatic carboxylic acid, aliphatic phosphoric acid, and aliphatic boric acid and a fatty alcohol containing a hydroxyl group, and an epoxy-modified ester obtained by further epoxy-modifying these esterified products. It is a monster. The ester compound (C) does not include an ethylenically unsaturated double bond-containing compound and an organic solvent. The ester compound (C) is roughly classified into a fatty acid ester (c1), a phosphoric acid ester (c2), and a boric acid ester (c3).

  The fatty acid ester (c1) is (1) an ester of a monobasic acid or polybasic acid having 4 to 22 carbon atoms and a monovalent alcohol having 22 or less carbon atoms, and (2) one having 18 to 22 carbon atoms. An ester of a basic acid and a tetravalent or lower alcohol having 22 or less carbon atoms and an epoxy-modified ester obtained by further modifying the ester of (3), (1) or (2) with an epoxy are preferable.

  The saturated monobasic acid having 4 to 22 carbon atoms is, for example, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylcaproic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, Examples include palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid, and behenic acid.

  Unsaturated monobasic acids having 4 to 22 carbon atoms are crotonic acid, palmitoleic acid, sabienoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, pinolenic acid, eleostearic acid, stearidonic acid, boseopentaene Acid, gadoleic acid, icosadienoic acid, icosatrienoic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, eicosapentaenoic acid, mead acid, arachidonic acid, erucic acid, docosadienoic acid, adrenic acid, ozbond acid, Examples include sardine acid and docosahexaenoic acid.

  Examples of the saturated dibasic acid having 4 to 22 carbon atoms include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedioic acid, and 1,12-dodecanediic acid. Examples include acids, 1,12-octadecanedioic acid, eicosanedioic acid, and the like.

  Examples of the unsaturated dibasic acid having 4 to 22 carbon atoms include maleic acid, fumaric acid, mesaconic acid, muconic acid and the like.

  Polybasic acids having 4 to 22 carbon atoms are isocitrate, aconitic acid, 1,2,3-propanetricarboxylic acid, 1,2,3-propenetricarboxylic acid, camphoric acid, isocamphoronic acid, ethanetetracarboxylic acid, butane. Examples thereof include tetracarboxylic acid, octanetetracarboxylic acid, ethylenetetracarboxylic acid, butenetetracarboxylic acid and the like.

  The monovalent saturated alcohol having 22 or less carbon atoms is, for example, methanol, ethanol, propanol, butanol, hexanol, 2-ethylhexanol, april alcohol, pelargon alcohol, caprin alcohol, undecyl alcohol, 2-butyloctanol, lauryl. Alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol (also known as palmityl alcohol), isocetyl alcohol, heptadecanol, stearyl alcohol, isostearyl alcohol, nonadecyl alcohol, eicosanol (also known as arachidyl alcohol) Octyldodecyl alcohol, heneicosanol, behenyl alcohol, 2- (2-butoxyethoxy) ethyl alcohol, 2- 2-methoxyethoxy) ethyl alcohol, and or alkylene oxide adducts thereof, and the like.

  Examples of the monovalent unsaturated alcohol having 22 or less carbon atoms include palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elide linoleyl alcohol, linolenyl alcohol, erucyl alcohol, and the like. An alkylene oxide adduct of

  Examples of the divalent to tetravalent alcohol having 18 or less carbon atoms include diols having 22 or less carbon atoms, ricinoleyl alcohol, glycerin, diglycerin, polyglycerin, and trimethylolpropane mentioned in the polyol (a1). , Pentaerythritol, sorbitol, etc., or alkylene oxide adducts thereof.

  In the fatty acid ester (c1), (1) Examples of the ester of a monobasic acid or polybasic acid having 4 to 22 carbon atoms and a monohydric alcohol having 22 or less carbon atoms include isopropyl caproate and lauryl caproate. , Stearyl caproate, cetyl caprylate, stearyl caprylate, cetyl 2-ethyl caproate, isocetyl 2-ethyl caproate, stearyl 2-ethyl caproate, stearyl caprate, hexyldecyl dimethyloctanoate, methyl laurate, lauric acid Butyl, hexyl laurate, cetyl laurate, stearyl laurate, isopropyl myristate, isocetyl myristate, stearyl myristate, myristyl myristate, octyldodecyl myristate, isopropyl palmitate, 2-ethyl palmitate Ruhexyl, lauryl palmitate, isostearyl palmitate, methyl stearate, butyl stearate, 2-ethylhexyl stearate, isocetyl stearate, stearyl stearate, octyldodecyl stearate, isotridecyl stearate, isosecil isostearate, isopropyl isostearate, Saturated fatty acid monoesters of monobasic acids and monohydric alcohols such as cholesteryl isostearate, isostearyl behenate, polyoxyethylene lauric acid methyl ester, polyoxyethylene lauric acid stearyl ester, polyoxyethylene stearic acid isopropyl ester;

  For example, lauryl methacrylate, methyl crotonate, butyl crotonate, methyl palmitate, octyldodecyl palmitate, methyl sabiate, methyl oleate, methyl oleate, isopropyl oleate, butyl oleate, octyl oleate, octyl oleate Dodecyl, methyl elaidate, methyl vaccenate, methyl linoleate, ethyl linoleate, isopropyl linoleate, butyl linoleate, octyldodecyl linoleate, ethyl linolenate, octyldodecyl linolenate, methyl pinolenate, methyl pinolenate, eleeo Methyl stearate, methyl stearidate, butyl stearidate, methyl boseopentenoate, methyl gadoleate, methyl icosadienoate, methyl icosatrienoate, eicosene Methyl, ethyl eicosenoate, isopropyl eicosenoate, methyl eicosadienoate, methyl eicosatrienoate, methyl eicosatetraenoate, methyl eicosapentaenoate, methyl medeate, methyl arachidate, methyl erucate, methyl docosadienoate, adrenic acid Unsaturated fatty acid monoesters of monobasic acids and monohydric alcohols such as methyl, methyl ozbondate, methyl sardate, methyl docosahexaenoate;

  For example, diethyl succinate, diisopropyl succinate, dibutyl succinate, dimyristyl succinate, diethyl glutarate, diethyl 3-methylglutarate, dibutyl glutarate, diethyl adipate, diisopropyl adipate, bis (2-butoxyethyl) adipate Bis (2- (2-butoxyethoxy) ethyl adipate), bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, diisostearyl adipate, diethyl pimelate, dibutyl pimelate, diethyl suberate , Diethyl azelate, diethyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisocetyl sebacate, dibutyloctyl sebacate, diisostearyl sebacate, dibuty 1,10-decandioate Saturated fatty acid diester of a dibasic acid and a monohydric alcohol and the like;

  For example, dimethyl maleate, diethyl maleate, diisopropyl maleate, dibutyl maleate, dimethyl fumarate, diisopropyl fumarate, dimethyl mesaconate, diethyl mesaconate, diisopropyl mesaconate, dibutyl mesaconate, dimethyl muconate, diethyl muconate, etc. An unsaturated fatty acid diester of a dibasic acid and a monohydric alcohol;

Trimethyl isocitrate, trimethyl aconitate, trimethoxypolyoxyethylene aconite, trimethyl 1,2,3-propanetricarboxylate, trimethyl 1,2,3-propenetricarboxylate, trimethyl camphorate, trimethoxypolyoxyethylene camphorate, Trimethyl isocamphorate, tetramethyl ethanetetracarboxylate, dimethylbutanetetracarboxylate, trimethylbutanetetracarboxylate, tetramethylbutanetetracarboxylate, tetramethyloctanetetracarboxylate, tetramethylethylenetetracarboxylate, tetramethylbutenetetracarboxylate Unsaturated polyvalent esters of polybasic acids such as monohydric alcohols;

  For example, monobasic acids and monovalents such as monoisopropyl succinate, monoethyl adipate, monoisodecyl adipate, monoisopropyl sebacate, monoisostearyl sebacate, monoethyl mesaconate, monoisopropyl mesaconate, dimethyl aconite, dimethyl camphorate And unsaturated fatty acid monoesters with alcohols.

  In addition, in the fatty acid ester (c1), (2) as an ester of a monobasic acid having 4 to 22 carbon atoms and a tetravalent or lower alcohol having 22 or less carbon atoms, for example, diethylene glycol dibutyrate or divaleric acid Diethylene glycol, neopentyl glycol dicaproate, diethylene glycol dicaproate, triethylene glycol dicaproate, oxyethylene dicaproate, dipropylene glycol dicaproate, polyoxypropylene dicaproate, diethylene glycol dienanthate, neopentyl glycol dicaprylate, ethylene glycol dicaprylate, Propylene glycol dicaprylate, polyoxyethylene dicaprylate, neopentyl glycol di2-ethylcaproate, diethylene glycol di2-ethylcaproate, di-2 Polyoxypropylene ethyl caproate, dipropylene glycol di2-ethylcaproate, dipropylene glycol di2-ethylcaproate, diethylene glycol dipelargonate, diethylene glycol dicaprate, propylene glycol dicaprate, polyoxyethylene dicaprate, neopentyl dilaurate Glycol, diethylene glycol dilaurate, polyoxyethylene dilaurate, polyoxypropylene dilaurate, neopentyl glycol dimyristate, diethylene glycol dimyristate, dipropylene glycol dimyristate, polyoxypropylene dimyristate, polyoxyethylene dimyristate , Polyoxypropylene dimyristate, diethylene glycol dipentadecylate, dipal Neopentyl glycol thiolate, diethylene glycol dipalmitate, polyoxyethylene dipalmitate, diethylene glycol dimargarate, neopentyl glycol distearate, ethylene glycol distearate, diethylene glycol distearate, polyoxyethylene distearate, polyoxypropylene distearate, disoxy stearate Saturated monobasic acids such as ricinoleyl acid, diethylene glycol diisostearate, polyoxyethylene diisostearate, propylene glycol diisostearate, polyoxypropylene diisostearate, diethylene glycol diarachidate, diethylene glycol dibehenate, polyoxyethylene bisphenol A laurate and the like Alcohol (aka: Geo) Saturated fatty acid diesters;

  For example, ethylene glycol dicrotonate, propylene glycol dicrotonate, polyoxyethylene dicrotonate, ethylene glycol dipalmitoleate, ethylene glycol disabienoate, ethylene glycol dioleate, polyoxyethylene dioleate, neopentyl glycol dioleate, hexyl glycol dioleate , Propylene glycol dioleate, polyoxypropylene dioleate, ethylene glycol dieleic acid, polyoxypropylene dielaidate, ethylene glycol dibacate, ethylene glycol dilinoleate, propylene glycol dilinoleate, neopentyl glycol dilinoleate, ethylene glycol dilinolenate, dilinolene Acid polyoxyethylene, propylene dilinolenate Recall, Polyoxyethylene dilinoleate, Neopentyl glycol dilinolenate, Ethylene glycol dipinolenate, Ethylene glycol dieleostearate, Ethylene glycol distearide, Ethylene glycol diboseopentaenoate, Ethylene glycol digadelate, Ethylene glycol diicosadienoate, Diicosatriene Ethylene glycol, dieicosenoic acid ethylene glycol, dieicosadienoic acid ethylene glycol, dieicosatrienoic acid ethylene glycol, dieicosatetraenoic acid ethylene glycol, dieicosapentaenoic acid ethylene glycol, dimedic acid ethylene glycol, diarachidic acid ethylene glycol, dierucic acid ethylene glycol, Didocosadienoic acid ethylene glycol, dia Unsaturated monobasic acids and dihydric alcohols such as ethylene glycol renate, ethylene glycol ethylene glycol, ethylene glycol diwasate, ethylene glycol didocosahexaenoate, polyoxyethylene di-2-ethylcaproate ether / caprate (also known as: Diols) and unsaturated fatty acid diesters;

  For example, caproic acid triglyceride, caprylic acid triglyceride, 2-ethylcaproic acid triglyceride, 2-ethylcaproic acid polyoxyethylene triglyceride, 2-ethylcaproic acid polyoxypropylene triglyceride, pelargonic acid triglyceride, capric acid triglyceride, lauric acid triglyceride, laurin Acid polyoxyethylene triglyceride, myristic acid triglyceride, myristic acid polyoxyethylene triglyceride, pentadecylic acid triglyceride, palmitic acid triglyceride, palmitic acid polyoxyethylene triglyceride, margaric acid, stearic acid diglyceride, stearic acid triglyceride, stearic acid polyoxyethylene triglyceride, Isostearic acid triglyceride, arachidic acid Reglycerides, behenic acid triglycerides, tricaproic acid trimethylolpropane, tricaprylic acid trimethylolpropane, tri2-ethylcaproic acid trimethylolpropane, tri-2-ethylcaproic acid polypolyoxyethylene trimethylolpropane, tricapric acid trimethylolpropane, dilauric acid tritriol Methylolpropane, trimethylolpropane trilaurate, polyethylene glycol trimethyloltrilaurate, trimethylolpropane dimyristate, trimethylolpropane trimyristate, trimethylolpropane tripalmitate, polyethyleneglycol trimethylolpropane tripalmitate, tristearic acid Trimethylolpropane, polyoxyethylenetrimethyltristearate Roll propane, trimethylolpropane triisostearate, pentaerythritol tetracaproate, pentaerythritol tetracaprylate, pentaerythritol tetra2-ethylcaproate, pentaerythritol tetracaprate, pentaerythritol tetralaurate, pentaerythritol tetramyristate, mono Pentaerythritol palmitate, pentaerythritol dipalmitate, pentaerythritol tripalmitate, pentaerythritol tetrapalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tetrastearate, pentaerythritol tetrastearate, pentaisostearate Erythritol, tetra-2-ethylca Diglyceryl proate, diglyceryl tetralaurate, diglyceryl tetramyristate, diglyceryl tetrapalmitate, diglyceryl tetrastearate, polyoxyethylene sorbite hexahexaethylcaproate, polyoxyethylene sorbitol hexalaurate, hexamyristine Acid polyoxyethylene sorbitol, hexapalmitic acid polyoxyethylene sorbitol, tristearic acid polyoxyethylene sorbitol, hexastearic acid polyoxyethylene sorbit, hexaisostearic acid polyoxyethylene sorbitol, polylauryl tetralaurate, polyglyceryl tetrastearate, hexastearin Saturated fatty acid polyvalent esters of saturated monobasic acids such as polyglyceryl acid and polyhydric alcohols;

  For example, crotonic acid triglyceride, palmitoleic acid triglyceride, sabienoic acid triglyceride, oleic acid diglyceride, oleic acid triglyceride, elaidic acid triglyceride, vaccenic acid triglyceride, linoleic acid diglyceride, linoleic acid triglyceride, linolenic acid diglyceride, linolenic acid triglyceride, pinolenic acid triglyceride, Eleostearic acid triglyceride, stearidonic acid triglyceride, boseopentaenoic acid triglyceride, gadedoic acid triglyceride, icosadienoic acid triglyceride, icosatrienoic acid triglyceride, eicosenoic acid triglyceride, eicosadienoic acid triglyceride, eicosatrienoic acid triglyceride, eicosatetraenoic acid triglyceride, eicosapentaenoic acid Trig Seride, Mead acid triglyceride, Arachidonic acid triglyceride, Erucic acid triglyceride, Docosadienoic acid triglyceride, Adrenic acid triglyceride, Ozbond acid triglyceride, Iwacic acid triglyceride, Docosahexaenoic acid triglyceride, Tetracrotonic acid pentaerythritol, Tetrapalmitoleic acid pentaerythritol, Tetrasabienoic acid penta Erythritol, Pentaerythritol monooleate, Pentaerythritol dioleate, Pentaerythritol trioleate, Pentaerythritol tetraoleate, Pentaerythritol tetraelainate, Pentaerythritol tetraboleate, Pentaerythritol tetralinoleate, Pentaerythritol dilinolenate, Trilinolene Pentaeri acid Lititol, pentaerythritol tetralinolenate, pentaerythritol tetrapinolenate, pentaerythritol tetraelestearate, pentaerythritol tetrastearidate, pentaerythritol tetrabotheopentanoate, pentaerythritol tetragadelate, pentacoledielate Erythritol, Tetraicosatrienoic acid pentaerythritol, Tetraicosenic acid pentaerythritol, Tetraicosadienoic acid pentaerythritol, Tetraicosatrienoic acid pentaerythritol, Tetraicosatetraenoic acid pentaerythritol, Tetraicosapentaenoic acid pentaerythritol, Tetramede Pentaerythritol acid, pentaerythritol tetraarachidonic acid, tetraerucic acid pen Taerythritol, pentaerythritol tetradocosadienoate, pentaerythritol tetraadrenoate, pentaerythritol tetraozbond acid, pentaerythritol tetriwasate, pentaerythritol tetradocosahexaenoate, crotonic acid polyoxyethylene triglyceride, palmitoleic acid polyoxyethylene triglyceride, linoleic acid Polyoxyethylene triglyceride, linolenic acid polyoxyethylene triglyceride, oleic acid polyoxyethylene triglyceride, tetrapalmitoleic acid polyoxyethylene pentaerythritol, tetralinoleic acid polyoxyethylene pentaerythritol, tetralinolenic acid polyoxyethylene pentaerythritol, hexacrotonic acid poly Oxyethylene sorbit, Oxapalmitoleic acid polyoxyethylene sorbite trioleic acid polyoxyethylene sorbite, tetraoleic acid polyoxyethylene sorbitol, hexaoleic acid polyoxyethylene sorbitol, hexaelaidic acid polyoxyethylene sorbitol, tetralinoleic acid polyoxyethylene sorbitol, hexalinoleic acid Unsaturated monobasic acids and polyhydric alcohols such as polyoxyethylene sorbit, tetralinolenic acid polyoxyethylene sorbit, hexalinolenic acid polyoxyethylene sorbit, hexastearidonic acid polyoxyethylene sorbit, hexaeicosenoic acid polyoxyethylene sorbit Unsaturated fatty acid polyesters of

  For example, glyceryl mono-2-ethylcaproate, glyceryl di-2-ethylcaproate, glyceryl tri-2-ethylhexanoate, glyceryl monobehenate, glyceryl monocaprylate, glyceryl tricaprylate, glyceryl trilaurate, glyceryl tricaprate, triisostearic acid Glyceryl, glyceryl dibehenate, glyceryl tribehenate, glyceryl tribehenate, polyoxyethylene glyceryl monolaurate, polyoxyethylene glyceryl monomyristate, polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl monooleate, mono-2-ethylcapron Trimethylolpropane acid, trimethylolpropane di-2-ethylcaproate, trimethylolpropane tri-2-ethylcaproate Monolauric acid polyoxyethylene trimethylolpropane, monomyristic acid polyoxyethylene trimethylolpropane, monostearic acid polyoxyethylenetrimethylolpropane, monooleic acid polyoxyethylenetrimethylolpropane, monolinoleic acid polyoxyethylenetrimethylolpropane, mono Linolenic acid polyoxyethylene trimethylolpropane, polyoxyethylene sorbitan monostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate Esters, polyoxyethylene glyceryl monoisostearate, pentaerythris Tall mono laurate, pentaerythritol monomyristate, pentaerythritol monostearate, pentaerythritol monooleate, fatty acid monoesters of monobasic acids with polyhydric alcohols such as pentaerythritol mono linoleic acid esters.

In the fatty acid ester (c1), the epoxy-modified ester obtained by further modifying the ester of (3), (1) or (2) with an epoxy includes the above unsaturated fatty acid monoester, unsaturated fatty acid diester, or unsaturated fatty acid polyvalent ester. An epoxy-modified ester obtained by allowing a peracid such as m-chloroperbenzoic acid or dimethyloxirane to act on the ester to epoxidize the olefinic double bond contained in the unsaturated fatty acid ester is exemplified.
The fatty acid ester (c1) can be used alone or in combination of two or more.

The phosphate ester (c2) is an ester compound obtained by dehydration condensation of phosphoric acid and the above-mentioned tetravalent or lower alcohol having 22 or less carbon atoms.
For example, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monobutyl phosphate, monohexyl phosphate, mono-2-ethylhexyl phosphate, monoapril phosphate, monopelargone phosphate, monocaprin phosphate, monoundecyl phosphate, phosphate Mono-2-butyloctyl, monolauryl phosphate, monotridecyl phosphate, monomyristyl phosphate, monopentadecyl phosphate, monopalmityl phosphate, monoisocetyl phosphate, monoheptadene phosphate, monostearyl phosphate, monoisostearyl phosphate, Monononadecyl phosphate, monoarachidyl phosphate, monooctyl dodecyl phosphate, monoheneicosane phosphate, monobehenyl phosphate, mono 2- (2-butoxyethoxy) ethyl phosphate, mono 2- (2-methoxyethoxy) ethyl phosphate Yama Phosphate saturated monocarboxylic esters such as alkylene oxide adducts thereof;

  For example, phosphate unsaturation such as monopalmitoleyl phosphate, monoelasyl phosphate, monooleyl phosphate, monolinoleyl phosphate, monoelyl phosphate phosphate, monolinoleyl phosphate, monoercyl phosphate, or alkylene oxide adducts thereof Monoesters;

  For example, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dihexyl phosphate, di-2-ethylhexyl phosphate, diapril phosphate, dipelargone phosphate, dicaprin phosphate, diundecyl phosphate, di-2-phosphate Butyloctyl, dilauryl phosphate, ditridecyl phosphate, dimyristyl phosphate, dipentadecyl phosphate, dipalmityl phosphate, diisocetyl phosphate, diheptadene phosphate, distearyl phosphate, diisostearyl phosphate, dinonadecyl phosphate, diarachidyl phosphate Dioctyldodecyl phosphate, diheneicosane phosphate, dibehenyl phosphate, di-2- (2-butoxyethoxy) ethyl phosphate, di-2- (2-methoxyethoxy) ethyl phosphate, or alkylene oxide adducts thereof Phosphoric acid saturated di Ester;

  For example, dipalmitoleyl phosphate, dieridyl phosphate, dioleyl phosphate, dilinoleyl phosphate, dielyl phosphate phosphate, dilinoleyl phosphate, dielsyl phosphate, or alkylene oxide adducts thereof ;

For example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, triapril phosphate, tripelagon phosphate, tricaprin phosphate, triundecyl phosphate, phosphate Tri-2-butyloctoctyl, trilauryl phosphate, tritridecyl phosphate, trimyristyl phosphate, tripentadecyl phosphate, tripalmityl phosphate, triisocetyl phosphate, triheptadene phosphate, tristearyl phosphate, triisostearyl phosphate, Trinonadecyl phosphate, triarachidyl phosphate, trioctyldodecyl phosphate, triheneicosane phosphate, ditribehenyl phosphate, tri-2- (2-butoxyethoxy) ethyl phosphate, tri-2- (2-methoxyethoxy) ethyl phosphate And Or phosphoric acid saturated triesters such as alkylene oxide adducts thereof;

  For example, phosphate unsaturation such as tripalmityl phosphate, trieriyl phosphate, trioleyl phosphate, trilinoleyl phosphate, trilinoleyl phosphate, trilinolenyl phosphate, trielsyl phosphate, or their alkylene oxide adducts Triester;

For example, for example, polyoxyethylene oleyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene octyl ether phosphate, polyoxyethylene decyl ether phosphate, etc. Polyoxyalkylene alkyl ether phosphate ester having 2 to 20 moles of addition of ethylene oxide (EO);

For example, polyoxyethylene oleyl phenyl ether phosphate, polyoxyethylene lauryl phenyl ether phosphate, polyoxyethylene cetyl phenyl ether phosphate, polyoxyethylene octyl phenyl ether phosphate, polyoxyethylene decylphenyl ether phosphate Examples thereof include polyoxyethylene alkylphenyl ether phosphates having 2 to 20 addition moles of ethylene oxide (EO) such as esters and polyoxyethylene ethyl phenyl ether phosphates.
The phosphate ester (c2) can be used alone or in combination of two or more.

The boric acid ester (c3) is an ester compound obtained by dehydration condensation between boric acid and the above-mentioned tetravalent or lower alcohol having 22 or less carbon atoms.
For example, methoxydiethylene glycol ether borate, methoxytriethylene glycol ether borate, methoxytetraethylene glycol ether borate, ethoxytriethylene glycol ether borate, ethoxydiethylene glycol ether borate, ethoxytetraethylene glycol ether borate Ester, propoxy triethylene glycol ether borate, triethylene glycol monobutyl ether borate, diethylene glycol monobutyl ether borate, butoxytetraethylene glycol ether borate, butoxytriethylene glycol ether borate, butoxytetraethylene glycol ether Borate ester Xypentoxydiethylene glycol ether borate, pentoxytriethylene glycol ether borate, 2-ethylhexyloxydiethylene glycol ether borate, diethylene glycol monopropyl ether ether borate, triethylene glycol monopropyl ether borate, polyethylene glycol mono Polyoxyalkylene alkyl ether borate esters having 2 to 20 moles of addition of ethylene oxide (EO) such as butyl ether borate ester, polyethylene glycol monopropyl ether borate ester, polyethylene glycol monobutyl ether borate ester;

  For example, dipropylene glycol monomethyl ether borate, dipropylene glycol monopropyl ether borate, tripropylene glycol monopropyl ether borate, dipropylene glycol monobutyl ether borate, dipropylene glycol monomethyl ether borate, tripropylene Propylene oxide (PO) such as propylene glycol monoethyl ether borate, tripropylene glycol monopropyl ether borate, tripropylene glycol monobutyl ether borate, polypropylene glycol monopropyl ether borate, polypropylene glycol monobutyl ether borate ) Polyoxyalkylene alkyl having 2 to 20 moles added Ether borate ester;

For example, polyoxyalkylene alkyl ether borate esters having 2-20 addition moles of butylene oxide (BO) such as polybutylene glycol monopropyl ether borate ester and polybutylene glycol monobutyl ether borate ester;

For example, di (glycerin) borate monostearate, di (glycerin) borate sesquistearate, di (glycerin) borate monooleate, polyoxyethylene di (glycerin) borate monopalinate (EO addition mole number: 6 to 20), Examples include glycerin ether borate esters such as polyoxyethylene di (glycerin) borate monooleate (EO addition mole number: 6 to 20).
The borate ester (c3) can be used alone or in combination of two or more.

The ester compound (C) preferably has a molecular weight (formula weight) of 200 to 2,000. When the molecular weight is in the above range, the compatibility with the polyurethane resin (A) is improved, so that the removability is improved by improving the transparency and cohesion, and the adherend is hardly contaminated.

  It is preferable to contain 1-100 weight part of ester compounds (C) with respect to 100 weight part of polyurethane resins (A), and 5-50 weight part is more preferable. When the ester compound (C) is in the above range, the adhesive layer can be sufficiently plasticized to improve flexibility, and further improve the maintenance of low adhesive strength in the microviscous region and the wet-spreading property of the pressure-sensitive adhesive film. be able to.

  Among these, the ester compound (C) is, for example, cetyl 2-ethylcaproate, 2-ethyl in terms of wet spreadability, removability, and suppression of adherend contamination in addition to industrial availability. Isocetyl caproate, stearyl 2-ethylcaproate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, methyl laurate, butyl laurate, hexyl laurate, hexyl dimethyloctanoate, methyl oleate, myristyl myristate, Isopropyl palmitate, 2-ethylhexyl palmitate, methyl stearate, butyl stearate, 2-ethylhexyl stearate, stearyl stearate, isotridecyl stearate, isopropyl isostearate, cholesteryl isostearate Lauryl methacrylate, isopropyl oleate, butyl oleate, octyl oleate, octyldodecyl oleate, neopentyl glycol di-2-ethylcaproate, polyoxyethylene di-2-ethylcaproate, propylene glycol dicaprylate, propylene glycol dicaprate , Propylene glycol diisostearate, bis {2- (2-butoxyethoxy) ethyl adipate}, bis (2-butoxyethyl) adipate, diisodecyl adipate, bis (2-ethylhexyl) adipate, di-2-ethylcaproic acid Neopentyl glycol, oxyethylene di-2-ethylcaproate (EO addition mole number: 4 to 16), glyceryl tri-2-ethylcaproate, glyceryl monocaprylate, glyceryl tricaprylate, Glyceryl behenate, glyceryl monobehenate, glyceryl tri-2-ethylcaproate, glyceryl trilaurate, glyceryl tricaprate, glyceryl triisostearate, 2-ethylcaproate polyoxyethylene triglyceride (EO addition moles: 2 to 16), poly Fatty acid esters such as oxyethylene bisphenol A laurate, glyceryl trioleate, trimethylolpropane tri2-ethylcaproate, triglyceride oleate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, Tri-2-ethylhexyl phosphate, trioctyl phosphate, polyoxyethylene oleyl ether phosphate ester (EO addition mole number: 2 to 16), Phosphoric esters such as polyoxyethylene lauryl ether phosphate (EO addition moles: 2 to 16), polyoxyethylene octyl ether phosphate (EO addition moles: 2 to 16), or triethylene glycol monopropyl Examples thereof include ether borate esters, polyethylene glycol monobutyl ether borate esters (EO addition mole number: 2 to 16), polyoxyethylene glycerine ether borate esters (EO addition mole number: 2 to 16), and the like.

<Ionic compound (D)>
Further, the ionic compound (D) will be described.
The pressure-sensitive adhesive of the present invention can further contain an ionic compound (D).
The ionic compound (D) is a liquid or solid ionic compound at normal temperature (25 ° C.). Examples of the ionic compound (D) include inorganic salts of alkali metals and organic salts of alkali metals. Examples of the ionic compound (D) include surfactants, ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate. Among these, alkali metal salts, liquid ionic compounds, and solid ionic compounds are preferable, and alkali metal salts and liquid ionic compounds are more preferable.

Examples of the alkali metal salt include metal salts composed of lithium, sodium, and potassium. The alkali metal salt is composed of a cation moiety composed of Li ⁺ , Na ⁺ and K ⁺ and various anion moieties. According to the kind of anion part, it can be divided into an inorganic salt and an organic salt. Examples of the alkali metal inorganic salt include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate (LiClO ₄ ), potassium chlorate, potassium nitrate, sodium nitrate, sodium carbonate, sodium thiocyanate, LiBr, LiI, LiBF _4. , LiPF ₆ , LiSCN and the like. From the viewpoints of conductivity and safety, sodium chloride, potassium chloride, lithium perchlorate and the like are preferable.

Examples of the alkali metal organic salt include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) IN, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) IN, Li (CF ₃ SO ₂ ) ₃ C and the like can be mentioned, and LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N Li (CF ₃ SO ₂ ) IN, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) IN, Li (CF ₃ SO ₂ ) ₃ C and the like are preferable, and Li (CF _{3 SO 2) 2 N, Li (} CF 3 SO 2) iN, Li (C 2 F 5 SO 2) 2 N, Li (C 2 F 5 SO 2) fluorine-containing lithium imide salts such as iN, in particular (perfluoroalkyl sulfonyl ) Imidolithium salt and the like.

  A liquid ionic compound is a compound that exhibits liquid properties at room temperature, and is composed of a cation component and an anion component. Examples of the cation component include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, and a pyrazolium. Examples thereof include a cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation.

The anion component only needs to be able to generate a liquid ionic compound. For example, Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , F (HF) _n ⁻ , (CN) ₂ N ⁻ , C ₄ F ₉ SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , C ₃ F ₇ COO ⁻ , ( CF ₃ SO ₂ ) (CF ₃ CO) N- ^{and the} like. Among these, an anionic component containing a fluorine atom is preferable because an ionic compound having a low melting point can be obtained.

  Examples of the liquid ionic compound include 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1 -Butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-hexylpyridinium tetrafluoroborate, 2-methyl-1-pyrrolinetetrafluoro Borate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-e Ru-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1 -Ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis (trifluoromethane Sulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl- -Methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1- Butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazole 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphine 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2,3 -Dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium Bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium vinyl (Trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N- Methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N- Methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) Imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3- Methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium (trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoro Acetamide, glycidyltrimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl Ru-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl- N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, -Dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl -N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluorome Sulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium Bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) Imido, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethyl Pentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N -Methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium Bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hex Ruammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-octyl- 4-methyl pyridium bis (fluorosulfonyl) imide etc. are mentioned.

It is preferable to contain 0.001-20 weight part of ionic compounds (D) with respect to 100 weight part of polyurethane resins (A). When the amount is within the above range, a sufficient antistatic function is exhibited, and whitening or bleeding out of the adhesive layer can be suppressed.
The ionic compound (D) can be used alone or in combination of two or more.

<Any material (E) of an ultraviolet shielding agent, an antioxidant, a light stabilizer, or a fluorescent brightening agent>
Next, the material (E) of any one of an ultraviolet shielding agent, an antioxidant, a light stabilizer, and a fluorescent brightening agent will be described.
The pressure-sensitive adhesive of the present invention may further contain a material (E) selected from the group consisting of an ultraviolet shielding agent, an antioxidant, a light stabilizer, and a fluorescent brightening agent.

Here, the ultraviolet shielding agent is a material that generally absorbs ultraviolet rays having a wavelength of about 200 to 380 nm, changes the energy into energy such as heat and infrared rays, and releases the ultraviolet rays.
Ultraviolet shielding agents include inorganic compounds and organic compounds. Examples of the inorganic compound include fine particles of metal oxide such as titanium dioxide, zinc oxide, iron oxide, cerium oxide, thallium oxide, lead oxide, and zirconium oxide. Among these, zinc oxide is preferable from the viewpoint of colorlessness and transparency.
Organic compounds include, for example, benzotriazole, triazine, cyanine, cinnamic acid, p-aminobenzoic acid, benzoate, benzophenone, 2-cyanopropenoic acid ester, indole, benzalmalonate , Salicylic acid type, oxalic acid anilide type, formamidine type, benzodithiol type, anthranilate type, camphor derivative type, benzalmalonate derivative type, resorcinol type, oxalinide type, coumarin derivative type and the like.

  In the organic compound, benzotriazole is, for example, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2 -(2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl -6- (tert-butyl) phenol and the like.

  Triazines include, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [hexyl) oxy] -phenol, 2,4,6-tris- (diisobutyl 4′- Amino-benzalmalonate) -s-triazine, 4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 -Dodecyl And oxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

  Examples of the benzophenone series include diphenylmethanone, methyldiphenylmethanone, 4-hydroxydiphenylmethanone, 4-methoxydiphenylmethanone, 4-octoxydiphenylmethanone, 4-decyloxydiphenylmethanone, and 4-dodecyloxydiphenyl. Methanone, 4-benzyloxydiphenylmethanone, 4,2 ′, 4′-trihydroxydiphenylmethanone, 2′-hydroxy-4,4′-dimethoxydiphenylmethanone, 4- (2-ethylhexyloxy) -2 -Hydroxy-diphenylmethanone, methyl o-benzoylbenzoate, benzoin ethyl ether and the like.

  Examples of the 2-cyanopropenoic acid ester include ethyl α-cyano-β, β-diphenylpropenoic acid ester, isooctyl α-cyano-β, β-diphenylpropenoic acid ester, and the like.

  Examples of the salicylic acid ester type include isocetyl salicylate, octyl salicylate, glycolic salicylate, and phenyl salicylate.

  The cinnamic acid system includes, for example, ethylhexylmethoxycinnamate, isopropylmethoxycinnamate, isoamylmethoxycinnamate, diisopropylmethylcinnamate, glyceryl-ethylhexanoate dimethoxycinnamate, methyl-α-carbomethoxycinnamate, methyl-α- And cyano-β-methyl-p-methoxycinnamate.

  Examples of the camphor derivative include benzylidene camphor, benzylidene camphor sulfonic acid, camphor benzalkonium methosulfate, terephthalylidene dicamphor sulfonic acid, polyacrylamide methylbenzylidene camphor, and the like.

  The oxalinide series includes, for example, 4,4′-di-octyloxy oxanilide, 2,2′-diethoxyoxy oxanilide, 2,2′-di-octyloxy-5,5′-di-tert- Butyl oxanilide, 2,2′-di-dodecyloxy-5,5′-di-tert-butyl oxanilide, 2-ethoxy-2′-ethyl oxanilide, N, N′-bis (3- (Dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxy oxanilide and the like.

  Examples of the coumarin derivative system include 7-hydroxycoumarin.

  Examples of the anthranilate system include compounds such as methyl anthranilate.

  Examples of the resorcinol group include compounds such as dibenzoyl resorcinol and bis (4-tert-butylbenzoyl resorcinol).

The benzoxazine system is 3-methyl-2- (2- (1-methyl-2,5-diethyl-1H-pyrrol-3-yl) ethenyl) -benzoxazolium chloride,
And 3-ethyl-2- (2- (1-ethyl-2,5-dimethyl-1H-pyrrol-3-yl) ethenyl) -benzoxazolium chloride.

  Examples of the benzalmalonate system include dimethicodiethylbenzalmalonate.

  Examples of the p-aminobenzoic acid system include diethylaminohydroxybenzoyl hexyl benzoate and the like.

  Antioxidants are antioxidants added to suppress the oxidation of components. For example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur antioxidant, etc. are mentioned.

Examples of the phenolic antioxidant include monophenolic, bisphenolic, and polymeric phenolic antioxidants.
Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β- (3, Monophenolic antioxidants such as 5-di-t-butyl-4-hydroxyphenyl) propionate;

  For example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6- t-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy) Bisphenol antioxidants such as -5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane;

  For example, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t -Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3 "-bis- (4′-Hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S— High molecular type phenolic antioxidants such as triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like can be mentioned.

  Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, and the like.

Examples of phosphorus antioxidants include triphenyl phosphite, trisnonyl phenyl phosphite, di-cresyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, and tris (2,4-di-tert-butylphenyl). Phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, etc. Can be mentioned.
Among these, a phenol-based antioxidant or a phosphorus-based antioxidant is preferable because it is difficult to be colored.
Antioxidants can be used alone or in combination of two or more.

A light stabilizer is a compound that reduces auto-oxidative degradation by radicals generated by light energy and suppresses resin degradation.
The light stabilizer is preferably a hindered amine compound (hereinafter abbreviated as “HALS”), a hindered phenol compound or the like, and more preferably HALS.

  HALS is, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine. -2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], 2 , 2′-thiobis (4-t-octylphenolate) alkylamine nickel, dibutylamino-1,3,5-triazine, N, N-bis (2,2,6,6-tetramethyl-4-piperidyl- Examples include 1,6-hexamethylenediamine, polycondensates of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, and the like.

  Examples of hindered phenol compounds include 4,4′-thiobis (6-tert-3-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′- Butylidene-bis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,6-di-tert-butylphenol, 4,4'-methylenebis (6-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4′-methylenebis (6-tert-butyl-o-cresol), 4,4′-thiobis (6-tert-butyl-o-cresol), 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) Butane, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, 1,3-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -2,2′-bis (2-dodecylthionitroxycarbonyl) propane, 1,6-bis (3 5-bi-tert-butyl-4-hydroxyphenylacetoxy) hexane, 6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-bis (n-octylthio) -1,3 5-triazine, tetrabis [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, n-octadecyl-3- (4′-hydride) Xy-3 ′, 5′-di-tert-butylphenyl) propionate, di-octadecyl-4-hydroxy-3,5-di-tert-butylbenzylphosphonate, di-ethyl-4-hydroxy-3,5-di -Tert-butylbenzylphosphonate and the like. The hindered phenolic compound can also be used as a phenolic antioxidant.

The fluorescent whitening agent (e4) is a kind of dye, and is a compound that has the effect of absorbing white light and converting it into pale light (fluorescence) to increase whiteness.
Examples of the optical brightener include benzoxazole, triazine, pyrazoline, and coumarin compounds.

  Material (E) can contain 0.001-20 weight part with respect to 100 weight part of polyurethane resins (A). When the material (E) is used in the above range, the ultraviolet shielding function and weather resistance are improved, and the transparency of the adhesive layer is improved.

<Hydrolysis inhibitor (F)>
The pressure-sensitive adhesive of the present invention may further contain a hydrolysis inhibitor.
When the hydrolysis inhibitor (F) is contained, the carboxyl group generated when the polyurethane resin (A) undergoes hydrolysis in a high temperature and high humidity atmosphere can be blocked.
The hydrolysis inhibitor (F) is preferably, for example, a carbodiimide, isocyanate, oxazoline, or epoxy system, and a carbodiimide is more preferable because hydrolysis can be more effectively suppressed.
The hydrolysis inhibitor (F) is preferably contained in an amount of 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, based on 100 parts by weight of the polyurethane resin (A). More preferred is 05 to 1.0 part by weight.
Hydrolysis inhibitors can be used alone or in combination of two or more.

  Note that. The hydrolysis inhibitor (F) is preferably used in combination with the material (E), and particularly preferably used in combination with an antioxidant. Specifically, a combination of a carbodiimide-based hydrolysis inhibitor and a phenol-based antioxidant is preferable, and a combination of a carbodiimide-based hydrolysis inhibitor, a phenol-based antioxidant, and a phosphorus-based antioxidant is more preferable. By using a hydrolysis inhibitor and an antioxidant in combination, hydrolysis resistance can be further improved, and decomposition and thermal yellowing of the hydrolysis inhibitor itself can be suppressed.

A carbodiimide-based hydrolysis inhibitor is a compound having a carbodiimide group.
Examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, naphthylcarbodiimide, and the like.
The polycarbodiimide compound is a high molecular weight polycarbodiimide produced by decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst.
Examples of the polycarbodiimide compound include 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, and 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 Examples include '-dicyclohexylmethane diisocyanate and tetramethylxylylene diisocyanate. The carbodiimidization catalyst was 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl. Phospholene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers.

<Other components (P)>
The pressure-sensitive adhesive of the present invention can contain other components as long as the problem can be solved.
Other components (P) include, for example, viewpoints such as polymerization curing shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, and coloring improvement. From the above, an organic or inorganic filler can be blended. The filler is composed of polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments, and the like. The shape of the filler is preferably, for example, particulate or fibrous. In addition, methods of adding flame retardants, storage stabilizers, thixotropy imparting agents, dispersion stabilizers, fluidity imparting agents, tackifiers, leveling agents, antifoaming agents, etc., are pressure sensitive adhesives as polymer blends or polymer alloys. It is also possible to dissolve, semi-dissolve or micro-disperse in the agent.

<Pressure sensitive adhesive>
The pressure-sensitive adhesive is also referred to as a pressure-sensitive adhesive, and is an adhesive that adheres by simply applying pressure at room temperature for a short time because it has a viscous property regardless of the solidification of the adhesive.
The pressure-sensitive adhesive of the present invention is a pressure-sensitive adhesive containing a polyurethane resin (A) and a reactive compound (B) having a functional group capable of reacting with a hydroxyl group.
As a monomer unit constituting the polyurethane resin (A), a polyol (a1) unit and a polyisocyanate (a2) unit are contained, and the polyurethane resin (A) has an aromatic ring in the main chain and has a side chain. Has an alkyl group having 4 to 22 carbon atoms, has a weight average molecular weight (Mw) of 10,000 to 500,000,10,000 to 500,000, and reacts with a hydroxyl group with respect to 100 parts by weight of the polyurethane resin (A). Containing 0.1 to 50 parts by weight of the reactive compound (B) having a functional group that can be used. As needed, an ester compound (C), an ionic compound (D), a material (E), and other components (P) are appropriately mixed.
Moreover, an ester compound (C), an ionic compound (D), a material (E), or another component (P) may be called arbitrary components.

  It is preferable that the viscosity of the pressure-sensitive adhesive of the present invention is appropriately adjusted according to the usage form. The pressure-sensitive adhesive of the present invention can use the following organic solvents in order to adjust the viscosity. In particular, organic solvents include alcohol solvents such as methanol, ethanol and isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate and butyl acetate, cyclohexane, toluene and xylene. It is preferable to use various organic solvents such as hydrocarbon solvents such as water, water, and mixtures thereof. However, care should be taken when using a solvent having active hydrogen that may react with the reactive compound (B), such as an alcohol solvent. Also, the viscosity can be reduced by heating the pressure sensitive adhesive without using an additional solvent.

  The viscosity of the pressure-sensitive adhesive of the present invention is preferably 3,000 to 10,000 mPa · s when measured with a B-type viscometer at 25 ° C. from the viewpoint of forming an adhesive layer. 8,000 to 8,000 mPa · s is more preferable. When the viscosity is less than 10,000 mPa · s, it becomes easy to form an adhesive layer having a thickness of 0.5 to 300 μm, and optical characteristics such as transmittance can be improved. Moreover, when the viscosity is 3,000 mPa · s or more, it becomes easy to control the thickness of the adhesive layer. In this embodiment, the film thickness, viscosity, or nonvolatile content concentration of the adhesive layer is appropriately set according to the use of the laminate.

<Method for producing pressure-sensitive adhesive>
As a method for producing a pressure-sensitive adhesive, first, after producing a polyurethane resin (A), an optional component is mixed, and a reactive compound (B) having a functional group capable of reacting with the hydroxyl group is contained. It can be a pressure sensitive adhesive.
The production of the pressure-sensitive adhesive is a first step of producing a polyurethane resin (A) by reacting the polyol (a1) and the polyisocyanate (a2), and the second step of mixing the polyurethane resin (A) and an optional component. The reactive compound (B) having a functional group capable of reacting with a hydroxyl group is mixed with the mixture obtained in the step 2 and the second step. In addition, when not mixing arbitrary components, the said 2nd process can be skipped.

<Method for producing polyurethane resin (A)>
The first step for producing the polyurethane resin (A) will be described.
The urethanization reaction for producing the polyurethane resin (A) by reacting the polyol (a1) and the polyisocyanate (a2) can be carried out in various ways, but is roughly classified into the following two methods.
[I] A method in which polyol (a1), polyisocyanate (a2), an organic solvent, and a catalyst are all charged and reacted.
[Ii] A method in which a polyol (a1), a catalyst and an organic solvent are charged into a flask, a polyisocyanate (a2) is dropped, and then a catalyst is additionally added as necessary.
[Ii] is preferable when the reaction is precisely controlled. The reaction temperature is preferably 120 ° C. or lower, and more preferably 50 to 100 ° C. When the reaction is carried out at a predetermined temperature, the reaction rate can be easily controlled and a polyurethane resin (A) having a predetermined weight average molecular weight and structure can be easily obtained. The urethanization reaction may be performed without a catalyst, but it is preferably performed in the presence of a catalyst at 80 to 100 ° C. for 1 to 20 hours.

The mixing ratio of the polyol (a1) and the polyisocyanate (a2) is that the polyurethane resin (A) needs to have at least one hydroxyl group, so the polyisocyanate is used with respect to 1 mol of the hydroxyl group in the polyol (a1). It is necessary that the number of isocyanate groups in (a2) be less than 1 mole, preferably 0.5 to 0.95 mole, and more preferably 0.6 to 0.9 mole. Within this range, the reactivity with the reactive compound (B) is improved, an adhesive layer having high transparency can be easily obtained, the adhesion to the curved surface portion is improved, and adherend contamination during peeling can be suppressed. .
The end point of the synthesis reaction is determined by the measurement of the isocyanate content by titration (% by weight) or the disappearance of the characteristic absorption based on the isocyanate group (NCO) by the infrared absorption spectrum (IR) measurement. In addition, the detail of the measuring method of isocyanate content by titration is described in an Example.

  The said catalyst can be used at the time of manufacture of a polyurethane resin (A). The reaction between an isocyanate group and a hydroxyl group is naturally fast, but in the presence of an organometallic compound catalyst, the reaction is further promoted and may be difficult to control. At this time, when a chelate compound is added, a chelate is formed with the organometallic compound, the catalytic ability is adjusted, and the reaction is easily controlled.

  Examples of the chelate compound include acetylacetone, dimethylglyoxime, oxine, dithizone, polyaminooxyacids such as ethylenediaminetetraacetic acid (also known as EDTA), oxycarboxylic acids such as citric acid, and condensed phosphoric acid. Among these, acetylacetone is preferable because it is soluble in an organic solvent, has volatility, and can be easily removed if necessary.

  Since the chelate compound remains in the pressure-sensitive adhesive, the reaction rate can be adjusted by acting on the reaction between the polyurethane resin (A) and the reactive compound (B). An excellent pressure-sensitive adhesive having an excellent life (also referred to as pot life) can be obtained.

An organic solvent can be used for producing the polyurethane resin (A). Reaction control is facilitated by using an organic solvent. Examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, Methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl-n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, Ketones such as methylcyclohexanone and isophorone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, acetic acid Esters such as cutyl, methyl lactate, propyl lactate, butyl lactate, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol dimethyl ether , Ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene Glycol and glycol ethers such as recall monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol mono Glycol acetates such as methyl ether acetate, saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane and isododecane, unsaturated hydrocarbons such as 1-hexene, 1-heptene and 1-octene, Cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane and decalin, and cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene and cyclododecene , Aromatic hydrocarbons such as benzene, toluene, xylene and the like, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide and the like.
Among these, ethyl acetate, toluene, and methyl ethyl ketone are preferable in terms of the solubility of the polyurethane resin (A) and the boiling point of the solvent.

What is necessary is just to determine the compounding quantity of an organic solvent suitably considering the composition of a polyurethane resin (A), a viscosity, or a non volatile matter density | concentration. The non-volatile component concentration other than the organic solvent at the time of synthesizing the polyurethane resin (A) is preferably 40 to 99% by weight, and more preferably 50 to 95% by weight. When the concentration is within a predetermined range, the reactivity is improved.
The organic solvent can be used alone or in combination of two or more.

The second step will be described.
The pressure-sensitive adhesive of the present invention can be blended with a polyurethane resin (A) by mixing arbitrary components with a mixer such as a Henschel mixer, a disper, an attritor, a high-speed mixer, or a homomixer. In mixing, an organic solvent can be used in combination as appropriate.

The third step will be described.
The pressure-sensitive adhesive of the present invention is further mixed with the reactive compound (B) after the second step and mixed with a mixer such as a Henschel mixer, a disper, an attritor, a high speed mixer, or a homomixer. can do. During mixing, if necessary, bubbles and bubbles contained in the pressure-sensitive adhesive can be removed by vacuum degassing, and unexpected foreign matters can be removed by filtration or the like.
Moreover, the reaction between the hydroxyl group contained in the polyurethane resin (A) and the reactive functional group in the reactive compound (B) may be at any timing after mixing. For example, the reaction does not proceed immediately after mixing (or only part of the reaction proceeds), and after applying a pressure-sensitive adhesive to the substrate, it reacts during heating and drying to form a crosslinked coating and adhere You may express performance. Also, the timing of mixing is not particularly limited. After one of the polyurethane resin (A) and the reactive compound (B) is applied to the surface of the substrate, the other is applied separately, and the reaction is performed at the time of heating and drying. May be advanced. Alternatively, the polyurethane resin (A) and the reactive compound (B) may be applied to separate substrate surfaces, the coated surfaces may be bonded together, and then heated and dried to allow the reaction to proceed. Preferably, a pressure-sensitive adhesive, which is a mixed solution of the polyurethane resin (A) and the reactive compound (B), is applied onto a substrate and is crosslinked and cured by heating to form an adhesive layer. The surface of the adhesive layer has re-peelable tackiness.

<Adhesive film>
The adhesive film of the present invention (also referred to as a pressure-sensitive adhesive film) is obtained by forming an adhesive layer composed of the above-mentioned pressure-sensitive adhesive on a base material (G) described later, and having a film-like substrate having a surface peel-treated. A material (also referred to as a release liner) may be laminated.
When manufacturing an adhesive film, after applying a pressure-sensitive adhesive to a substrate described later by an appropriate method according to a conventional method, the pressure-sensitive adhesive contains a liquid medium such as an organic solvent or water. When the liquid medium is removed by a method such as heating, or when the pressure-sensitive adhesive does not contain a liquid medium that should be volatilized, the molten adhesive layer is cooled and solidified, An adhesive layer can be formed. For example, a pressure-sensitive adhesive is applied to the release treatment surface of the release liner, dried, and a method of creating a substrate by pasting it together, or a pressure-sensitive adhesive is directly applied to a substrate other than the release liner, and dried. There is a method in which the release treatment surface of the release liner is bonded to the surface of the adhesive layer.

  The method for applying the pressure sensitive adhesive is not particularly limited. For example, various well-known methods such as Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, kiss coater, lip coater, comma coater, blade coater, knife coater, reverse coater, spin coater, dip coater, etc. Can be applied. Moreover, it can select without particular restriction | limiting also about forms, such as thin film coating or thick film coating.

  When using the pressure sensitive adhesive of this invention and forming an adhesive layer, 0.5-300 micrometers is preferable and, as for the film thickness of an adhesive layer, 1-100 micrometers is more preferable. When the film thickness is in the above range, the adhesive film can be used as a protective film to obtain a sufficient adhesive force.

  The basic laminated structure of the adhesive film is a single-sided adhesive film such as a substrate / adhesive layer / release liner, or a double-sided adhesive film such as a release liner / adhesive layer / substrate / adhesive layer / release liner. Thus, the laminated body laminated | stacked on the release liner is called adhesive film. At the time of use, the release liner is peeled off and the adhesive layer is attached to the adherend. The pressure-sensitive adhesive is not only adhesive when the adhesive layer touches the adherend when it is attached, but also an adhesive other than the pressure-sensitive adhesive (hereinafter simply referred to as an adhesive). Unlike sticking, it is necessary to have a cohesive force for maintaining the sticking state while having a tack and appropriate hardness without being completely solidified during sticking. The cohesive force greatly depends on the molecular weight and crosslink density. Thus, the laminated body laminated | stacked on the structure of a base material / adhesion layer / adhered body is called sticking laminated body. When the sticking laminate is used for optical purposes, it is called an optical laminate. In the case of an electronic member, it is called an electronic laminate.

The adhesive film using the pressure-sensitive adhesive of the present invention is preferably used for surface protection film applications such as optical members and electronic members, and the pressure-sensitive adhesive contains two or more substrates (G) (of the substrate An adhesive layer is formed by bonding a base substrate of an adhesive film and a substrate (referred to as an adherend) to which the other substrate is bonded. The substrate may be a wood, a metal plate, a plastic plate, a film-like substrate, a glass plate, a paper processed product, etc., but when used for an optical member, since it needs transparency, a plastic plate, It is necessary to comprise a highly transparent material such as a film substrate or a glass plate. However, in applications that do not require transparency such as electronic members, if a transparent film or a transparent glass plate is used as one substrate, the other substrate is not a transparent substrate, for example, wood, A substrate made of a material such as a metal plate, a plastic plate, or a paper processed product can also be used.
At the time of bonding, as described above, an adhesive film is prepared, and the release liner is peeled off and attached to the adherend, or a pressure sensitive adhesive is directly injected between the two base materials and attached. In either case, it is not limited, but it is preferable in terms of “removability” to reattach the adhesive laminate in which the film is attached to a substrate such as a glass surface, which is attached via an adhesive film. .

  As described above, examples of the release liner include those obtained by subjecting the surface of a film-like substrate such as cellophane, various plastic films, and paper to a release treatment. Moreover, as a film-form base material, the thing of a single layer may be used, and the thing in the multilayer state formed by laminating | stacking a some base material can also be used. Moreover, when a transparent film (H) is used, the said laminated body can be used suitably for an optical use. From the viewpoint of obtaining good optical properties, the above laminate is called an optical laminate, and the transparent film (H) used is, for example, transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropic properties. It is preferable that it is comprised from the thermoplastic resin which is excellent in optical characteristics, such as.

  Such various transparent films (H) are also referred to as various plastic films or plastic sheets. For example, polyvinyl alcohol film (also referred to as PVA film), polytriacetyl cellulose film (also referred to as TAC film), polypropylene film (also referred to as PP film), polyethylene film (also referred to as PE film), polycycloolefin film (also referred to as COP film) ), Polyolefin-based resin films such as ethylene-vinyl acetate copolymer film (also referred to as EVA film), polyester-based resins such as polyethylene terephthalate film (also referred to as PET film) and polybutylene terephthalate film (also referred to as PBT film). Film, polycarbonate resin film (also called PC film), polynorbornene resin film, polyarylate resin film, poly Crylic acid ester resin film, polyphenylene sulfide resin film (also called PPS film), polystyrene resin film (also called PST film), polyamide resin film (also called PA film), polyimide resin film ( Also referred to as a PI film), oxirane resin films, and the like. Among these substrates, it is particularly preferable to use a sheet-like substrate such as a PVA film, a TAC film, a COP film, a polyester resin film, or a PC film as the transparent film (H).

In addition, the transparent film (H) has a surface with physical treatment such as corona discharge, plasma treatment, flame treatment, etc., chemical treatment that modifies the film surface with acid or alkali, etc. Films with a substantial increase in surface area of the substrate, or metal oxides such as silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium on the surface, or non-metallic inorganic oxides For the pressure-sensitive adhesive, such as a plastic film on which is vapor-deposited, one that has been subjected to an easy adhesion treatment or one that has been provided with functionality for each application can be suitably used.
When the transparent film (H) is used as a protective film, the opposite surface where the adhesive layer is not formed is subjected to a release treatment by adding a fatty acid amide, polyethyleneimine, a long-chain alkyl-based additive, etc. A coating layer made of any appropriate release agent such as a system, a long chain alkyl system, or a fluorine system can be provided.

  Moreover, in this invention, it is set as the optical film (I) by which the adhesive layer which consists of a pressure-sensitive adhesive agent was formed on the said transparent film using the transparent film (H) as a base material (G) for the purpose of optical use. Is also possible. Here, as the optical film (I), the transparent film (H) can be used as an optical film as it is, and the transparent film (H) itself having a special function is used. Is also possible. Here, the special function is intended to have optical functions such as light transmission light diffusion, light collection, refraction, scattering, and haze. These transparent films (H) can be used alone or in combination of several kinds when used as the optical film (I). In the present invention, an adhesive film can be prepared by forming an adhesive layer made of the pressure-sensitive adhesive on at least one surface of the optical film (I), and laminated on a liquid crystal cell or the like. It can also be used for applications.

  When the optical laminate of the present invention is used as a surface protection film, the transparent film (H) is used as the substrate (G), and the adhesive layer and glass of the adhesive film formed from the pressure-sensitive adhesive of the present invention are sequentially formed. It is a laminated one. Here, the transparent film (H) is preferably a polyester resin film. A glass plate is preferably used as the substrate used as the adherend.

  The thickness of the transparent film (H) used for the surface protective film can be set to any thickness depending on the application. In order to fully express the effect of the pressure-sensitive adhesive of the present application, the thickness is preferably 5 μm to 300 μm, more preferably 15 μm to 150 μm.

  The adhesive film of the present invention preferably has high transparency when used as a protective film. Due to the high transparency of the surface protective film, it is possible to accurately inspect the surface of the optical member or the electronic member while it is adhered. The surface protective film of the present invention has a haze of preferably 5% or less, more preferably 2% or less. The details of the haze measurement are described in the examples.

  The adhesive film of the present invention has been described by taking a polyester resin film as an example of the transparent film (H). However, the present invention is not limited to polyester resin films, and it is easy to construct a laminate that can be suitably used for optical applications in other embodiments using other transparent films (H) and other various substrates. Should be understood. For example, it can be preferably used for various electronic parts-related members such as liquid crystal displays, plasma displays, touch panels, electrode peripheral members, glass members such as surface protection films, building materials and vehicle window glass, and plastics such as polyolefin, ABS, and polyacryl. It can also be used for metal such as cardboard, wood, plywood, stainless steel, and aluminum.

  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.

<Synthesis of polyurethane resin>
(Synthesis Example 1)
The following monomers {polyol (a1), polyisocyanate (a2)}, catalyst are added to a polymerization tank and a dropping apparatus of a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing tube. The organic solvent was charged at the following ratios.

[Polymerization tank]
DD (a1-1) 8.54 parts BA4PO (a1-2) 56.48 parts FF3320 (a1-2) 9.56 parts Toluene (organic solvent) 13.16 parts DBU (catalyst) 0.0023 parts [drip apparatus ]
HDI (a2) 25.40 parts Toluene (organic solvent) 1.57 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 80 ° C. with stirring in a nitrogen atmosphere, and the mixture containing the HDI (a2) and the organic solvent was added from the dropping device over 1 hour. The reaction was started dropwise. The reaction was continued for 2 hours with further stirring. Then, after confirming that the characteristic absorption (2,270 cm ⁻¹ ) based on NCO in the IR chart has disappeared, 51.96 parts of ethyl acetate was added to adjust the nonvolatile content concentration (NV) to 60%. The reaction was terminated by cooling to ° C. This polyurethane resin (A) solution is colorless and transparent in appearance, solution viscosity (Vis) 6,800 mPa · s (25 ° C.), weight average molecular weight (Mw) 107,000, and hydroxyl value (OHV) 13.4 mgKOH / G.

(Synthesis Examples 2-68)
In the materials described in Tables 1 and 2, the polyol (a1), polyisocyanate (a2), toluene (organic solvent), and catalyst are all charged into the polymerization tank, and the polyisocyanate (a2) and toluene (organic solvent) are added dropwise. Each of the polyurethane resins of Synthesis Examples 2 to 68 was synthesized in the same manner as in Synthesis Example 1 except that the contents were changed so as to be charged. The compounds used as monomers listed in Tables 1 and 2 represent the total value (parts) of the amount charged to the polymerization tank and the amount charged to the dropping device.
However, in Synthesis Example 59, polyisocyanate (a2) was changed to IPDI. In Synthesis Example 60, polyisocyanate (a2) was changed to TDI. In Synthesis Example 61, the catalyst was changed to dioctyltin dilaurate, and all the organic solvents in the dropping device were changed to acetylacetone. In Synthesis Example 63, polyisocyanate (a2) was changed to TDI, and the organic solvent in the dropping device was not used.

  The solution appearance (25 ° C.), solution viscosity (Vis), weight average molecular weight (Mw), and hydroxyl value (OHV) of the obtained polyurethane resin solution were determined according to the methods described below, and the results are shown in Tables 3 and 4. . Moreover, it described also about the measuring method of acid value (AV), residual amount (%) of isocyanate group (NCO), and glass transition temperature (Tg).

<< Solution appearance >>
The appearance of the obtained polyurethane resin solution was visually observed under the condition of 25 ° C. It is good if it is colorless and transparent.

<< Solution viscosity (Vis) >>
The solution of the obtained polyurethane resin was measured at 25 ° C. with a B-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) under the conditions of rotor No. 3, rotation speed 0.5 to 100 rpm, and rotation for 1 minute. (MPa · s).

《Average molecular weight》
For the measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw), GPC (gel permeation chromatography) manufactured by Showa Denko KK was used. The determination of the number average molecular weight (Mn) and the weight average molecular weight (Mw) was a conversion value of polystyrene as a standard substance.
Device name: Showa Denko GPC (Gel Permeation Chromatography) “Shodex GPC System-21”
Column: Tosoh GMHXL: 4 Tosoh HXL-H: 1 In series.
Mobile phase solvent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Column temperature: 40 ° C

<< Hydroxyl value (OHV) >>
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Next, 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for 1 hour. To this, phenolphthalein test solution was added as an indicator and held for 30 seconds. Thereafter, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until the solution turned 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)

《Acid value (AV)》
About 1 g of a sample was accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. 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 was determined by the following formula. The acid value was a numerical value of the dry state of the resin (unit: mgKOH / g).
Acid value (mgKOH / g) = {(5.611 × a × F) / S} / (Nonvolatile content concentration / 100)
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<< Residual amount of isocyanate group (NCO) (%) >>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask and mixed with 25 ml of chlorobenzene and di-n-butylamine / o-dichlorobenzene (weight ratio: di-n-butylamine / o-dichlorobenzene = 1 / 24.8). Add 10 ml of solution and dissolve. To this, 80 g of methanol and bromophenol blue reagent were added as indicators and titrated with a 0.1N alcoholic hydrochloric acid solution. Titration was continued until the solution was yellowish green and held for 30 seconds. The NCO residual amount (%) was determined by the following formula.
NCO residual amount (%) = [0.42 × (BC) × F] / S
Where S: Amount of sample collected (g)
B: Consumption of 0.1N alcoholic hydrochloric acid solution required for sample titration (ml)
C: Consumption of 0.1N alcoholic hydrochloric acid solution required for titration of blank test (ml)
F: Potency of 0.1N alcoholic hydrochloric acid solution

<< 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.
About 10 mg of a sample is put in an aluminum pan, weighed and set in a differential scanning calorimeter, and kept for 5 minutes at a temperature of 100 ° C. using the same type of aluminum pan without a sample as a reference. It was rapidly cooled to 120 ° C. Then, it heated up with the temperature increase rate of 10 degree-C / min, and determined the glass transition temperature (Tg, unit: degreeC) from the obtained DSC chart.

  Abbreviations of materials used in Synthesis 1 to 68 are shown below. In Tables 1 and 2, the numerical value represents part, and the blank means no blending.

・ Low molecular weight polyol (a1-1)
DD: Dimer diol (PRIPOL 2033 (CRODA Coating & Polymers)), BEPG: 2-butyl-2-ethyl-1,3-propanediol, ODD: 1,12-octadecanediol, MPD: 2-methyl- 1,3-propanediol, BMO: benzene-1,3-dimethanol, GLY glycerin / polyether polyol (a1-2)
BA4EO: BA-4 glycol (Mn = 400, hydroxyl value = 280, acid value <0.1, aromatic ring-containing linear liquid type) [manufactured by Nippon Emulsifier Co., Ltd.], BA4PO: BA-P4 glycol (Mn = 450, hydroxyl value) = 250, acid value <0.1, linear liquid type containing aromatic ring) [manufactured by Nippon Emulsifier Co., Ltd.], PEG1000: PEG1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear waxy type) , Diol) [manufactured by Sanyo Chemical Industries], PP1000: Newpol PP-1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type, diol) [manufactured by Sanyo Chemical Industries] , PP2000: Newpol PP-2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear liquid type, diol) [manufactured by Sanyo Chemical Industries, Ltd.] F3320: Primepole FF-3320 (Mn = 3,000, hydroxyl value = 56, acid value <0.5, linear liquid trifunctional type) [manufactured by Sanyo Chemical Industries, Ltd.], G3000: Adeka polyether G-3000B (Mn = 3,000, hydroxyl value = 56, acid value <0.5, linear liquid trifunctional type, triol) (manufactured by Adeka)
・ Polyester polyol (a1-3)
P1010: Kuraray polyol P1010 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type, diol) [manufactured by Kuraray Co., Ltd.], P1011: Kuraray polyol P1011 (Mn = 1,000, hydroxyl value) = 112, acid value <0.5, linear liquid type, aromatic diol) [manufactured by Kuraray Co., Ltd.], P1030 Kuraray polyol P1030 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, aromatic ring) Containing linear liquid type (Kuraray Co., Ltd.), P2013: Kuraray polyol P2013 (Mn = 2,000, hydroxyl value = 56, acid value <1, aromatic ring containing linear liquid type) (Kuraray Co.), F1010: Kuraray polyol F1010 (Mn = 1,000, hydroxyl value = 168, acid value <0.5, linear liquid trifunctional type)
・ Polyamide polyol (a1-4)
TPAE: TPAE617 (Mn = 15,000, hydroxyl value = 16, acid value = 1, linear type, diol) [Fuji Kasei Kogyo Co., Ltd.]
Polycarbonate polyol (a1-5)
C1015N: Kuraray polyol C-1015N (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear liquid type, diol) [manufactured by Kuraray Co., Ltd.]
・ Polyisocyanate (a2)
HDI: hexamethylene diisocyanate, IPDI: 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, TDI: 2,4-tolylene diisocyanate / catalyst DBU: diazabicycloundecene, DOTDL: dioctyltin dilaurate / organic solvent ACAC: acetylacetone, TOL: toluene, EAC: ethyl acetate

Using the polyurethane resin obtained in the above synthesis examples, pressure sensitive adhesives were prepared by the following methods, respectively.
(Examples 1-152, Comparative Examples 1-30)
According to the weight ratio (parts) described in Tables 5 to 10 for the obtained polyurethane resin and the reactive compound (B), the optional components were optionally added to the polyurethane resin 100 parts by weight ratio listed in Table 2. (Parts) were mixed, and ethyl acetate was added as an organic solvent to adjust the non-volatile content concentration to 50% to obtain a pressure-sensitive adhesive. The obtained pressure-sensitive adhesive was applied to each substrate, dried, cured, and bonded to create an adhesive film, which was evaluated by the following method. Each result is shown to Tables 11-16.

<< Evaluation of pot life >>
About the obtained pressure-sensitive adhesive, after blending, the viscosity at 25 ° C. was changed every 8 hours until 8 hours later using a B-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.), and the rotor No. Measurement was performed under conditions of 3, 25 ° C., 12 rpm, and 1 minute rotation, and pot life was evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: Viscosity increase rate up to 8 hours is less than 50%. Good.
Δ: Viscosity increasing rate up to 8 hours is 50% or more and less than 100%. Can be used practically.
X: Solution layer separation or turbidity occurs in less than 8 hours, gelation occurs, or viscosity increase rate is recognized to be 100% or more. Not practical.
Here, the viscosity increase rate was calculated by the following method.
Viscosity increase rate (%) = 100 × {(viscosity after 8 hours storage) − (viscosity immediately after adjustment)} / (viscosity immediately after adjustment)

<Evaluation of coatability>
The obtained pressure-sensitive adhesive was dried on a 38 μm-thick polyethylene terephthalate film (Therapy MF: manufactured by Toray Film Processing Co., Ltd.) (hereinafter referred to as “release liner”) as a substrate. Was applied to a thickness of 25 μm and dried with hot air at 100 ° C. for 2 minutes to form an adhesive layer. Next, a 100 μm thick polyethylene terephthalate film (PET film) was bonded to the coated surface to produce an adhesive film composed of 100 μm thick PET film / adhesive layer / release liner. And the state of the adhesive layer surface (coating surface) after peeling a release liner was observed visually and evaluated in three steps. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: A smooth coated surface was obtained. Good.
Δ: Some repelling and foaming are observed at the end of the coated surface. Can be used practically.
×: Repelling, foaming and streaking were observed on the coated surface. Bad.

<< Evaluation of optical characteristics >>
The obtained pressure-sensitive adhesive was coated on the release liner so that the thickness after drying was 50 μm, and dried with hot air at 100 ° C. for 2 minutes to form an adhesive layer. Next, a separate release liner was bonded to the adhesive layer to produce an adhesive film in which the adhesive layer was sandwiched between the release liners, and cured for 7 days in an environment of 23 ° C. and 50% relative humidity.
Next, both release liners were removed, the appearance of the adhesive layer alone was visually determined, and haze was measured with “NDH-300A (Nippon Denshoku Industries Co., Ltd.)”. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No cloudiness or the like is observed, and HAZE: less than 0.5. Good.
Δ: No cloudiness or the like is observed, but HAZE: 0.5 or more and less than 2, and can be used without any practical problem.
X: Cloudiness is observed or HAZE: 2 or more. Bad.

<< Evaluation of workability >>
Each adhesive film prepared by the same method as in the above << Evaluation of coatability >> was cured for 7 days in an environment of 23 ° C and 50% relative humidity. Then, it cut | judged to 100 mm in width x 100 mm in length, it piled up 20 sheets of this, and the state of the adhesion layer protruding from the edge part of an adhesive film at the time of pressing on the conditions of 40 degreeC-60Kg / cm < ² > for 1 hour is as follows. It was evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No protruding adhesive layer is observed. Good.
Δ: Protrusion of the adhesive layer of less than 0.3 mm is observed, but can be used practically.
X: Protrusion of the adhesive layer of 0.3 mm or more is observed. Bad.

<< Evaluation of wet spreadability >>
The obtained pressure-sensitive adhesive is coated on a 50 μm-thick polyethylene terephthalate film (PET film) as a substrate so that the thickness after drying is 15 μm, and dried with hot air at 100 ° C. for 2 minutes. Then, an adhesive layer was formed. Next, a 38 μm release liner (Therapel MF: manufactured by Toray Film Processing Co., Ltd.) was bonded to the coated surface to prepare an adhesive film having a structure of 50 μm thick PET film / adhesive layer / release liner, and a 23 ° C. relative humidity of 50%. Cured for 7 days in the environment. And this adhesive film was cut | judged to width 100mm x length 100mm, and it was set as the measurement sample. Next, a float glass plate having a thickness of 2 mm, a width of 150 mm, and a length of 150 mm is brought into contact with the float glass plate in a state where only one side of the adhesive layer from which the release liner of the adhesive film has been peeled is inclined by 45 °. The time (seconds) required for the entire sample surface to come into contact with the glass plate (wet spread on the glass plate) was evaluated as the wet spread property in the following three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: Wetting spread time is less than 2 seconds. Good.
Δ: Wetting and spreading time is 2 seconds or more and less than 4 seconds. Can be used practically.
X: Time to spread wet is 4 seconds or more. Bad.

<Measurement of peel strength>
Each of the adhesive films prepared by the same method as the above << Evaluation of wettability >> is cut into a width of 25 mm x a length of 100 mm, the release liner is peeled off, and the exposed adhesive layer is a non-alkali glass plate having a thickness of 1.2 mm. The film was attached using a laminator in an environment of 23 ° C. and 50% relative humidity. Then, it hold | maintained for 20 minutes in the autoclave of conditions of 50 degreeC and 5 atmospheres, and obtained the measurement sample. The measurement sample was allowed to stand at 23 ° C. for 1 day, and was then peeled at a peeling speed of 300 mm / min and a peeling angle using a tensile tester (“Tensilon” manufactured by Orientec Co., Ltd.) in an environment of 23 ° C. and 50% relative humidity. The peel strength was measured under the condition of 180 degrees (measurement of peel strength one day after bonding). Further, after the measurement sample was allowed to stand for 14 days in an environment of 23 ° C. and 50% relative humidity, the peel strength was measured by the same method (measurement of peel strength after 14 days of bonding). This peel strength was evaluated as an adhesive strength in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: Adhesive strength is less than 10.0 (mN / 25 mm). Good.
Δ: Adhesive strength is 10.0 (mN / 25 mm) or more and less than 15.0 (mN / 25 mm). Can be used practically.
X: Adhesive force is 15.0 (mN / 25 mm) or more. Poor and impractical.

<< Evaluation of removability (reworkability) >>
Each adhesive film created by the same method as in the above << Evaluation of wettability >> is cut into a size of 25 mm x 150 mm, the release liner is peeled off, and a laminator is attached to a 2 mm thick float glass plate, An optical laminate of an adhesive film and a glass plate was obtained by holding in an autoclave at 50 ° C. and 5 atm for 20 minutes.
The adhesive film of this laminated body was peeled off at a speed of 50 mm / min in the direction of 180 °, and the fogging of the glass surface after peeling was visually observed and evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
○: No cloudiness and no problem in practical use. Very good.
Δ: Some cloudiness is observed, but there is no practical problem. Good.
X: Transfer of the pressure-sensitive adhesive is recognized over the entire surface, and is not practical.

<< Evaluation of durability (heat resistance, heat and humidity resistance) >>
As a heat resistance test, an adhesive film prepared by the same method as the above << Evaluation of wettability >> was cut into a width of 100 mm and a length of 100 mm. Next, the release liner of the adhesive film is removed, and the exposed adhesive layer is applied to one side of a 1.2 mm-thick alkali-free glass plate under a 50 ° C. atmosphere at a pressure of 5 kg / cm ² and held in an autoclave for 20 minutes. And then left in an atmosphere at 80 ° C. for 500 hours. After standing, the temperature was returned to 25 ° C., and the adhesive film was floated and peeled off, and the occurrence of foaming was visually observed and evaluated in three stages.
As a heat and humidity resistance test, a sample was prepared in the same manner as the heat resistance test, and left in a constant temperature and humidity chamber at 60 ° C. and a relative humidity of 90% for 500 hours. . After standing, the temperature was returned to 25 ° C., and the adhesive film was floated and peeled off, and the occurrence of foaming was visually observed and evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
Foaming is a state in which relatively large bubbles are generated at the interface between the adhesive layer and the glass (other than the peripheral edge).
The floating / peeling is a state where the polarizing film adhesive film is lifted from the glass and peeled off.
Each evaluation standard is as follows.
○: No foaming, floating or peeling occurs. Good.
Δ: Minor occurrence of foaming, floating or peeling with a diameter of 0.5 mm or less is observed, but it can be used practically.
X: Remarkable generation | occurrence | production, such as foaming, a float, peeling, is recognized over the whole surface. Cannot be used practically.

The materials used in Examples and Comparative Examples are shown below. In Table 2, a blank means no blending.
Polyurethane resin Compounds obtained in each synthesis example shown in Tables 1 and 2 (Synthesis Examples 1 to 68)
Reactive compound (B) having a functional group capable of reacting with a hydroxyl group
HDI / TMP: trimethylolpropane adduct of hexamethylene diisocyanate, HDI / Nu: trimer having isocyanurate ring of hexamethylene diisocyanate, IPDI / TMP: 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate Trimethylolpropane adduct, XDI / TMP: trimethylolpropane adduct of xylylene diisocyanate, MAS: 3-aminopropyltrimethoxysilane, EPS: 3-glycidoxypropyltrimethoxysilane, PMMM: pentamethoxymethylolmelamine・ Ester compound (C)
OLM: Methyl oleate, RS735: Polyethylene glycol diethylhexanoate (“ADEKA SIZER RS735” manufactured by ADEKA), POEOP: polyoxyethylene octyl ether phosphate ester, T-80: polyoxyethylene di (glycerin) borate monooleate ( EO addition mole number: 6 to 20) [“Emalbon T-80” manufactured by Toho Chemical Co., Ltd.]
・ Ionic compounds (D)
OPFI: 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide compound (E)
BZI: 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]] (benzotriazole ultraviolet shielding agent), CAE: Ethyl α-cyano-β, β-diphenylpropenoic acid ester (2-cyanoacrylic acid UV shielding agent), TBPP: tris (2,4-di-tert) -butylphenyl) phosphite (phosphorus antioxidant) AO50: phenolic antioxidant [“Adekastab AO-50” manufactured by Adeka Corporation], TMPSE: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (HALS light stabilizer), EZCG: Fluorescent dye [EZCG8006 made by Easy Bright]
・ Antihydrolysis agent (F)
CBI: Carbodiimide [Nisshinbo Co., Ltd., trade name Carbodilite V-09GB]
・ Other ingredients (P)
FTR Petroleum resin [Mitsui Chemicals "FTR8100"]

As described above, the pressure-sensitive adhesive of the present invention is optical in Examples 1-4, 8-29, 33-41, 46-50, 54-79, 83-125, 128-131, 135-152. In any of the characteristics, workability, wettability, peel strength, re-peelability, heat resistance, and heat and humidity resistance, the “△” evaluation (practical level) is 3 or less out of 10 items. “Excellent” for evaluation (good level).
Moreover, in Examples 5-7, 30-32, 42-45, 51-53, 80-82, 126, 127, 132-134, "△" evaluation (practical level) of each evaluation is among 13 items. Since it is 4 to 10 and there is no “x” evaluation (defect level), it can be used practically without any problem.
On the other hand, in Comparative Examples 1 to 30, any of pot life, coatability, optical properties, workability, wettability, peel strength, re-peelability, heat resistance, and moist heat resistance is extremely inferior. I understand.

  The pressure-sensitive adhesive according to the present invention has excellent durability such as heat resistance and heat-and-moisture resistance, and also has excellent wet spreading properties, so that it can be used in the building field (for example, exterior, interior, equipment, etc.), electrical equipment Applications other than protective films in a wide range of fields (such as home appliances, kitchen equipment, air conditioning, etc.), transport equipment (eg, ships, automobiles, etc.), furniture, sundries, and other industrial fields other than optics. Can also be used.

Claims (13)

A pressure-sensitive adhesive containing a polyurethane resin (A) and a reactive compound (B) having a functional group capable of reacting with a hydroxyl group,
As a monomer unit constituting the polyurethane resin (A), it contains a polyol (a1) unit and a polyisocyanate (a2) unit,
The polyurethane resin (A) has an aromatic ring in the main chain, an alkyl group having 4 to 22 carbon atoms and a hydroxyl group in the side chain, and a weight average molecular weight of 10,000 to 500,000.
A pressure-sensitive adhesive containing 0.1 to 50 parts by weight of a reactive compound (B) having a functional group capable of reacting with a hydroxyl group with respect to 100 parts by weight of the polyurethane resin (A). In a total of 100% by weight of monomer units constituting the polyurethane resin (A),
The polyol (a1) unit is 70 to 99% by weight,
1 to 30% by weight of polyisocyanate (a2) unit,
The pressure-sensitive adhesive according to claim 1, wherein   The pressure-sensitive adhesive according to claim 1 or 2, wherein the polyol (a1) contains a diol having an aromatic ring.   The pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the polyol (a1) contains a polyol having 3 or more hydroxyl groups.   The pressure sensitive adhesive according to any one of claims 1 to 4, wherein the aromatic ring content in the polyurethane resin (A) is 2 to 30% by weight.   The pressure-sensitive adhesive according to any one of claims 1 to 5, wherein the polyisocyanate (a2) contains a diisocyanate.   Reactive compound (B) contains polyisocyanate (b1), The pressure sensitive adhesive in any one of Claims 1-6 characterized by the above-mentioned.   Furthermore, ester compound (C) is included, The pressure sensitive adhesive in any one of Claims 1-7 characterized by the above-mentioned.   Furthermore, an ionic compound (D) is contained, The pressure sensitive adhesive in any one of Claims 1-8 characterized by the above-mentioned.   The pressure sensitive adhesive film by which the contact bonding layer formed from the pressure sensitive adhesive in any one of Claims 1-9 was laminated | stacked on the at least one surface of the base material (G).   The pressure-sensitive adhesive film according to claim 10, wherein the substrate (G) is a transparent film (H).   The pressure-sensitive adhesive film according to claim 11, wherein the transparent film (H) is an optical film (I).   An optical laminate in which the optical film (I), an adhesive layer formed from the pressure-sensitive adhesive according to any one of claims 1 to 9, and glass are sequentially laminated.