JP6702122B2 - Pressure-sensitive adhesive, pressure-sensitive adhesive film and optical laminate - Google Patents

Description

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

  Display devices such as liquid crystal displays, which are used in various devices such as household electronic devices such as electronic calculators, electronic timepieces, mobile phones, and televisions, and televisions, are becoming larger in size, and particularly liquid crystal televisions and plasma televisions. Is significantly larger. Further, in recent years, touch panel type liquid crystal displays such as smartphones and tablets have been rapidly spread, 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 so that they can be used in harsh vehicle environments such as high temperature and high humidity environments.

Conventionally, a surface protective film is generally attached to an exposed surface of an optical member such as a liquid crystal display in order to prevent the surface from being soiled or scratched during processing, assembly, inspection, transportation, or the like. In particular, the surface protection film for optical members may be repeatedly stuck and peeled during the manufacturing process, so that the sticking is easy (wetting and spreading on the adherend) and the surface of the optical member is contaminated during peeling. Removability that does not occur (also referred to as reworkability) is required. In addition, as the optical member becomes thinner, the optical member itself becomes more susceptible to cracking. The surface protection film must have the property of being capable of peeling with a weaker force (light peeling property) while having adhesiveness. Is coming. Furthermore, the surface protection film is also required to have high durability such that it does not foam or peel off from the adherend even when it is exposed to heat or wet heat.
A layered product such as an optical member to which this surface protection film is adhered can be easily peeled off, and foaming, floating, and peeling do not occur even under a severe environment such as high temperature or high temperature and high humidity conditions. Therefore, a pressure sensitive adhesive containing an acrylic resin or a pressure sensitive adhesive containing a silicone resin has been used.
However, in the case of pressure-sensitive adhesives containing acrylic resin, the adhesive strength may be significantly increased with the passage of time after application due to insufficient cohesive strength of the adhesive layer itself, or adhesive residue may occur during peeling. However, there is a problem in using it as a surface protection film for a member such as an optical member or an electronic member which is particularly liable to be mixed with foreign matter.
In addition, since the pressure-sensitive adhesive layer of the silicone resin is liable to contaminate the adherend with the silicone resin after peeling, there is a problem in using the silicone resin as a surface protection film for a member such as an optical member or an electronic member which requires particularly low contamination. It was

Therefore, as a pressure-sensitive adhesive that does not use an acrylic resin or a silicone resin, Patent Document 1 discloses a pressure-sensitive adhesive that includes a polyurethane resin that uses a polyether polyol as a polyol.
Further, Patent Document 2 discloses a polyurethane resin using polyester polyol as a polyol, and a pressure-sensitive adhesive containing a carboxylic acid ester.

JP, 2006-182795, A JP, 2005-7226, A

However, the conventional pressure-sensitive adhesive made of a polyurethane resin of Patent Document 1 has a problem that although cohesive force is reduced and adhesive residue is liable to occur, although flexibility is exhibited and adhesive force is improved.
Further, the pressure-sensitive adhesive of Patent Document 2 using a polyurethane resin using polyester polyol as a polyol component has high cohesive force and can suppress adhesive residue, but is exposed to a high temperature environment or a high temperature and high humidity environment. After that, there was a problem that the removability was low due to floating and peeling from the adherend.

  The present invention provides a pressure-sensitive adhesive and a pressure-sensitive adhesive film which are excellent in removability and are less likely to be lifted or peeled off from an adherend after being exposed to a high temperature environment or a high temperature and high humidity environment. And

  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, and constitutes the polyurethane resin (A). As a monomer unit, a polyol (a1) unit and a polyisocyanate (a2) unit are contained, and the polyurethane resin (A) has a carbonate structure in the main chain and does not have an aromatic ring. 000 to 500,000, and 0.1 to 50 parts by weight of the reactive compound (B) having a functional group capable of reacting with a hydroxyl group is contained with respect to 100 parts by weight of the polyurethane resin (A).

  According to the present invention described above, by using the polyurethane resin (A) having a carbonate structure in the main chain, the adhesion to the substrate is improved, and the removability, heat resistance, moist heat resistance and transparency are excellent. A pressure sensitive adhesive film was obtained. Further, the pressure-sensitive adhesive film did not cause foaming or peeling after being exposed to a high temperature environment or a high temperature and high humidity environment, and an effect of not contaminating an adherend at the time of peeling was obtained.

  The present invention can provide a pressure-sensitive adhesive and a pressure-sensitive adhesive film which have excellent removability and are less likely to be lifted or peeled off from an adherend after being exposed to a high temperature environment or a high temperature and high humidity environment.

The pressure-sensitive adhesive of the present invention contains 0.1 to 50 parts by weight of a reactive compound (B) having a functional group capable of reacting with the hydroxyl group, relative to 100 parts by weight of a polyurethane resin (A). The feature is that it is an agent.
The pressure-sensitive adhesive of the present invention is preferably used as a pressure-sensitive adhesive film having an adhesive layer formed by coating and a substrate.
Note that in this specification, a film, a tape, and a sheet are synonyms.
The components of the pressure sensitive adhesive will be specifically described below.

z
<Polyurethane resin (A)>
The polyurethane resin (A) is a resin containing a polyol (a1) unit and a polyisocyanate (a2) unit, and is a resin obtained by polymerizing the polyol (a1) and the polyisocyanate (a2).

<<Polyol (a1)>>
The polyol (a1) as used herein is a polyol having no aromatic ring. The polyol (a1) is preferably a diol having no aromatic ring. When the polyol (a1) is a diol, the cohesive force of the urethane resin (A) is improved, and since it does not have an aromatic ring, thermal yellowing is suppressed and the adhesive force of the pressure-sensitive adhesive to the glass plate is improved. It becomes possible to reduce to a re-peelable fine viscosity region (for example, adhesive strength of less than 10.0 mN/25 mm). Examples of such polyol (a1) include aliphatic polyol (a1-1), polyether polyol (a1-2), polyester polyol (a1-3), polyamide polyol (a1-4), and polycarbonate polyol (a1-5). ), and other polyols (a-6). The polyol (a1) includes a diol and a polyol having 3 or more hydroxyl groups.

  Examples of the aliphatic polyol (a1-1) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol. , 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-butyl-3-ethyl-1,5-pentane Diol, 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, etc. Aliphatic diols;

  For example, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediethanol, cyclopentadienedimethanol, 2,5-norbornanediol, 1,3-adamantanediol, dimerdiol. Alicyclic diols such as;

  Examples thereof include glycerin, sorbitol, trimethylolpropane, trimethylolbutane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, mannitol, dipentaerythritol, and other aliphatic polyols having three or more hydroxyl groups. Be done.

The polyol (a1) uses the chain-like aliphatic diol or alicyclic diol in order to reduce the tack (tackiness) of the pressure-sensitive adhesive and control the adhesiveness in a slightly viscous region. Is preferred. Among the chain-like aliphatic diols, it is preferable to use an aliphatic diol having an alkyl group having 1 to 8 carbon atoms in the side chain, because the flexibility of the polyurethane resin (A) is further improved. Examples of the chain aliphatic diol or alicyclic diol include 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, neopentyl glycol and 2,4. -Diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,12-dodecanediol, and dimerdiol are more preferable.
Here, the dimer diol is an unsaturated fatty acid such as linoleic acid, oleic acid and linolenic acid, a carboxylic acid having 18 carbon atoms such as a dry oil fatty acid or a semi-dry oil fatty acid obtained from tall oil, cottonseed oil, soybean oil and the like. Is a 36-carbon aliphatic diol obtained by further completely hydrogenating a dimer acid obtained by thermal polymerization of a dimer acid, and is obtained as a mixture of geometric isomers of a dimer diol having a branched structure or a cyclohexane ring. It is a compound. Examples of commercially available products include PRIPOL-2030 and 2033 [manufactured by CRODA Coating & Polymers] and Sovermol-908 [manufactured by BASF].
The chain-like aliphatic here means an acyclic chain-like carbon compound, and the cyclic carbon compound is defined as an alicyclic group.

  Moreover, 50-800 are preferable and, as for the number average molecular weight (Mn) of aliphatic polyol (a1-1), 60-600 are more preferable. When the number average molecular weight is in this range, the pseudo-crystallinity of the polyether polyol (a1-2), polyester polyol (a1-3), polyamide polyol (a1-4), or polycarbonate polyol (a1-5) described below is Since it breaks down, the viscosity of the polyurethane resin (A) is easily suppressed and the coating processability is further improved. Further, since the cohesive force is further increased, the removability is further improved.

A well-known polyether polyol can be used as the polyether polyol (a1-2). The polyether polyol (a1-2) is a polyoxyalkylene polyol obtained by ring-opening addition polymerization of an alkylene oxide with an initiator having 2 to 4 active hydrogen atoms. Examples of the initiator include the above aliphatic polyol (a1-1) and aliphatic amines (for example, alkylenediamine such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, monoethanolamine, diethanolamine). Alkanolamines) and the like. Among these, the aliphatic diols described above as the aliphatic polyol (a1-1) are more preferable from the viewpoint of improving the wettability and spreadability to the adherend when the pressure-sensitive adhesive is applied.
The initiator may be used alone or in combination of two or more.

  Examples of the alkylene oxide include compounds having a polyoxyalkylene skeleton obtained 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, polyethylene propylene glycol (ethylene oxide/propylene oxide copolymer), polyethylene tetramethylene glycol (ethylene oxide/tetramethylene oxide copolymer), polypropylene glycol, poly Examples thereof include tetramethylene glycol. Further, alkyl polyalkylene glycol obtained by ring-opening polymerization of alkylene oxide using the above aliphatic polyol (a1-1) as an initiator, cycloalkyl polyalkylene glycol, or bisphenol such as bisphenol A or bisphenol F with ethylene oxide, propylene oxide or the like. Examples thereof include polyalkylene polyols having an aromatic ring formed by adding alkylene oxide. Among these, when a polyalkylene polyol having no alkylene oxide skeleton and having no aromatic ring is used, the pressure-sensitive adhesive can obtain good wet spreadability. For example, polypropylene glycol having a methyl group in its side chain is particularly preferable from the viewpoint of achieving both adhesiveness in the slightly viscous region and wet spreadability.

  As for the polyether polyol (a1-2), for example, PEG400 (Mn=400, hydroxyl value=275, acid value<0.5, linear liquid type), PEG600 (Mn=600, hydroxyl value=180) are commercially available products. , Acid value <0.5, linear liquid type), PEG1000 (Mn = 1,000, hydroxyl value = 112, acid value <0.5, linear wax type), PEG2000 (Mn = 2,000, hydroxyl value = 56, acid value <0.5, linear wax type), PEG4000N (Mn = 3,000, hydroxyl value = 37, acid value <0.5, linear wax type), PEG10000 (Mn = 10,000, hydroxyl group) Value = 11, acid value <0.5, linear solid type), Newpol PP-400 (Mn = 400, hydroxyl value = 275, acid value <0.5, linear liquid type), Newpol PP-1000 (Mn). =1,000, hydroxyl value=112, acid value<0.5, linear liquid type), Newpol PP-2000 (Mn=2,000, hydroxyl value=56, acid value<0.5, linear liquid type) , Newpol PP-4000 (Mn=4,000, hydroxyl value=28, acid value<0.5, linear liquid type), Newpol 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) [above, Sanyo Chemical Industry Co., Ltd.] ;

  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];

  EXCENOL420 (Mn=400, hydroxyl value=280, acid value<0.03, linear liquid type), EXCENOL1020 (Mn=1,000, hydroxyl value=112, acid value<0.05, linear liquid type), EXCENOL2020( Mn=2,000, hydroxyl value=56, acid value<0.05, linear liquid type), EXCENOL3020 (Mn=3,000, hydroxyl value=35, acid value<0.03, linear liquid type), EXCENOL510 ( Mn=4,000, hydroxyl value=28, acid value<0.05, linear liquid type), EXCENOL1030 (Mn=1,000, hydroxyl value=160, acid value<0.05, linear liquid trifunctional type), EXCENOL240 (Mn=3,000, hydroxyl value=56, acid value<0.05, linear liquid trifunctional type), EXCENOL820 (Mn=4,900, hydroxyl value=34, acid value<0.05, linear liquid 3 Functional type), EXCENOL823 (Mn=5,100, hydroxyl value=33, acid value<0.05, linear liquid trifunctional type) [above, manufactured by Asahi Glass Co., Ltd.];

  PTG1000 (Mn=1,000, hydroxyl value=110, acid value<0.05, linear wax type), PTG2000 (Mn=2,000, hydroxyl value=56, acid value<0.05, linear wax type) ), PTG3000 (Mn=3,000, hydroxyl value=36, acid value<0.05, linear wax type) [above, Hodogaya Chemical Co., Ltd.];

  PTMG1000 (Mn=1,000, hydroxyl value=110, acid value<0.05, linear wax type), PTMG2000 (Mn=2,000, hydroxyl value=56, acid value<0.05, linear wax type) ) [Above, manufactured by Mitsubishi Chemical Corporation];

  BLAUNONGL-9 (Mn=650, hydroxyl value=259, acid value<0.05, linear liquid trifunctional type), BLAUNONGL-20 (Mn=1,300, hydroxyl value=127, acid value<0.05, linear) Liquid trifunctional type), BLAUNONGL-26 (Mn=1,700, hydroxyl value=100, acid value<0.05, linear liquid trifunctional type) [above, manufactured by Aoki Yushi Kogyo KK];

  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, NOF Corporation] and the like.

The polyester polyol (a1-3) can be obtained by a condensation reaction between the aliphatic polyol (a1-1) and a polycarboxylic acid.
Examples of the known polycarboxylic acid used for obtaining the polyester polyol (a1-3) include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, and chloromaleic acid. , Fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride and other aliphatic dicarboxylic acids and their anhydrides;

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

  For example, 4-methylcyclohexane-1,2,3-tricarboxylic acid, (1a,2a,4a)-1,2,4-cyclohexanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2 , Trifunctional or higher polycarboxylic acids such as 3,4-pentanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and ethylenetetracarboxylic acid, and anhydrides thereof;

  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, but the glass of the pressure-sensitive adhesive is also usable. Considering the wettability and spreadability to another substrate such as a plate (also referred to as an adherend), the above-mentioned aliphatic or alicyclic dicarboxylic acid and its anhydride are preferable. These may be used alone or in combination of two or more.

  As the polyester polyol (a1-3), a commercially available product can be used, and Kuraray polyol P510 (Mn=500, hydroxyl value=224, acid value<0.5, linear liquid type), Kuraray polyol P1010 (Mn=1, 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 (Mn=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 group) Value=112, acid value<0.5, linear liquid type), Kuraray polyol PNOA2014 (Mn=2,000, hydroxyl value=56, acid value<0.5, linear liquid type), Kuraray polyol F1010 (Mn=1) 2,000, 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.];

  URICH-62 (Mn=430, hydroxyl value=260, acid value<4.0, linear liquid type), URICY-202 (Mn=980, hydroxyl value=115, acid value<1.0, linear liquid type), URICY-332 (Mn=910, hydroxyl value=123, acid value<1.0, linear liquid type), URICSE-3506 (Mn=3,500, hydroxyl value=32, acid value<1.0, white solid Type), URICH-52 (Mn=840, hydroxyl value=200, acid value<3.0, white solid trifunctional type) [above, manufactured by Ito Oil Co., Ltd.];

  For example, PLACCEL205 (Mn=530, hydroxyl value=212, acid value<1.0, linear liquid type), PLACCEL208 (Mn=830, hydroxyl value=135, acid value<1.0, linear wax type), PLACCEL210 (Mn=1,000, hydroxyl value=114, acid value<1.0, linear wax type), PLACCEL220 (Mn=2,000, hydroxyl value=56, acid value<1.0, linear wax type), PLACCEL230 (Mn=3,000, hydroxyl value=37, acid value<1.0, linear wax type), PLACCEL240 (Mn=4,000, hydroxyl value=28, acid value<1.0, linear wax type) ), PLACCEL303 (Mn=300, hydroxyl value=540, acid value<1.5, linear liquid trifunctional type), PLACCEL305 (Mn=550, hydroxyl value=305, acid value<1.0, linear liquid trifunctional type) ), PLACCEL308 (Mn=850, hydroxyl value=195, acid value<1.5, linear liquid trifunctional type), PLACCEL309 (Mn=950, hydroxyl value=187, acid value<1.0, linear liquid trifunctional type) ), PLACCEL312 (Mn=1,250, hydroxyl value=135, acid value<1.0, white solid trifunctional type), PLACCEL320 (Mn=2,000, hydroxyl value=84, acid value<1.0, White solid trifunctional type), PLACCEL420 (Mn=1,000, hydroxyl value=224, acid value<1.0, linear liquid tetrafunctional type) [above, manufactured by Daicel];

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, Kyowa Hakko Chemical Co., Ltd.]
Etc. can be mentioned.

The polyamide polyol (a1-4) can be synthesized by subjecting the polyamide polyol formed by the condensation reaction with the above-mentioned polycarboxylic acid and polyamine to the condensation reaction of the aliphatic polyol (a1-1) with the molecular terminal.
As the polyamine, any polyamine having two or more amino groups can be used without 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 menthenediamine, isophoronediamine, 1,3-(bisaminomethyl)cyclohexane, 1,4-(bisaminopropyl)cyclohexane, 4,4′-methylenebis(2-methylcyclohexylamine), norbornanediamine. A cyclic diamine;

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

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

Among these, the polyamine is preferably an aliphatic diamine or an alicyclic diamine, in consideration of the wettability and spreadability of the pressure-sensitive adhesive to the adherend.
Polyamines can be used alone or in combination of two or more.

  As the polyamide polyol (a1-4), commercially available products include, for example, TPAE617 (Mn=15,000, Tg=90° C., hydroxyl value=16, acid value=1, linear type) [above, Fuji Chemical Industry Co., Ltd. Manufactured] and the like.

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

General formula [1]:-[-OR- ^l- O-CO-] _m-
(In the formula, R ¹ represents a divalent organic residue, and m represents an integer of 1 or more.)

Polycarbonate polyol (a1-5) acts on (I) reaction of aliphatic polyol (a1-1) with carbonic acid ester, or (II) aliphatic polyol (a1-1) with phosgene in the presence of alkali. It can be synthesized by a reaction or the like.
Examples of the carbonic acid ester include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate and the like.

  Since the polycarbonate polyol (a1-5) has a carbonate structure as a linking group, the cohesive force of the polyurethane resin (A) is increased, and the polycarbonate polyol (a1-5) has excellent heat resistance, hydrolysis resistance, and weather resistance. Furthermore, the removability is particularly excellent in a harsh environment.

The commercially available product of the polycarbonate polyol (a1-5) is, for example, Oximer N112 (Mn=1,000, Tg=60° C., hydroxyl value=112, acid value<0.5, linear type) (manufactured by Perstorp). ;
Duranol T6001 (Mn=1,000, hydroxyl value=110, acid value<0.05, linear liquid type), Duranol T6002 (Mn=2,000, hydroxyl value=56, acid value<0.05, linear liquid type) ), 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];

  ETERNACOLLUH-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.];

  BENEBiOLNL1010DB (Mn=1,000, hydroxyl value=110, acid value<0.05, linear solid type), BENEBiOLNL2010DB (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)[ Above, manufactured by Mitsubishi Chemical Co., Ltd.];

  PLACECELCD205 (Mn=500, hydroxyl value=225, acid value<0.1, linear liquid type), PLACCELCD210 (Mn=1,000, hydroxyl value=116, acid value<0.1, linear wax type), PLACCELCD220 (Mn=2,000, hydroxyl value=56, acid value<0.1, linear wax type) [above, manufactured by Daicel];

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. can be mentioned.

  The other polyol (a1-6) is a polyol that does not belong to the aliphatic polyols (a1-1) to (a1-5), and contains at least one ionic functional group, 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 hydrogenated diene in which the diene skeleton is saturated with hydrogen atoms.

  Among the polyols containing at least one ionic functional group, the ionic functional group means a quaternary ammonium group, a tertiary amino group, a carboxylate group, a carboxyl group, a sulfonate group, a sulfonic acid group, a phosphonium group. And 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 into ionic functional groups by neutralization with ammonia, tertiary amines, acetic acid, etc. or by a quaternization reaction. 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)kyl. Carboxyl group-containing polyol compounds such as herbic acid and 2,2-bis(hydroxymethyl)butanoic acid, and also hydrogen atoms of ammonia such as N,N-bis(2-hydroxypropyl)aniline and N-methyldiethanolamine are hydrocarbon groups. Examples of the polyol include a substituent-containing polyol and the like.

  Examples of commercially available polyols having a siloxane skeleton include 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, 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) ) [Above, manufactured by Toray Dow Corning Co., Ltd.] and the like.

  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, Nippon Soda Co., Ltd. ];

  Epol (Mn=2,500, 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) ) [Above, manufactured by Idemitsu Kosan Co., Ltd.] and the like. The diene skeleton also includes an olefin skeleton obtained by hydrogenating the diene skeleton.

The polyol (a1) other than the aliphatic polyol (a1-1) preferably has a number average molecular weight (Mn) of 200 to 50,000, more preferably 400 to 30,000, and even more preferably 600 to 10,000. When the number average molecular weight (Mn) is in the above range, it is easy to obtain a viscosity suitable for coating, and therefore handling during coating is excellent. Further, it becomes easy to give the polyurethane resin (A) an appropriate cohesive force and sufficient flexibility, and it becomes possible to exhibit sufficient tackiness in the slightly viscous region. Further, the pressure-sensitive adhesive film produced from the pressure-sensitive adhesive can further suppress floating and peeling under a severe environment such as high temperature and high humidity. Thus, when the polyol (a1) is used, a pressure sensitive adhesive having excellent adhesion and wettability can be easily obtained.
The weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene conversion values measured by gel permeation chromatography (GPC). Details of the GPC measurement method are described in Examples.

The polyol (a1) other than the aliphatic polyol (a1-1) preferably has a hydroxyl value of 2 to 560 mgKOH/g, more preferably 4 to 280 mgKOH/g, and further preferably 4 to 200 mgKOH/g. When the hydroxyl value is in the above range, a viscosity suitable for coating is easily obtained, and thus handling during coating is excellent. Further, it becomes easy to give the polyurethane resin (A) an appropriate cohesive force and sufficient flexibility, and it becomes possible to exhibit sufficient tackiness in the slightly viscous region. Further, the pressure-sensitive adhesive film produced from the pressure-sensitive adhesive can further suppress floating and peeling under a severe environment such as high temperature and high humidity. Thus, when the polyol (a1) is used, a pressure sensitive adhesive having excellent adhesion and wettability can be easily obtained.
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, and the details of the measuring method are described in Examples.

  When the polyol (a1) has a glass transition temperature (Tg), it is not particularly limited, but is preferably −80 to 80° C., more preferably −70 to 40° C. When the glass transition temperature (Tg) is within the above range, the pressure-sensitive adhesive containing the polyurethane resin (A) has sufficient tackiness and cohesive force, so that cohesive failure of the adhesive layer is maintained while maintaining adhesiveness. Suppress and prevent floating and peeling. The details of the measuring method will be described in Examples.

The polyurethane resin (A) used in the present invention needs to have a carbonate structure in the main chain. In order to obtain this carbonate structure, it is necessary to use the polycarbonate polyol (a1-5) as the polyol (a1). The amount of the polycarbonate polyol (a1-5) used is preferably 1 to 80% by weight, and more preferably 5 to 60% by weight, based on the total amount of the polyol (a1). When the polycarbonate polyol (a1-5) is in the above range, the pressure-sensitive adhesive film produced from the pressure-sensitive adhesive does not float or peel even under a harsh environment such as high temperature and high humidity and after peeling. It is possible to obtain good removability without contaminating the adherend.
Further, when a polyol having an alkyl group having 1 to 8 carbon atoms in the side chain is used, the viscosity of the pressure-sensitive adhesive can be reduced, and thus the coatability is further improved. In addition, the pressure-sensitive adhesive film exhibits a good adhesive force in a slightly viscous region and further has an improved wettability and spreadability.

Further, it is preferable that the polyol (a1) is used in combination with a diol and a “trifunctional or more functional polyol” having three or more hydroxyl groups. The polyurethane resin (A) using a trifunctional or higher functional polyol has good wettability and spreadability, and can introduce a hydroxyl group that can serve as a cross-linking point with the reactive compound (B), which will be described later. Hopefully, it can be applied to surface protection film.
Among these, in order to achieve a high degree of compatibility between removability, adhesiveness in a slightly viscous region, and wet spreadability, the polycarbonate diol and the polyether polyol (a1-2) contained in the polycarbonate polyol (a1-5) are included. It is particularly preferable to use the polyether triol contained in the above.

<<Polyisocyanate (a2)>>
The polyisocyanate (a2) as used herein refers to a polyisocyanate having no aromatic ring. Examples of the polyisocyanate (a2) include aliphatic polyisocyanate and alicyclic polyisocyanate. In addition, an aliphatic means an acyclic carbon compound, and a cyclic carbon compound is defined as an alicyclic group.
Further, the polyisocyanate (a2) may have three or more isocyanate groups, but a diisocyanate having two isocyanate groups is preferable from the viewpoint of imparting flexibility as the density of the polyurethane urea resin is reduced.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (alias: HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodeca. Examples thereof include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

The alicyclic polyisocyanate is, 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-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, norbornene diisocyanate, dimer acid diisocyanate and the like can be mentioned. ..
Among these, aliphatic polyisocyanates such as hexamethylene diisocyanate (alias: HDI), alicyclic polyisocyanates such as isophorone diisocyanate (alias: IPDI), 4,4′-methylenebis(cyclohexyl isocyanate) (alias: hydrogenated MDI) It is preferable to use a non-yellowing type or hardly yellowing type diisisoanate having no aromatic ring, such as, from the viewpoint of weather resistance and tackiness.

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 a high level of coating suitability of the pressure-sensitive adhesive and cohesiveness and cohesive strength of the adhesive layer at a high level. Is preferred, and more preferably 30,000 to 400,000. When Mw is in the above range, cohesive force and the like are further improved, so that floating and peeling can be further suppressed and wettability and spreadability are further improved. The weight average molecular weight and the number average molecular weight are polystyrene conversion values measured by a gel permeation chromatography (GPC) method. Details of the GPC measurement method are described in Examples.

  The hydroxyl value (OHV) of the polyurethane resin (A) is preferably 0.1 to 50 mgKOH/g, more preferably 0.5 to 30 mgKOH/g. When the hydroxyl value (OHV) is within 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, so that the pressure-sensitive adhesive has sufficient cohesive force. While maintaining the above, it becomes easy to develop the adhesive force in the slightly viscous region. In addition, it is easy to maintain durability such as heat resistance and moist-heat resistance even under severe conditions such as high temperature and high humidity after aging. When peeled off, contamination such as fogging and adhesive residue on the adherend is suppressed.

  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 viscosity is preferably 3,000 to 10,000 mPa·s (25° C.) at a nonvolatile concentration of 60% by weight. When the viscosity is within this range, the coating processability is improved while maintaining a sufficient cohesive force, which is preferable.

  The polyurethane resin preferably contains 80 to 99% by weight of the polyol (a1) and 1 to 20% by weight of the polyisocyanate (a2), and 85 to 98% by weight of the polyol (a1) in all the monomers used for the synthesis. %, and the polyisocyanate (a2) is more preferably contained in the range of 2 to 15% by weight. When the polyol (a1) and the polyisocyanate (a2) are in the above ranges, the viscosity suitable for coating is maintained, so that the polyurethane resin (A) is excellent in handling during coating. Since the pressure-sensitive adhesive containing this polyurethane resin (A) is easy to obtain an appropriate cohesive force and sufficient flexibility, when the produced pressure-sensitive adhesive film is attached to an adherend such as a glass plate, it becomes wet. It has excellent spreadability and removability, and can be further suppressed from floating and peeling even under severe conditions such as high temperature and high humidity after sticking.

<Reactive compound (B) having functional group capable of reacting with hydroxyl group>
In the present 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 parts by weight with respect to 100 parts by weight of the polyurethane resin (A). It is necessary to contain it, and 1 to 30 parts by weight is more preferable. When the reactive compound (B) is in this range, not only the heat resistance and the 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 the harsh environment is improved. Floating, peeling and foaming can be further suppressed.

Further, the polyurethane resin (A) has a hydroxyl group. Therefore, examples of the reactive 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 in the molecule capable of reacting with the hydroxyl group of the polyurethane resin (A) in order to impart crosslinkability.
In particular, the polyisocyanate (b1) is preferably used because it is excellent in the adhesiveness after the crosslinking reaction and the adhesiveness to the base material described later.

  The polyisocyanate (b1) is a compound having a plurality of isocyanate groups in the molecule. The polyisocyanate (b1) can be classified into an aliphatic polyisocyanate, an alicyclic polyisocyanate, or an aromatic polyisocyanate. As the aliphatic polyisocyanate and the alicyclic polyisocyanate, the aliphatic polyisocyanate and the alicyclic polyisocyanate described in the above polyisocyanate (a2) can be used.

  Aromatic polyisocyanates include, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (also known as 2,4-TDI), and 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"-triphenylmethane 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'-diphenylmethane diisocyanate (alias: 4,4-MDI), 1,3-naphthalenediyl diisocyanate (alias: 1,3-NDI), 1,5 -Naphthalenediyl diisocyanate (also known as 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-tetramethylxylylene diisocyanate and the like.

  The polyisocyanate (b1) is also preferably a compound having 3 or more isocyanate groups. Such polyisocyanates (b1) are preferably adducts of various polyisocyanates with polyols such as 2-methylpentane-2,4-diol and trimethylolpropane, trimers having an isocyanurate ring, and the like. Further, polyphenylmethane polyisocyanate (also known as PAPI), and polyisocyanate-modified products thereof are also preferable. As the polyisocyanate modified product, a carbodiimide group, a uretdione group, a uretonimine group, a buret group reacted with water, an isocyanurate group, 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. As the polyisocyanate (b1), a blocked isocyanate in which an isocyanate group is blocked by using a blocking agent can also be used.

  A catalyst can be used in combination with the polyisocyanate (b1). The use of the catalyst accelerates the crosslinking reaction between the hydroxyl groups of the polyurethane resin (A) and the isocyanate groups. 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 (alias: DBU) and the like.

Examples of the organometallic compound include tin compounds and non-tin compounds.
Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, and the like. Examples thereof 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 dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate. -Iron-based compounds such as iron ethylhexanoate and iron 2,4-pentadionate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate. , Zirconium naphthenate and the like.
Among them, diazabicycloundecene (alias: DBU), dibutyltin dilaurate (alias: DBTDL), tin 2-ethylhexanoate and the like are preferable from the viewpoint of reactivity and hygiene.
The catalyst can be used alone or in combination of two or more kinds.

  The polyisocyanate (b1) is, in particular, in terms of cross-linking reactivity, an adduct body of diisocyanate such as HDI, TDI, MDI, IPDI with trimethylolpropane, a buret body reacted with water, and an isocyanurate ring-forming trimeric compound. The body is preferably used, but from the viewpoints of maintaining the adhesive strength in the slightly viscous region and reducing the density, an HDI or IPDI adduct with trimethylolpropane, a buret body reacted with water, or isocyanurate. Ring-forming trimers are particularly preferred.

  The silane compound (b2) is, for example, an alkyl-based alkoxysilane, an aryl-based alkoxysilane, a carbamate-based alkoxysilane, a vinyl-based alkoxysilane, a halogen-based alkoxysilane, a (meth)acryloyl-based alkoxysilane, a mercapto-based alkoxysilane, or an imidazole-based alkoxy. Examples thereof 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, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldiacetoxy Silane, dimethylbis(methoxyethoxy)silane, dimethylbis(methoxypropoxy)silane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldiacetoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyl Alkyl-based alkoxysilanes such as ethyldiisopropoxysilane, methylethyldiacetoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, methylpropyldiisopropoxysilane, and methylpropyldiacetoxysilane;

  For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldiphenyldimethoxysilane. Aryl-based alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, and 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) ) Pentyltributoxysilane, (3-carbamateethyl)propylsilyltrichloride, (3-carbamateethyl)propyltrimethylsilane, (3-carbamateethyl)propyldimethylsilane, 3-carbamateethyl)propyltributylsilane, (3-carbamate Carbamate-based alkoxysilanes such as ethyl)ethyl-p-xylenetriethoxysilane and (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, Vinyl- and allyl-based alkoxysilanes such as diallyldiisopropoxysilane, methylallyldimethoxysilane, methylallyldiethoxysilane, methylallyldiisopropoxysilane, and methylallyldiacetoxysilane;

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

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

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

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

  For example, isocyanate-based alkoxysilanes such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and 3-isocyanatepropyltripropoxysilane;

  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, and 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-cyclohexyl Aminopropyltrimethoxysilane, 2-cyclohexylaminoethylthiomethyltrimethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-phenylaminopropyltrimethoxysilane, N-[2-(vinylbenzylamino)ethyl ]-3-Aminopropyltrimethoxysilane, 2-(2-aminoethylthioethyl)triethoxysilane, 3-piperazinopropylmethyldimethoxysilane, 3-piperazinopropyltrimethoxysilane, 3-ureidopropyltriethoxy Examples include amino-based alkoxysilanes such as silane.

In addition, as the silane compound (b2), an oligomer silane obtained by hydrolyzing and condensing a mixture of two or more silanes to form an oligomer can be used.
Among these, a silane compound having no aromatic ring is preferable from the viewpoint of wettability and spreadability with respect to the adherend.
In addition, the silane compound (b2) is a methyltrimethoxysilane, a methyltriethoxysilane, an ethyltrimethoxysilane, and an ethyl group in terms of a condensation reaction with a hydroxyl group of the polyurethane resin (A) and an improvement in adhesion to the surface of the base material. Alkyl alkoxysilane such as triethoxysilane, 3-mercaptopropyltrimethoxysilane, mercapto alkoxysilane such as 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, epoxy alkoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, imidazole alkoxysilanes such as 3-(2-imidazolin-1-yl)propyltriethoxysilane, 3-aminopropyltrisilane Methoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, 2-cyclohexylaminoethyl Amino-based alkoxysilanes such as thiomethyltrimethoxysilane and trimethylsilyldimethylamine, and isocyanate-based alkoxysilanes such as 3-isocyanatepropyltriethoxysilane are preferable.
The silane compound (b2) can be used alone or in combination of two or more kinds.

Examples of the methylol melamine compound (b3) include a methylol melamine derivative obtained by condensing melamine and formaldehyde, and a compound obtained by reacting these with a lower alcohol such as methyl alcohol, ethyl alcohol, or isopropyl alcohol and the like, and etherification. .. The methylolmelamine compound (b3) is, for example, monomethylolmelamine, dimethylolmelamine, trimethylolmelamine (alias: cearicin), tetramethylolmelamine, pentamethylolmelamine, pentamethoxymethylolmelamine, hexamethylolmelamine, hexamethoxymethylolmelamine, 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, pentamethoxymethylolmelamine and hexamethoxymethylmelamine are preferable from the viewpoint of condensation reaction with the hydroxyl group of the polyurethane resin (A) and improvement of adhesion to the surface of the substrate.

  The methylol melamine compound (b3) can be used alone or in combination of two or more kinds.

  In addition to the polyisocyanate (b1), the silane compound (b2), and the methylolmelamine-based compound (b3), the reactive compound (B) has excellent adhesiveness after the crosslinking reaction and adhesion to the substrate. The polyisocyanate (b1) is preferable in terms of achieving both high flexibility and wet spreadability by controlling the crosslinking density.

<Ester compound (C)>
The pressure-sensitive adhesive of the present invention may further contain an ester compound (C).
The ester compound (C) can impart a plasticizing effect to the adhesive layer after coating and further improve the wettability and spreadability of the pressure-sensitive adhesive film to an adherend such as a glass plate. Further, after the pressure-sensitive adhesive film is attached to the adherend, the peeling at the time of peeling becomes light, so that workability is improved. In addition, contamination such as adhesive residue on the adherend can be suppressed. The components other than the polyurethane resin (A) and the reactive compound (B) having a functional group capable of reacting with a hydroxyl group are optional components.

  The ester compound (C) is a fatty acid ester (c1) having 8 to 100 carbon atoms, a phosphoric acid ester (c2) having 4 to 80 carbon atoms, a borate ester (c3) having 8 to 100 carbon atoms, and the ester (c1). To (c3) at least one selected from the group consisting of epoxy modified esters. However, the ester compound (C) does not include the compound (A) and the reactive compound (B).

  The fatty acid ester (c1) having 8 to 100 carbon atoms is preferably an ester of a monobasic acid or polybasic acid having 22 or less carbon atoms and an alcohol having 4 or less valences, and further (1) having 4 to 22 carbon atoms. An ester of a monobasic acid or a polybasic acid and a monohydric alcohol having 22 or less carbon atoms, (2) a monobasic acid having 18 to 22 carbon atoms, and a tetrahydric or less alcohol having 22 or less carbon atoms An ester and an epoxy-modified ester obtained by further modifying the ester of (3)(1) or (2) with epoxy are preferable.

  Saturated-basic acids having 4 to 22 carbon atoms include, for example, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylcaproic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, Examples thereof include palmitic acid, margaric acid, stearic acid, isostearic acid, arachidic acid and behenic acid.

  Unsaturated monobasic acids having 4 to 22 carbon atoms include 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, ozbondic acid, Examples thereof 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-dodecanedioic acid. Acid, 1,12-octadecanedioic acid, eicosanedioic acid and the like can be mentioned.

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

  The polybasic acid having 4 to 22 carbon atoms includes isocitric acid, aconitic acid, 1,2,3-propanetricarboxylic acid, 1,2,3-propenetricarboxylic acid, camphoronic acid, isocamphoronic acid, ethanetetracarboxylic acid, butane. Examples thereof include tetracarboxylic acid, octane tetracarboxylic acid, ethylene tetracarboxylic acid and butene tetracarboxylic acid.

  Monovalent saturated alcohols having 22 or less carbon atoms include, for example, methanol, ethanol, propanol, butanol, hexanol, 2-ethylhexanol, april alcohol, pelargone alcohol, caprin alcohol, undecyl alcohol, 2-butyloctanol, and 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) Also referred to as ), octyldodecyl alcohol, heneicosanol, behenyl alcohol, 2-(2-butoxyethoxy)ethyl alcohol, 2-(2-methoxyethoxy)ethyl alcohol, and the like, or alkylene oxide adducts thereof.

  Monovalent unsaturated alcohols having 22 or less carbon atoms include, for example, palmitolyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elide linoleyl alcohol, linolenyl alcohol, erucyl alcohol, or the like. The alkylene oxide adduct of

  Examples of the dihydric to tetrahydric alcohol having 18 or less carbon atoms include, for example, diols having 22 or less carbon atoms, ricinoleyl alcohol, glycerin, diglycerin, polyglycerin and trimethylolpropane, which are mentioned in the polyol (a1). , Pentaerythritol, sorbitol and the like, or alkylene oxide adducts thereof.

  Examples of the fatty acid ester (c1) having 8 to 100 carbon atoms include (1) as an ester of a monobasic acid or polybasic acid having 4 to 22 carbon atoms and a monohydric alcohol having 22 or less carbon atoms, for example, capron. Isopropyl acid, lauryl caproate, stearyl caproate, cetyl caprylate, stearyl caprylate, cetyl 2-ethylcaproate, stearyl 2-ethylcaproate, stearyl caprate, cetyl laurate, stearyl laurate, isopropyl myristate, myristin Acid isocetyl, stearyl myristate, octyldodecyl myristate, lauryl palmitate, isostearyl palmitate, isocetyl stearate, octyldodecyl stearate, isocesyl isostearate, isostearyl behenate, polyoxyethylene laurate methyl ester, polyoxyethylene Saturated fatty acid monoesters of monobasic acids such as lauric acid stearyl ester and polyoxyethylene stearic acid isopropyl ester;

  For example, methyl crotonate, butyl crotonate, methyl palmitoleate, octyldodecyl palmitoleate, methyl sabienate, methyl oleate, methyl oleate, isopropyl oleate, butyl oleate, octyldodecyl oleate, methyl elaidate, vaccenic acid. Methyl, methyl linoleate, ethyl linoleate, isopropyl linoleate, butyl linoleate, octyldodecyl linoleate, ethyl linolenate, octyldodecyl linolenate, methyl pinolenate, methyl pinolenate, methyl eleostearate, methyl stearidate, Butyl stearidate, methyl boseopentanoate, methyl gadelate, methyl icosadienoate, methyl icosatrienoate, methyl eicosenoate, ethyl eicosenoate, isopropyl eicosenoate, methyl eicosadienate, methyl eicosatrienoate, methyl eicosatetraenoate, e Unsaturated fatty acid monoesters of monobasic acids and monohydric alcohols, such as methyl icosapentaenoate, methyl meadate, methyl arachidonic acid, methyl erucate, methyl docosadienoate, methyl adrenate, methyl ozbondate, methyl iwasate, and methyl docosahexaenoate. ester;

  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 Dibasic acids such as diethyl azelate, diethyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisocetyl sebacate, dibutyloctyl sebacate, diisostearyl sebacate, and dibutyl 1,10-decanedioate, and monohydric alcohols. Saturated fatty acid diesters of;

  For example, a dibasic acid such as diethyl maleate, diisopropyl maleate, dibutyl maleate, diisopropyl fumarate, dimethyl mesaconate, diethyl mesaconate, diisopropyl mesaconate, dibutyl mesaconate, dimethyl muconate, diethyl muconate and a monohydric alcohol. Unsaturated fatty acid diesters with;

Trimethyl isocitrate, trimethyl aconitate, trimethoxy polyoxyethylene aconitate, trimethyl 1,2,3-propane tricarboxylate, trimethyl 1,2,3-propene tricarboxylate, trimethyl camphoroneate, trimethoxy polyoxyethylene camphoroneate, Trimethyl isocamphorone, tetramethyl ethanetetracarboxylate, dimethyl butanetetracarboxylate, trimethyl butanetetracarboxylate, tetramethyl butanetetracarboxylate, tetramethyl octanetetracarboxylate, tetramethyl ethylenetetracarboxylate, tetramethyl butenetetracarboxylate Unsaturated fatty acid polyhydric esters of polybasic acids such as and monohydric alcohols;

  For example, unsaturated fatty acid monoesters of monobasic alcohols and polybasic acids such as monoisodecyl adipate, monoisopropyl sebacate, monoisostearyl sebacate, monoethyl mesaconate, monoisopropyl mesaconate, dimethyl aconitate, and dimethyl camphoroneate are Can be mentioned. These may be used alone or in combination of two or more.

  The fatty acid ester (c1) having 8 to 100 carbon atoms is, for example, a diester of (2) a monobasic acid having 18 to 22 carbon atoms and a tetravalent or less alcohol having 22 or less carbon atoms, such as diester. Butyrate diethylene glycol, divalerate ethylene glycol, dicaproate neopentyl glycol, dicaproate diethylene glycol, dicaproate triethylene glycol, dicaproate oxyethylene, dicaproate dipropylene glycol, dicaproate polyoxypropylene, dienanthate diethylene glycol, dicaprylate neopentyl Glycol, ethylene glycol dicaprylate, polyoxyethylene dicaprylate, neopentyl glycol di2-ethylcaproate, diethylene glycol di2-ethylcaproate, polyoxypropylene di2-ethylcaproate, dipropylene glycol di2-ethylcaproate , Dipropylene glycol di2-ethylcaproate, diethylene glycol dipelargonate, diethylene glycol dicaprate, polyoxyethylene dicaprate, neopentyl glycol dilaurate, diethylene glycol dilaurate, polyoxyethylene dilaurate, polyoxypropylene dilaurate, dimyristic acid Neopentyl glycol, diethylene glycol dimyristate, dipropylene glycol dimyristate, polyoxypropylene dimyristate, polyoxyethylene dimyristate, polyoxypropylene dimyristate, diethylene glycol dipentadecylate, neopentyl glycol dipalmitate, dipalmitin Acid diethylene glycol, polyoxyethylene dipalmitate, diethylene glycol dimargaric acid, neopentyl glycol distearate, ethylene glycol distearate, diethylene glycol distearate, polyoxyethylene distearate, polyoxypropylene distearate, ricinoyl distearate, diethylene stearate diethylene glycol, diisostearin Saturated fatty acid diesters of saturated monobasic acids such as polyoxyethylene acid, polyoxypropylene diisostearate, diethylene glycol diarachidate, diethylene glycol dibehenate and the like, and divalent alcohols (also known as diols);

  For example, ethylene glycol dicrotonate, propylene glycol dicrotonate, polyoxyethylene dicrotonate, ethylene glycol dipalmitoleate, ethylene glycol disabienate, ethylene glycol dioleate, polyoxyethylene dioleate, neopentyl glycol dioleate, hexyl glycol dioleate. , Propylene glycol dioleate, polyoxypropylene dioleate, ethylene glycol dielaidate, polyoxypropylene dielaidate, ethylene glycol dibacenoate, ethylene glycol dilinoleate, propylene glycol dilinoleate, neopentyl glycol dilinoleate, ethylene glycol dilinolenate , Polyoxyethylene dilinolenate, propylene glycol dilinolenate, polyoxyethylene dilinoleate, neopentyl glycol dilinolenate, ethylene glycol dipinolenate, ethylene glycol dieleostearate, ethylene glycol distearidate, ethylene glycol diboseopentaenoate, digadrain Acid ethylene glycol, diicosadienoic acid ethylene glycol, diicosatrienoic acid ethylene glycol, dieicosenoic acid ethylene glycol, dieicosadienoic acid ethylene glycol, dieicosatrienoic acid ethylene glycol, dieicosatetraenoic acid ethylene glycol, dieicosapentaenoic acid ethylene glycol, dimead acid ethylene glycol, Ethylene glycol diarachidonic acid, ethylene glycol dierucate, ethylene glycol didocosadienoate, ethylene glycol diadrenate, ethylene glycol diozbondate, ethylene glycol diiwasate, ethylene glycol didocosahexaenoate, polyoxyethylene di-2-ethylcaproate ether/caprate ester Unsaturated fatty acid diesters of unsaturated monobasic acids such as and dihydric alcohols (also known as diols);

  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, lauric acid Acid polyoxyethylene triglyceride, myristic acid triglyceride, myristic acid polyoxyethylene triglyceride, pentadecyl 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 triglyceride, behenic acid triglyceride, trimethylolpropane tricaproate, trimethylolpropane tricaprylate, trimethylolpropane tri-2-ethylcaproate, polypolyoxyethylene trimethylolpropane tri-2-ethylcaproate, tricapric triacid Methylolpropane, trimethylolpropane dilaurate, trimethylolpropane trilaurate, polyethylene glycol trimethylolpropane trilaurate, trimethylolpropane dimyristate, trimethylolpropane trimyristate, trimethylolpropane tripalmitate, polyethylene glycol tripalmitate Methylolpropane, trimethylolpropane tristearate, polyoxyethylene trimethylolpropane tristearate, trimethylolpropane triisostearate, pentaerythritol tetracaproate, pentaerythritol tetracaprylate, pentaerythritol tetra-2-ethylcaproate, tetracaprin Acid pentaerythritol, tetralauric acid pentaerythritol, tetramyristic acid pentaerythritol, tetrapalmitic acid pentaerythritol, tetrastearic acid pentaerythritol, tetraisostearic acid pentaerythritol, tetra-2-ethylcaproic acid diglyceryl, tetralauric acid diglyceryl, tetra Diglyceryl myristate, Diglyceryl tetrapalmitate, Diglyceryl tetrastearate, Polyoxyethylene sorbitate hexa-2-ethylcaproate, Hexalaurate poly Oxyethylene sorbit, hexamyristic acid polyoxyethylene sorbit, hexapalmitic acid polyoxyethylene sorbit, tristearic acid polyoxyethylene sorbit, hexastearic acid polyoxyethylene sorbit, hexaisostearic acid polyoxyethylene sorbit, tetralauric acid polyglyceryl, tetra Saturated fatty acid polyhydric ester of saturated monobasic acid such as polyglyceryl stearate, polyglyceryl hexastearate and the like;

  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, gadoleic acid triglyceride, icosadienoic acid triglyceride, icosatrienoic acid triglyceride, eicosenoic acid triglyceride, eicosadienoic acid triglyceride, eicosatrienoic acid triglyceride, eicosatetraenoic acid triglyceride, eicosapentaenoic acid Triglyceride, meadic acid triglyceride, arachidonic acid triglyceride, erucic acid triglyceride, docosadienoic acid triglyceride, adrenic acid triglyceride, ozbondic acid triglyceride, iwasic acid triglyceride, docosahexaenoic acid triglyceride, tetracrotonic acid pentaerythritol, tetrapalmitoleic acid pentaerythritol, tetrasabienoic acid penta Erythritol, pentaerythritol dioleate, pentaerythritol trioleate, pentaerythritol tetraoleate, pentaerythritol tetraelaidate, pentaerythritol tetrabacenoate, pentaerythritol tetralinoleate, pentaerythritol dilinolenate, pentaerythritol trilinolenate, tetralinolene. Acid pentaerythritol, pentaerythritol tetrapinolenic acid, pentaerythritol tetraeleostearate, pentaerythritol tetrastearic acid, pentaerythritol tetraboseopentaenoate, pentaerythritol tetragadenate, pentaerythritol tetricosadienoate, tetrico Pentaerythritol satrienoate, Pentaerythritol tetraeicosenoate, Pentaerythritol tetraeicosadienoate, Pentaerythritol tetraeicosatrienoate, Pentaerythritol tetraeicosatetraenoate, Pentaerythritol tetraeicosapentaenoate, Pentaerythritol tetrameate, Pentaerythritol tetraarachidonic acid, Pentaerythritol tetraerucate, Tetradocosadiene Acid pentaerythritol, tetraadrenic acid pentaerythritol, tetraozozene acid pentaerythritol, tetryvasiic acid pentaerythritol, tetradocosahexaenoic acid pentaerythritol, crotonic acid polyoxyethylene triglyceride, palmitoleic acid polyoxyethylene triglyceride, linoleic acid polyoxyethylene triglyceride, linolene Acid polyoxyethylene triglyceride, oleic acid polyoxyethylene triglyceride, tetrapalmitoleic acid polyoxyethylene pentaerythritol, tetralinoleic acid polyoxyethylene pentaerythritol, tetralinolenic acid polyoxyethylene pentaerythritol, hexacrotonic acid polyoxyethylene sorbit, hexapalmitolein Acid polyoxyethylene sorbit trioleic acid polyoxyethylene sorbit, tetraoleic acid polyoxyethylene sorbit, hexaoleic acid polyoxyethylene sorbit, hexaelaidic acid polyoxyethylene sorbit, tetralinoleic acid polyoxyethylene sorbit, hexalinoleic acid polyoxy Unsaturated monobasic acids and polyhydric alcohols such as ethylene sorbit, tetralinolenic acid polyoxyethylene sorbit, hexalinolenic acid polyoxyethylene sorbit, hexastearidonic acid polyoxyethylene sorbit, hexaeicosenoic acid polyoxyethylene sorbit Saturated fatty acid polyvalent ester;

  For example, polyoxyethylene glyceryl monolaurate, polyoxyethylene glyceryl monomyristate, polyoxyethylene glyceryl monostearate, polyoxyethylene glyceryl monooleate, polyoxyethylene trimethylolpropane monolaurate, polyoxyethylene trimethylol monomyristate. Propane, Polyoxyethylene trimethylol propane monostearate, Polyoxyethylene trimethylol propane monooleate, Polyoxyethylene trimethylol propane monolinoleate, Polyoxyethylene trimethylol propane monolinolenate, Polyoxyethylene sorbitan monostearate , Sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, monoisostearate polyoxyethylene glyceryl, pentaerythritol monolaurate, penta Examples thereof include fatty acid monoesters of monobasic acids and polyhydric alcohols such as erythritol monomyristic acid ester, pentaerythritol monostearic acid ester, pentaerythritol monooleic acid ester, and pentaerythritol monolinoleic acid ester.

The fatty acid ester (c1) having 8 to 100 carbon atoms is the above-mentioned unsaturated fatty acid monoester, unsaturated fatty acid diester, as an epoxy-modified ester obtained by further modifying the ester of (3) (1) or (2) with epoxy. Alternatively, an epoxy modification obtained by reacting an unsaturated fatty acid polyvalent ester with a peracid such as m-chloroperbenzoic acid or dimethyloxirane to epoxidize the olefinic double bond contained in the unsaturated fatty acid ester Esters can be mentioned.
The fatty acid ester (c1) having 8 to 100 carbon atoms can be used alone or in combination of two or more kinds.

The phosphoric acid ester having 4 to 80 carbon atoms (c2) is an ester compound obtained by dehydration condensation of phosphoric acid and the above tetravalent or lower alcohol.
For example, monobutyl phosphate, monohexyl phosphate, mono-2-ethylhexyl phosphate, monoapril phosphate, monopelargon phosphate, monocaprin phosphate, monoundecyl phosphate, mono-2-butyloctyl phosphate, monolauryl phosphate, phosphorus Acid monotridecyl phosphate, monomyristyl phosphate, monopentadecyl phosphate, monopalmityl phosphate, monoisocetyl phosphate, monoheptadene phosphate, monostearyl phosphate, monoisostearyl phosphate, monononadecyl phosphate, monoarachidyl phosphate, monooctyldodecyl phosphate. Phosphoric acid such as monoheneicosyl phosphate, monobehenyl phosphate, mono-2-(2-butoxyethoxy)ethyl phosphate, mono-2-(2-methoxyethoxy)ethyl phosphate, or an alkylene oxide adduct thereof. Saturated monoesters;

  For example, monopalmityl phosphate, monoelaidyl phosphate, monooleyl phosphate, monolinoleyl phosphate, monoeline linoleyl phosphate, monolinolenyl phosphate, monoerucyl phosphate, or phosphate unsaturated such as alkylene oxide adducts thereof. Monoester;

  For example, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dihexyl phosphate, di2-ethylhexyl phosphate, diapril phosphate, diperargone phosphate, dicaprin phosphate, diundecyl phosphate, di2-butyloctyl phosphate, Dilauryl phosphate, ditridecyl phosphate, dimyristyl phosphate, dipentadecyl phosphate, dipalmityl phosphate, diisocetyl phosphate, diheptadene phosphate, distearyl phosphate, diisostearyl phosphate, dinonadecyl phosphate, diarachidyl phosphate, dioctyl phosphate. Saturated phosphoric acid diesters such as dodecyl, diheneicosan phosphate, dibehenyl phosphate, di2-(2-butoxyethoxy)ethyl phosphate, di2-(2-methoxyethoxy)ethyl phosphate, or their alkylene oxide adducts. ;

  For example, dipalmitrail phosphate, dielaidyl phosphate, dioleyl phosphate, dilinoleyl phosphate, dielidelinoleyl phosphate, dilinolenyl phosphate, diersyl phosphate, or unsaturated phosphate diesters of these alkylene oxide adducts and the like. ;

  For example, triethyl phosphate, tripropyl phosphate, tributyl phosphate, trihexyl phosphate, tri-2-ethylhexyl phosphate, triapril phosphate, tripelargone phosphate, tricaprin phosphate, triundecyl phosphate, tri-2-butyloctyl phosphate. Octyl, trilauryl phosphate, tritridecyl phosphate, trimyristyl phosphate, tripentadecyl phosphate, tripalmityl phosphate, triisocetyl phosphate, triheptadene phosphate, tristearyl phosphate, triisostearyl phosphate, trinonadecyl phosphate, phosphorus Acid triarachidyl, trioctyldodecyl phosphate, triheneicosan phosphate, ditribehenyl phosphate, tri-2-(2-butoxyethoxy)ethyl phosphate, tri-2-(2-methoxyethoxy)ethyl phosphate, or these Phosphoric acid saturated triesters such as alkylene oxide adducts;

  For example, tripalmitoleyl phosphate, trielaidyl phosphate, trioleyl phosphate, trilinoleyl phosphate, trielidolinoleyl phosphate, trilinolenyl phosphate, triercyl phosphate, or unsaturated phosphates such as alkylene oxide adducts thereof. Triester;

  For example, ethylene oxide such as polyoxyethylene oleyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene octyl ether phosphate, and polyoxyethylene decyl ether phosphate. Polyoxyalkylene alkyl ether phosphate having 2 to 20 moles of (EO) added;

For example, polyoxyethylene oleyl phenyl ether phosphate, polyoxyethylene lauryl phenyl ether phosphate, polyoxyethylene cetyl phenyl ether phosphate, polyoxyethylene octyl phenyl ether phosphate, polyoxyethylene decyl phenyl ether phosphate Examples thereof include polyoxyethylene alkylphenyl ether phosphates having an addition mole number of 2 to 20 of ethylene oxide (EO) such as esters and polyoxyethylene ethylphenyl ether phosphates.
The phosphoric acid ester (c2) having 4 to 80 carbon atoms can be used alone or in combination of two or more kinds.

The boric acid ester (c3) having 8 to 100 carbon atoms is an ester compound obtained by dehydration condensation of boric acid and the above-mentioned tetravalent or lower alcohol.
For example, methoxytetraethylene glycol ether borate ester, ethoxytriethylene glycol ether borate ester, ethoxytetraethylene glycol ether borate ester, propoxytriethylene glycol ether borate ester, triethylene glycol monobutyl ether borate ester, diethylene glycol monobutyl ether Boric acid ester, butoxytetraethylene glycol ether boric acid ester, butoxytriethylene glycol ether boric acid ester, butoxytetraethylene glycol ether boric acid ester, butoxypentoxydiethylene glycol ether boric acid ester, pentoxytriethylene glycol ether boric acid ester, 2 -Ethylhexyloxydiethylene glycol ether borate, diethylene glycol monopropyl ether ether borate, triethylene glycol monopropyl ether borate, polyethylene glycol monobutyl ether borate, polyethylene glycol monopropyl ether borate, polyethylene glycol monobutyl ether borate Addition number of ethylene oxide (EO) such as acid ester Polyoxyalkylene alkyl ether borate ester having a mole number of 2 to 20;

  For example, dipropylene glycol monoethyl ether borate ester, dipropylene glycol monopropyl ether borate ester, tripropylene glycol monopropyl ether borate ester, dipropylene glycol monobutyl ether borate ester, tripropylene glycol monoethyl ether borate ester , Tripropylene glycol monopropyl ether borate, tripropylene glycol monobutyl ether borate, polypropylene glycol monopropyl ether borate, polypropylene glycol monobutyl ether borate, etc. A polyoxyalkylene alkyl ether borate ester;

  For example, polybutylene glycol monopropyl ether borate ester, polybutylene glycol monobutyl ether borate ester, and other polyoxyalkylene alkyl ether borate ester having an addition mole number of 2 to 20 of butylene oxide (BO);

  For example, di(glycerin)borate monostearate, di(glycerin)borate sesquistearate, di(glycerin)borate monooleate, polyoxyethylene di(glycerin)borate monopalminate (EO addition mole number: 6 to 20), Examples thereof include glycerin ether borate esters such as polyoxyethylene di(glycerin)borate monooleate (EO addition mole number: 6 to 20). These may 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 within the above range, the compatibility with the polyurethane resin (A) is improved, the transparency and the cohesive force are improved, the removability is improved, and the adherend is less likely to be contaminated.

  The ester compound (C) is preferably contained in an amount of 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polyurethane resin (A). When the ester compound (C) is in the above range, the adhesive layer can be sufficiently plasticized, so that the flexibility is improved, the low adhesive strength is maintained in the slightly viscous region, and the wet spreadability of the pressure-sensitive adhesive film is further improved. .

  Among these, the ester compound (C) is isopropyl myristate, isocetyl myristate, octyldodecyl myristate in addition to industrial availability, wettability, removability, and suppression of adherend contamination. , Methyl oleate, isopropyl oleate, butyl oleate, neopentyl glycol di2-ethylcaproate, polyoxyethylene di2-ethylcaproate, bis{2-(2-butoxyethoxy)ethyl} adipate, adipic acid Bis(2-butoxyethyl), bis(methoxypolyoxyethylene) adipate (EO addition mole number: 2 to 30), diisodecyl adipate, bis(2-ethylhexyl) adipate, neopentyl glycol di-2-ethylcaproate , Fatty acid esters such as di-2-ethylcaproic acid oxyethylene (EO addition mole number: 4 to 16), 2-ethylcaproic acid polyoxyethylene triglyceride (EO addition mole number: 2 to 16), and phosphoric acid tri-2 -Ethylhexyl, trioctyl phosphate, polyoxyethylene oleyl ether phosphate ester (EO addition mole number: 2 to 16), polyoxyethylene lauryl ether phosphate ester (EO addition mole number: 2 to 16), polyoxyethylene octyl ether Phosphoric acid ester such as phosphoric acid ester (EO addition mole number: 2 to 16), triethylene glycol monopropyl ether borate ester, polyethylene glycol monobutyl ether borate ester (EO addition mole number: 2 to 16), poly Oxyethylene glycerin ether borate ester (EO addition mole number: 2 to 16) is preferable.

<Ionic compound (D)>
The pressure-sensitive adhesive of the present invention may further contain an ionic compound (D).
The ionic compound (D) is a liquid or solid ionic compound at room 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) also include surfactants, ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate and the like. 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 portion composed of Li ⁺ , Na ⁺ and K ⁺ and various anion portions. Depending on the type of anion part, it is classified into inorganic salts and organic salts. Examples of the inorganic salts of alkali metals 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 viewpoint of conductivity and safety, sodium chloride, potassium chloride, lithium perchlorate and the like are preferable.

The alkali metal organic salts, e.g., sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene _{sulfonate, 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. Among _{these, 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) A fluorine-containing lithium imide salt such as ₅ SO ₂ )IN, particularly a (perfluoroalkylsulfonyl)imide lithium salt is preferable.

  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. The cation component is, for example, 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, a pyrazolium. Examples thereof include cations, pyrazolinium cations, tetraalkylammonium cations, trialkylsulfonium cations and tetraalkylphosphonium cations.

The anion component may be any liquid ionic compound that can be generated, 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, the anion 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, and 1-butyl-3-methylpyridinium trifluoromethanesulfonate. -Butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl)imide, 1-hexylpyridinium tetrafluoroborate, 2-methyl-1-pyrroline tetrafluoro Borate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, 1-ethylcarbazole tetrafluoroborate, 1-ethyl-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 perfluorobutane sulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(penta Fluoroethanesulfonyl)imide, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl)methide, 1-butyl-3-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 perfluorobutane Sulfonate, 1-Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium bromide, 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, tetrahexyl ammonium Bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis(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 trifluoride Methane sulfonate, glycidyl trimethyl ammonium bis (trifluoromethane sulfonyl) imide, glycidyl trimethyl ammonium bis (pentafluoroethane sulfonyl) imide, 1-butylpyridinium (trifluoromethane sulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethane Sulfonyl)trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl)trifluoroacetamide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (trifluoromethanesulfonyl)trifluoro Acetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, 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,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-hexyl ammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-heptyl ammonium 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(trifluoromethane) Sulfonyl)imide, N,N-dimethyl-N,N-dihexylammonium bis(trifluoromethanesulfonyl)imide, trimethylheptyl ammonium 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)imide , N,N-diethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, triethylpropylammonium bis(trifluoromethanesulfonyl)imide, triethyl Pentyl ammonium bis(trifluoromethanesulfonyl)imide, triethylheptyl ammonium 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-hexylammonium bis(trifluoromethanesulfonyl) Imide, trioctylmethylammonium bis(trifluoromethanesulfonyl)imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluoro) Examples thereof include sulfonyl)imide.

The ionic compound (D) is preferably contained in 0.001 to 20 parts by weight with respect to 100 parts by weight of the polyurethane resin (A). Within the above range, a sufficient antistatic function is exhibited, and whitening and bleeding out of the adhesive layer can be suppressed.
The ionic compound (D) can be used alone or in combination of two or more kinds.

  The pressure-sensitive adhesive of the present invention may further contain a compound (E) selected from the group consisting of an ultraviolet ray shielding agent, an antioxidant, a light stabilizer, and an optical brightener.

Here, the ultraviolet shielding agent is a compound that generally absorbs ultraviolet rays having a wavelength of about 200 to 380 nm, converts them into energy such as heat and infrared rays, and emits them.
The ultraviolet shielding agent includes an inorganic compound and an organic compound. Examples of the inorganic compound include fine particles of metal oxides 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.
Examples of the organic compound include 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.

  Examples of the benzotriazole type include 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6[(2H-benzotriazol-2-yl)phenol]], 2-(2H-benzo. Triazol-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.

  Triazine-based compounds 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) -Dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and the like.

  Examples of the benzophenone type include diphenylmethanone, methyldiphenylmethanone, 4-hydroxydiphenylmethanone, 4-methoxydiphenylmethanone, 4-octoxydiphenylmethanone, 4-decyloxydiphenylmethanone, 4-dodecyloxy. Diphenylmethanone, 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 can be mentioned.

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

  Examples of the salicylate ester-based agent include isocetyl salicylate, octyl salicylate, glycol salicylate, and phenyl salicylate.

  The cinnamic acid type is, for example, ethylhexylmethoxycinnamate, isopropylmethoxycinnamate, isoamylmethoxycinnamate, diisopropylmethylcinnamate, glyceryl-ethylhexanoate dimethoxycinnamate, methyl-α-carbomethoxycinnamate, methyl-α- Cyano-β-methyl-p-methoxycinnamate and the like can be mentioned.

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

  Oxalinide compounds include, 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′-ethoxyoxanilide and the like can be mentioned.

  Examples of the coumarin derivative system include 7-hydroxycoumarin.

  Examples of the anthranilate system include compounds such as methylanthranilate.

  Examples of the resorcinol-based compound include compounds such as dibenzoylresorcinol and bis(4-tert-butylbenzoylresorcinol).

Benzoxazine-based compounds include 3-methyl-2-(2-(1-methyl-2,5-diethyl-1H-pyrrol-3-yl)ethenyl)-benzoxazolium chloride,
3-ethyl-2-(2-(1-ethyl-2,5-dimethyl-1H-pyrrol-3-yl)ethenyl)-benzoxazolium chloride and the like can be mentioned.

  Examples of the benzalmalonate system include dimethicodiethylbenzalmalonate.

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

  Antioxidants are antioxidants that are added to suppress the oxidation of components. For example, phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. may be mentioned.

Examples of phenolic antioxidants include monophenolic, bisphenolic, and polymeric phenolic antioxidants.
Examples of the monophenol antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β-(3,3. 5-di-t-butyl-4-hydroxyphenyl)propionate and the like can be mentioned.

  Examples of the bisphenol antioxidant include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis. (3-Methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3- t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5.5]undecane and the like.

  Polymeric phenolic antioxidants include, for example, 1,1,3-tris(2-methyl-4-hydroxy-5-t-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-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-based antioxidants include triphenyl phosphite, trisnonylphenyl 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.
Of these, phosphorus-based antioxidants are preferable because they are difficult to color.
The antioxidants can be used alone or in combination of two or more kinds.

The light stabilizer is a compound that reduces auto-oxidative decomposition due to radicals generated by light energy and suppresses resin deterioration.
The light stabilizer is preferably a hindered amine compound (hereinafter abbreviated as "HALS"), a hindered phenol compound, and 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 thereof include polycondensates of 1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine.

  Examples of the hindered phenol-based compound 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-dodecylthionitoxycarbonyl)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′-hydroxy-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 can be mentioned. The hindered phenolic compound can also be used as a phenolic antioxidant.

The fluorescent whitening agent is a kind of dye, and is a compound that absorbs ultraviolet rays and converts it into pale light (fluorescence) to increase whiteness.
Examples of the fluorescent whitening agent include benzoxazole-based, triazine-based, pyrazoline-based and coumarin-based compounds.

  The compound (E) may be contained in an amount of 0.001 to 20 parts by weight based on 100 parts by weight of the polyurethane resin (A). When the compound (E) is used in an appropriate range, for example, 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 (F).
When the hydrolysis inhibitor (F) is contained, the polyurethane resin (A) can block the carboxyl groups generated when hydrolysis occurs in a high temperature and high humidity atmosphere.
The hydrolysis inhibitor (F) is preferably, for example, a carbodiimide-based, isocyanate-based, oxazoline-based, or epoxy-based agent, and a carbodiimide-based agent is preferable because hydrolysis can be suppressed more effectively.
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, and even more preferably 0.1 to 2.0 parts by weight based on 100 parts by weight of the polyurethane resin (A). More preferably, it is from 05 to 1.0 parts by weight.
The hydrolysis inhibitor (F) can be used alone or in combination of two or more kinds.

  Incidentally. The hydrolysis inhibitor (F) is preferably used in combination with the compound (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 the hydrolysis inhibitor and the antioxidant together, the hydrolysis resistance is further improved, and the decomposition and thermal yellowing of the hydrolysis inhibitor itself can be suppressed.

The carbodiimide-based hydrolysis inhibitor is a compound having a carbodiimide group.
Examples of the monocarbodiimide compound include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide and naphthylcarbodiimide.
The polycarbodiimide compound is a high molecular weight polycarbodiimide produced by a decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst.
The polycarbodiimide compound is, for example, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether. Diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4 Examples thereof include'-dicyclohexylmethane diisocyanate and tetramethylxylylene diisocyanate. The carbodiimidization catalyst is 1-phenyl-2-phospholen-1-oxide, 3-methyl-2-phospholen-1-oxide, 1-ethyl-3-methyl-2-phospholen-1-oxide, 1-ethyl. Examples thereof include 2-phospholen-1-oxide and phospholene oxides such as 3-phospholene isomers thereof.

The pressure-sensitive adhesive of the present invention may contain other components as long as the problems can be solved.
Other components include, for example, organic reduction from the viewpoints of reduction in shrinkage due to polymerization, reduction in coefficient of thermal expansion, improvement in dimensional stability, improvement in elastic modulus, viscosity adjustment, improvement in thermal conductivity, improvement in strength, improvement in toughness, and improvement in coloring. Alternatively, an 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. Further, a flexibility imparting agent, a plasticizer, a flame retardant, a storage stabilizer, an antioxidant, an ultraviolet absorber, a thixotropy imparting agent, a dispersion stabilizer, a fluidity imparting agent, a tackifier and a defoaming agent are added. The method can also be dissolved, semi-dissolved or microdispersed in the pressure sensitive adhesive as a polymer blend or polymer alloy.

<Pressure sensitive adhesive>
The pressure-sensitive adhesive is also called a pressure-sensitive adhesive, and is an adhesive that adheres only by 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.
The polyurethane resin (A) contains a polyol (a1) unit and a polyisocyanate (a2) unit as monomer units constituting the polyurethane resin (A), and the polyurethane resin (A) has a carbonate structure in its main chain and has an aromatic ring. It has a weight average molecular weight of 10,000 to 500,000, 10,000 to 500,000 and does not have 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). It contains 1 to 50 parts by weight.

  The pressure-sensitive adhesive of the present invention preferably has its viscosity appropriately adjusted depending on the usage form. The pressure-sensitive adhesive of the present invention can use an organic solvent to adjust the viscosity. Examples of the organic solvent include alcohol solvents such as methanol, ethanol, and isopropyl alcohol, but solvents having no active hydrogen capable of reacting with the above-mentioned reactive compound (B), such as acetone, methyl ethyl ketone, and methyl isobutyl. Various organic solvents such as ketone solvents such as ketones, ester solvents such as methyl acetate, ethyl acetate and butyl acetate, and hydrocarbon solvents such as cyclohexane, toluene and xylene are more preferable. It is also possible to reduce the viscosity by heating the pressure sensitive adhesive without the use of additional solvent.

  The pressure-sensitive adhesive of the present invention preferably has a viscosity of 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. More preferably, it is 1,000 to 8,000 mPa·s. When the viscosity is 10,000 mPa·s or less, 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. Further, when the viscosity is 3,000 mPa·s or more, it is easy to control the thickness of the adhesive layer.

<Method for manufacturing pressure-sensitive adhesive>
As the method for producing the pressure-sensitive adhesive, first, after producing the polyurethane resin (A), optional components are mixed to contain the reactive compound (B) having a functional group capable of reacting with the hydroxyl group. It can be a pressure sensitive adhesive.
The production of the pressure-sensitive adhesive is carried out by reacting the polyol (a1) and the polyisocyanate (a2) with the first step of producing the polyurethane resin (A), and the second step of mixing the polyurethane resin (A) with an arbitrary component. It is obtained by mixing the mixture obtained in the above step and the second step with the reactive compound (B) having a functional group capable of reacting with a hydroxyl group. The second step can be omitted when the optional components are not mixed.

<Method for producing polyurethane resin (A)>
The first step of 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 by various methods, but is roughly classified into the following two methods.
[I] A method in which the polyol (a1), the 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, polyisocyanate (a2) is added dropwise, and then a catalyst is additionally added as needed.
[Ii] is preferable when the reaction is precisely controlled. The reaction temperature is preferably 120°C or lower, more preferably 50 to 100°C. When the reaction is carried out at a predetermined temperature, the reaction rate is easily controlled and the polyurethane resin (A) having a predetermined weight average molecular weight and structure is easily obtained. The urethanization reaction is preferably carried out 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 such that the polyurethane resin (A) needs to have at least one hydroxyl group. It is necessary that the isocyanate group in (a2) is less than 1 mol, preferably 0.5 to 0.95 mol, more preferably 0.6 to 0.9 mol. Within this range, the reactivity with the reactive compound (B) is improved, an adhesive layer with high transparency is easily obtained, the adhesion to the curved surface part is improved, and contamination of the adherend during peeling can be suppressed. ..
The end point of the synthesis reaction is judged by measuring the isocyanate content (% by weight) by titration, or by disappearing the characteristic absorption based on the isocyanate group (NCO) by measuring the infrared absorption spectrum (IR). Details of the method for measuring the isocyanate content by titration will be described in Examples.

  The above-mentioned catalyst (preferably an organometallic compound) can be used during the production of the polyurethane resin (A). The reaction between the isocyanate group and the hydroxyl group is originally fast, but in the presence of a catalyst, the reaction may be further promoted, which may make control difficult. At this time, if 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, polyaminooxy acids such as ethylenediaminetetraacetic acid (alias: EDTA), oxycarboxylic acids such as citric acid, condensed phosphoric acid, and the like. Among these, acetylacetone is preferable because it is soluble in an organic solvent and has volatility.

  Since the chelate compound remains in the pressure-sensitive adhesive, it also acts on the reaction between the polyurethane urea resin (A) and the reactive compound (B) to adjust the reaction rate, resulting in storage stability. An excellent pressure sensitive adhesive is obtained.

An organic solvent can be used for producing the polyurethane resin (A). The use of an organic solvent facilitates reaction control. 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, and 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, methyl Cyclohexanone, ketones such as isophorone, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, esters such as 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 monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether, etc. Glycol and glycol 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 Ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomer Glycol acetate such as chill ether acetate, saturated hydrocarbon such as n-hexane, isohexane, n-nonane, isononane, dodecane and isododecane, unsaturated hydrocarbon such as 1-hexene, 1-heptene and 1-octene, cyclohexane, cyclo Cyclic saturated hydrocarbons such as heptane, cyclooctane, cyclodecane, and decalin, cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, cyclounsaturated hydrocarbons such as cyclododecene, benzene, toluene, In addition to aromatic hydrocarbons such as xylene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide and the like can be mentioned.
Among these, ethyl acetate, toluene, and methyl ethyl ketone are preferable from the viewpoint of the solubility of the polyurethane resin (A) and the boiling point of the solvent.

The blending amount of the organic solvent may be appropriately determined in consideration of the composition of the polyurethane resin (A), the viscosity, the concentration of nonvolatile components, and the like. The concentration other than the organic solvent at the time of synthesizing the polyurethane resin (A) is preferably 50 to 100% by weight, more preferably 60 to 95% by weight. When the concentration is within the predetermined range, the reactivity is improved.
The organic solvent may be used alone or in combination of two or more kinds.

The second step will be described.
The pressure-sensitive adhesive of the present invention can be prepared by blending the polyurethane resin (A) with optional components and mixing with a mixer such as a Henschel mixer, a disper, an attritor, a high speed mixer, or a homomixer. When mixing, an organic solvent can be appropriately used together.

The third step will be described.
After the second step, the pressure-sensitive adhesive of the present invention is further mixed with a reactive compound (B) and mixed with a mixer such as a Henschel mixer, a disper, an attritor, a high speed mixer, or a homomixer. can do. At the time of mixing, air bubbles and foaming contained in the pressure-sensitive adhesive can be removed by vacuum deaeration, and unexpected foreign matters can be removed by filtration or the like, if necessary.
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 a part of the reaction proceeds), and after applying the pressure-sensitive adhesive to the substrate, it reacts during heating and drying to bond while forming a cross-linked coating film. Performance may be exhibited. The timing of mixing is also not particularly limited, and after applying one of the polyurethane resin (A) and the reactive compound (B) to the surface of the base material, the other is separately applied, and the reaction is performed during heating and drying. May proceed. Alternatively, the polyurethane resin (A) and the reactive compound (B) may be coated on different substrate surfaces, the coated surfaces may be bonded together, and then heat-dried to allow the reaction to proceed. It is preferable to apply a pressure-sensitive adhesive, which is a mixed liquid of the polyurethane resin (A) and the reactive compound (B), onto a base material and to crosslink and cure by heating to form an adhesive layer. The surface of the adhesive layer has removable tackiness.

<Pressure sensitive adhesive film>
Next, the pressure sensitive adhesive film will be described.
The pressure-sensitive adhesive film of the present invention (hereinafter referred to as an adhesive film) includes a substrate and an adhesive layer which is a cured product of the pressure-sensitive adhesive. The surface of the adhesive layer that is not in contact with the base material is generally laminated with a film-like base material (also referred to as a release liner) whose surface has been subjected to a release treatment just before use.
The adhesive film can be produced, for example, by applying a pressure-sensitive adhesive to the release-treated surface of the release liner, drying it, and bonding the base material together, or by directly applying the pressure-sensitive adhesive to a base material other than the release liner. Examples include a method of coating and drying, and a method in which a release-treated surface of a release liner is attached to the surface of the adhesive layer to prepare.
Examples of the constitution of the adhesive film include base material/adhesive layer (single-sided adhesive film), adhesive layer/base material/adhesive layer (double-sided adhesive film), release liner/adhesive layer/release liner.

The method for applying the pressure-sensitive adhesive is not particularly limited. For example, various known methods such as Meyer 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.
The drying temperature is usually about 50 to 200°C.

  The thickness of the adhesive layer is usually about 0.5 to 300 μm, preferably 1 to 100 μm.

Examples of the base material include wood, metal, plastic, glass plate, paper, synthetic paper, and non-woven fabric.
The plastic is preferably a film or plate, more preferably a film.
Examples of the plastic film include a polyvinyl alcohol film (also called PVA film), a polytriacetyl cellulose film (also called TAC film), a polypropylene film (also called PP film), a polyethylene film (also called PE film), a polycycloolefin film ( COP film), a film of a polyolefin resin such as an ethylene-vinyl acetate copolymer film (also called an EVA film), a polyethylene terephthalate film (also called a PET film), a polybutylene terephthalate film (also called a PBT film), etc. Polyester-based resin film, polycarbonate-based resin film (also referred to as PC film), polynorbornene-based resin film, polyarylate-based resin film, polyacrylic acid ester-based resin film, polyphenylene sulfide resin film (also PPS film) Examples thereof include a polystyrene resin film (also referred to as a PST film), a polyamide resin film (also referred to as a PA film), a polyimide resin film (also referred to as a PI film), and an oxirane resin film.
Among the plastic films, a transparent film such as a PVA film, a TAC film, a COP film, a polyester resin film, and a PC film is more preferable.
Examples of the glass plate include general soda glass, and surface glass of liquid crystal cells, displays, and touch panels.
The base material may be used alone or as a laminate.

The substrate can be improved in adhesion with the adhesive layer by subjecting the surface of the substrate to an easy-adhesion treatment.
The easy adhesion treatment is preferably dry treatment, wet treatment, or physical treatment, for example.
Examples of the dry treatment include corona discharge, plasma treatment, flame treatment and the like.
The wet treatment includes, for example, a method of modifying the surface with acid or alkali.

The base material can be given a physical treatment or an optical function, for example.
Examples of the optical function include light transmission, light diffusion, light collection, refraction, light scattering, and haze. Examples of the method of imparting an optical function include a method of kneading a compound expressing the optical function into a film, and a method of forming a functional layer containing the compound on a transparent film.
Examples of the physical treatment include a method of forming irregularities on the surface and a method of forming a metal film by vapor deposition or sputtering of a metal oxide. Examples of the metal oxide include oxides of silicon, aluminum, magnesium, calcium, potassium, tin, sodium, boron, titanium, lead, zirconium, yttrium, and other metals.

  The surface of the base material that does not come into contact with the adhesive layer can be subjected to known release (release) treatment.

  The thickness of the base material is preferably about 5 μm to 300 μm, more preferably 15 μm to 150 μm.

The release liner can use the base material described above as the base material.
For the release treatment of the release liner, for example, a silicone compound or a fluorine compound can be used.

The adhesive film can be used, for example, for permanent adhesion and re-peeling, but re-peeling is preferable, and surface protection is more preferable. When the adhesive film is used for surface protection, it has excellent removability, and after being exposed to a high-temperature environment or a high-temperature and high-humidity environment, it is difficult to lift or peel off from the adherend.
Examples of the adherend include metal, plastics, and glass.

  When the adhesive film is used for the purpose of protecting the surface of an optical member or an electronic member, for example, it is possible to perform an inspection with the adhesive film attached to an adherend. The haze of the adhesive film (also referred to as a surface protection film) of the present invention is preferably 5% or less, more preferably 2% or less. The details of the haze measurement will be described in Examples.

  The adhesive film can be preferably used, for example, as a liquid crystal display, a plasma display, a touch panel, a member related to various electronic parts such as an electrode peripheral member, a surface protective film, a glass member such as a building material and a window glass of a vehicle, and the like. It can also be used for plastics such as acrylic, cardboard, wood, plywood, metals such as stainless steel and aluminum.

The optical layered body of the present invention includes an optical film, an adhesive layer that is a cured product of a pressure-sensitive adhesive, and a glass plate.
As the optical film, the optical film is preferably the transparent film or a transparent film provided with an optical function. The transparent film is more preferably a polyester resin film. Physical processing or optical function can be imparted to the transparent film. The optical film can be used alone or by appropriately selecting a laminate.
The glass plate is preferably the glass described above.
The thickness of the glass plate is usually about 10 μm to 5 mm.

  In the optical layered body of the present invention, the optical film and the adhesive film including the adhesive layer, which is a cured product of the pressure-sensitive adhesive, can be peeled from the glass plate. On the other hand, it goes without saying that the adhesive film does not have to be peeled from the glass plate depending on the mode of use.

  Hereinafter, specific examples of the present invention will be described 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 urea resin>
(Synthesis example 1)
The following monomers {polyol (a1), polyisocyanate (a2)}, catalyst are used in the reaction tank and the dropping device of the polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introducing pipe. , And an organic solvent were charged at the following ratios.

[Polymerization tank]
C-1015N(a1-5) 11.66 parts EXCENOL820(a1-2) 84.66 parts Toluene (organic solvent) 30.00 parts Dioctyltin dilaurate (catalyst) 0.016 parts [Dripping device]
HDI (a2) 3.67 parts Ethyl acetate (organic solvent) 12.88 parts

After replacing the air in the polymerization tank with nitrogen gas, the temperature was raised to 80° C. under stirring in a nitrogen atmosphere, and the mixture containing 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 disappeared, 6 parts of acetylacetone and 17.2 parts of ethyl acetate were added to adjust the nonvolatile concentration to 60%, The reaction was completed by cooling to 25°C. This polyurethane resin (A) solution had a solution viscosity (Vis) of 7,500 mPa·s (25° C.) and a weight average molecular weight (Mw) of 270,000.

(Synthesis examples 2 to 16)
Polyol (a1), polyisocyanate (a2), toluene (organic solvent), and the catalyst listed in Table 1 were all charged into a polymerization tank, and polyisocyanate (a2) and ethyl acetate (organic solvent) were added to a dropping device. A polyurethane resin (A) was synthesized in the same manner as in Synthesis Example 1 except that the charging was changed. The compounds used as monomers shown in Table 1 represent the total value (parts) of the amount charged into the polymerization tank and the amount charged into the dropping device.
However, in Synthesis Examples 26 and 27, the polyisocyanate (a2) was changed to IPDI and TDI, respectively. Further, in Synthesis Example 30, the catalyst was changed to DBU.

  The solution appearance (25° C.), solution viscosity (Vis), and weight average molecular weight (Mw) of the resulting polyurethane resin solution were determined according to the methods described below, and the results are shown in Table 1. In addition, a method for measuring the acid value (AV), hydroxyl value (OHV), residual amount (%) of isocyanate group (NCO), and glass transition temperature (Tg) is also described.

<Appearance of solution>
The solution 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 urea resin was measured at 25° C. with a B-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) under the conditions of rotation speed of 0.5 to 100 rpm and rotation for 1 minute to obtain a solution viscosity (mPa).・S).

<<Average molecular weight>>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography). The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined by using the converted value of polystyrene as a standard substance.
Device name: Showa Denko GPC (gel permeation chromatography) "Shodex GPC System-21"
Column: Tohso GMHXL: 4 and Tosoh HXL-H: 1 These were connected in series.
Mobile phase solvent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml/min Column temperature: 40°C

<<Hydroxyl value (OHV)>>
About 1 g of the sample was precisely weighed in a ground-in stopper Erlenmeyer flask, and 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution was added and dissolved. Next, 5 ml of an acetylating agent (25 g of acetic anhydride dissolved in pyridine to a volume of 100 ml) was added, and the mixture was stirred for 1 hour. To this, phenolphthalein reagent solution was added as an indicator and held for 30 seconds. Then, the solution was titrated with a 0.1N alcoholic potassium hydroxide solution until it turned pink.
The hydroxyl value was calculated by the following formula. The hydroxyl value was the numerical value of the dry state of the resin (unit: mgKOH/g).
Hydroxyl value (mgKOH/g)=[{(ba)×F×28.25}/S]/(nonvolatile component concentration/100)+D
However, S: sampling amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Empty experiment consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution D: acid value (mgKOH/g)

<Acid value (AV)>
About 1 g of a sample was precisely weighed in a ground-in stopper Erlenmeyer flask, and 100 ml of a toluene/ethanol (volume ratio: toluene/ethanol=2/1) mixed solution was added and dissolved. To this, a phenolphthalein reagent solution was added as an indicator, held for 30 seconds, and then titrated with a 0.1N alcoholic potassium hydroxide solution until the solution became pink.
The acid value was calculated by the following formula. The acid value is the numerical value of the dry state of the resin (unit: mgKOH/g).
Acid value (mgKOH/g)={(5.611×a×F)/S}/(nonvolatile matter concentration/100)
However, S: sampling amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: titer of 0.1N alcoholic potassium hydroxide solution

<<Residual amount (%) of isocyanate group (NCO)>>
About 1 g of the sample was precisely weighed in a ground-in stopper Erlenmeyer flask, and 25 ml of chlorobenzene and di-n-butylamine/o-dichlorobenzene (weight ratio: di-n-butylamine/o-dichlorobenzene=1/24.8). Add 10 ml of the mixed solution and dissolve. To this, 80 g of methanol and bromphenol blue reagent were added as indicators, and titrated with a 0.1N alcoholic hydrochloric acid solution. Titration was continued until the solution turned yellow green and was held for 30 seconds. The NCO residual amount (%) was calculated by the following formula.
NCO residual amount (%)=[0.42×(B−C)×F]/S
However, S: sampling amount (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 in blank test (ml)
F: titer of 0.1N alcoholic hydrochloric acid solution

<Glass transition temperature (Tg)>
A robot DSC (differential scanning calorimeter, “RDC220” manufactured by Seiko Instruments Inc.) was connected to an “SSC5200 disk station” (manufactured by Seiko Instruments Inc.) and used for measurement.
Approximately 10 mg of the sample was placed in an aluminum pan, weighed and set in a differential scanning calorimeter, and the same type of aluminum pan without the sample was used as a reference, and the sample was held at a temperature of 100° C. for 5 minutes, followed by using liquid nitrogen. Quenched to 120°C. Then, the temperature was raised at a temperature rising rate of 10° C./min, and the glass transition temperature (Tg, unit:° C.) was determined from the obtained DSC chart.

The abbreviations of the materials used in Synthesis 1 to 30 are shown below. In addition, in Table 1, a blank column means no compounding. The unit of the hydroxyl value and the acid value (mgKOH/G) is omitted.
-Aliphatic polyol (a1-1)
BEPG: 2-butyl-2-ethyl-1,3-propanediol, ODD: 1,12-octadecanediol/polyether polyol (a1-2)
PEG1000: PEG1000 (Mn=1,000, hydroxyl value=112, acid value<0.5, linear wax type, diol) [manufactured by Sanyo Chemical Industries], PP-1000: Newpol PP-1000 (Mn=1) 2,000, hydroxyl value=112, acid value<0.5, linear liquid type, diol) (manufactured by Sanyo Chemical Industry Co., Ltd.), PP-2000: Newpol PP-2000 (Mn=2,000, hydroxyl value=56, Acid value <0.5, linear liquid type, diol) (manufactured by Sanyo Kasei Co., Ltd.), G3000: ADEKA POLYETHER G-3000B (Mn=3,000, hydroxyl value=56, acid value<0.5, linear liquid Type, triol) [manufactured by Adeka], GP4000: Newpol GP-4000 (Mn=4,000, hydroxyl value=28, acid value<0.5, linear liquid trifunctional type) [manufactured by Sanyo Chemical Industries], E820: EXCENOL820 (Mn=4,900, hydroxyl value=34, acid value<0.05, linear liquid trifunctional type) [manufactured by Asahi Glass Co., Ltd.], G-750: UNIOX G-750 (Mn=750, hydroxyl value) =224, acid value <0.05, linear liquid trifunctional type)
-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], P1011: Kuraray polyol P1011 (Mn=1,000, hydroxyl value) =112, acid value <0.5, linear liquid type, aromatic diol) (manufactured by Kuraray Co., Ltd.), Y202: URICY-202 (Mn=980, hydroxyl value=115, acid value<1.0, linear liquid type) , Diol) [made by Ito Oil Co., Ltd.]
・Polyamide polyol (a1-4)
TPAE: TPAE617 (Mn=15,000, hydroxyl value=16, acid value=1, linear type, diol) [manufactured by Fuji Chemical Industry 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], C1090: Kuraray polyol C-1090 (Mn=1, 000, hydroxyl value=112, acid value<0.5, linear liquid type), T6001: Duranol T6001 (Mn=1,000, hydroxyl value=110, acid value<0.05, linear liquid type) [Asahi Kasei Chemicals Corporation Made)
・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 resins obtained in the above synthesis examples, pressure sensitive adhesives were prepared by the following methods.
(Examples 1 to 108, Comparative Examples 1 to 10)
According to the weight ratio (parts) of the obtained polyurethane resin (A) and the reactive compound (B) shown in Table 2, 100 parts of the polyurethane resin was used, and other materials were listed in Table 2 as needed. The pressure-sensitive adhesive was obtained by blending in a weight ratio (parts) and adjusting the nonvolatile concentration to 60% by adding ethyl acetate as an organic solvent. The obtained pressure-sensitive adhesive was applied to each base material, dried, cured and bonded to prepare an adhesive film, which was evaluated by the following methods. The respective results are shown in Table 3.

<<Evaluation of pot life>>
About the obtained pressure sensitive adhesive, after compounding, the viscosity at 25° C. was set every 1 hour until 8 hours later, using a B-type viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.), rotor M3, 25° C., 12 rpm. The measurement was carried out under the condition of rotation for 1 minute, and the pot life was evaluated in 3 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 increase rate up to 8 hours is 50% or more and less than 100%. Practically usable x: Separation or turbidity of the solution layer occurs, gelation occurs, or viscosity increase rate is 100% or more in less than 8 hours. Not practical.
Here, the viscosity increase rate was calculated by the following method.
Viscosity increase rate (%)=100×{(viscosity after storage for 8 hours)-(viscosity immediately after adjustment)}/(viscosity immediately after adjustment)

<<Evaluation of coatability>>
The obtained pressure-sensitive adhesive was used as a substrate on a release-treated polyethylene terephthalate film having a thickness of 38 μm (Cerapeal MF: manufactured by Toray Film Co., Ltd.) (hereinafter, referred to as “release liner”), and the thickness after drying. Having a thickness of 25 μm and dried with hot air at 100° C. for 2 minutes to form an adhesive layer. Then, a 100 μm thick polyethylene terephthalate film (PET film) was attached to the coated surface to prepare an adhesive film composed of 100 μm thick PET film/adhesive layer/release liner. Then, the state of the adhesive layer surface (coated surface) after the release liner was peeled off was visually observed and evaluated in three levels. 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. Practically usable.
Poor: Repelling, foaming and streaking were observed on the coated surface. Not practical.

<<Evaluation of optical characteristics>>
The pressure-sensitive adhesive thus obtained 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. Then, a separately prepared release liner was attached to the adhesive layer to prepare an adhesive film in which the adhesive layer was sandwiched by the release liner, and cured at 23° C. and 50% relative humidity for 7 days.
Next, both release liners were removed, the appearance of the adhesive layer alone was visually judged, and the haze was measured by "NDH-300A (Nippon Denshoku Industries Co., Ltd.)". In the case of “○” or “△” evaluation, there is no problem in actual use.
◯: Haze is not observed, and Haze is less than 0.5. Good.
B: Haze: 0.5 or more and less than 2, although no cloudiness is observed, practically usable.
X: Haze is observed, or Haze: 2 or more. Not practical.

<Evaluation of workability>
The adhesive film produced by the same method as the above-mentioned “Evaluation of coatability” was aged for 7 days in an environment of 23° C. and 50% relative humidity. After that, it was cut into a width of 100 mm and a length of 100 mm, 20 sheets of this were stacked, and the state of the adhesive layer protruding from the edge of the adhesive film when pressed for 1 hour under the condition of 40° C.-60 Kg/cm ² was as follows. It was evaluated in three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
◯: No protrusion of the adhesive layer is observed. Good.
Δ: Adhesive layer protrusion of less than 0.3 mm is observed, but it can be used practically.
X: The protrusion of the adhesive layer of 0.3 mm or more is observed. Not practical.

<<Evaluation of wettability>>
Apply the obtained pressure-sensitive adhesive to a polyethylene terephthalate film (PET film) having a thickness of 50 μm as a base material so that the thickness after drying becomes 15 μm, and dry with hot air at 100° C. for 2 minutes. Then, the adhesive layer was formed. Then, a 38 μm release liner (Cerapeal MF: manufactured by Toray Film Co., Ltd.) is attached to the coated surface to prepare an adhesive film having a constitution of 50 μm thick PET film/adhesive layer/release liner, and 23° C. and 50% relative humidity. It was cured in the environment for 7 days. Then, this adhesive film was cut into a width of 100 mm and a length of 100 mm to obtain a measurement sample. Next, a float glass plate having a thickness of 2 mm, a width of 150 mm, and a length of 150 mm was brought into contact with only one side of the adhesive layer from which the release liner of the adhesive film had been peeled off, in a state of being inclined at 45° to the float glass plate, and then the hand The time (seconds) required for the entire surface of the sample to come in contact with the glass plate (to spread on the glass plate) was evaluated as the wet spreadability in the following three stages. In the case of “○” or “△” evaluation, there is no problem in actual use.
◯: Wet spreading time is less than 2 seconds. Good.
Δ: Wetting and spreading time is 2 seconds or more and less than 4 seconds. Practically usable.
×: Wet spreading time is 4 seconds or more. Not practical.

<<Measurement of peel strength>>
The adhesive film prepared by the same method as the above-mentioned “Evaluation of wettability” is cut into a width of 25 mm and a length of 100 mm, the release liner is peeled off, and the exposed adhesive layer is formed into a 1.2 mm-thick non-alkali glass plate. It was attached using a laminator in an environment of 23° C. and 50% relative humidity. Then, it was kept in an autoclave under conditions of 50° C. and 5 atm for 20 minutes to obtain a measurement sample. After leaving the measurement sample at 23° C. for 1 day, at a temperature of 23° C. and a relative humidity of 50%, using a tensile tester (“Tensilon” manufactured by Orientec Co., Ltd.), a peeling speed of 300 mm/min and a peeling angle. The peel strength was measured under the condition of 180 degrees (measurement of peel strength one day after lamination). Further, the measurement sample was left in an environment of 23° C. and a relative humidity of 50% for 14 days, and then the peeling strength was measured by the same method (peeling strength measurement 14 days after bonding). The peel strength was evaluated as an adhesive strength in three levels. In the case of “○” or “△” evaluation, there is no problem in actual use.
◯: Peel strength is less than 10.0 (mN/25 mm). Good.
Δ: Peel strength is 10.0 (mN/25 mm) or more and less than 15.0 (mN/25 mm). Practically usable.
X: Peel strength is 15.0 (mN/25 mm) or more. Not practical.

<<Evaluation of removability (reworkability)>>
The adhesive film prepared by the same method as the above-mentioned “Evaluation of wettability” was cut into a size of 25 mm×150 mm, the release liner was peeled off, and affixed to a float glass plate having a thickness of 2 mm using a laminator, 50 It was kept in an autoclave under the condition of 5° C. for 20 minutes to obtain an optical laminate of an adhesive film and a glass plate.
The adhesive film of this laminate was peeled off in the direction of 180 degrees at a speed of 50 mm/min, and the cloudiness of the glass surface after peeling was visually observed and evaluated in three levels. 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 problem in practical use. Good.
X: Transfer of the pressure-sensitive adhesive was observed on the entire surface, which is not practical.

<Durability (heat resistance, moist heat resistance) evaluation>
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. Then, the release liner of the adhesive film was peeled off, and the exposed adhesive layer was applied to one side of a 1.2 mm-thick non-alkali glass plate under a pressure of 5 kg/cm ^{2 in} an atmosphere of 50° C. and kept in the autoclave for 20 minutes. After bonding, they were left in an atmosphere of 80° C. for 500 hours. After being left standing, the temperature was returned to 25° C., the floating/peeling of the adhesive film, and the state of foaming were visually observed, and evaluated in three levels.
As a moist heat resistance test, a sample was prepared in the same manner as the heat resistance test, and left in a constant temperature and humidity bath at 60° C.-90% relative humidity for 500 hours. After being left standing, the temperature was returned to 25° C., the floating/peeling of the adhesive film, and the state of foaming were visually observed, and evaluated in three levels. 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 edges).
Floating/peeling is a state in which the polarizing film adhesive film is lifted from the glass and peeled off.
The respective evaluation criteria are as follows.
◯: No foaming, floating or peeling occurred. Good.
Δ: A slight occurrence of foaming, floating, or peeling with a diameter of 0.5 mm or less is recognized, but it is practically usable.
X: Significant occurrences such as foaming, floating, and peeling are recognized on the entire surface. Not practical.

Materials used in Examples and Comparative Examples are shown below. In Table 2, the blank column means no compounding.
-Polyurethane resin Compound obtained in each synthesis example described in Table 1 (Synthesis examples 1 to 30)
.Reactive compound (B) having a functional group capable of reacting with a hydroxyl group
HDI/TMP: hexamethylene diisocyanate trimethylolpropane adduct, HDI/Nu: hexamethylene diisocyanate trimer having isocyanurate ring, IPDI/TMP: 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate Trimethylolpropane adduct, XDI/TMP: xylylenediisocyanate trimethylolpropane adduct, MAS: 3-aminopropyltrimethoxysilane, EPS: 3-glycidoxypropyltrimethoxysilane, PMMM: pentamethoxymethylolmelamine・Ester compound (C)
OLM: Methyl oleate (carbon number: 19), RS735: Polyethylene glycol diethylhexanoate [“ADEKA Sizer RS735” manufactured by ADEKA CORPORATION (EO addition mole number: 13, carbon number: 18)], POEOP: polyoxyethylene octyl ether Phosphate ester (MO addition mole number: 5, carbon number: 42), T80: polyoxyethylene di(glycerin) borate monooleate (EO addition mole number: 6 to 20, carbon number: 36 to 64) [Toho Chemical Co., Ltd.] Made "Emalbon T-80"]
・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-based UV shielding agent), CAE: Ethyl α-cyano-β,β-diphenylpropenoic acid ester (2-cyanoacrylic acid type ultraviolet shielding agent), TBPP: tris(2,4-di-tert)-butylphenyl)phosphite (phosphorus type antioxidant) , AO50: Phenolic antioxidant [“ADEKA STAB AO-50” manufactured by ADEKA CORPORATION), TMPSE bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (HALS light stabilizer), EZCG: fluorescence Dye [EZCG8006 made by Easy Bright Co., Ltd.]
・Hydrolysis inhibitor (F)
CBI: Carbodiimide [Nisshinbo, trade name Carbodilite V-09GB]
・Other ingredients (P)
FTR Petroleum-based tackifying resin ["FTR8100" manufactured by Mitsui Chemicals, Inc.]

As described above, the pressure-sensitive adhesive of the present invention has the following properties: Examples 1 to 3, 7 to 24, 28 to 53, 55 to 80, 83 to 99, optical characteristics, processability, wet spreadability, peel strength, In all of the peelability, heat resistance, and moist heat resistance, the "△" evaluation (practical level) is 3 or less out of 10 items, and the others are all "○" evaluation (good level), which is excellent. I understand.
Further, in Examples 4 to 6, 25 to 27, 54, 81 and 82, the “Δ” evaluation (practical level) of each evaluation was 4 to 10 out of 13 items, and the “x” evaluation (not practical). Since there is no level), it can be used without any practical problems.
On the other hand, in Comparative Examples 1 to 15, any one of pot life, coatability, optical characteristics, processability, wettability, peel strength, removability, heat resistance, and moist heat resistance is extremely poor. I understand.

  The pressure-sensitive adhesive according to the present invention has excellent durability such as heat resistance and wet heat resistance, and also has excellent wet spreadability, so that it can be used in the construction field (for example, exterior, interior, equipment, etc.), electrical equipment. Applications other than protective films in a wide range of fields (for example, home appliances, kitchen equipment, air conditioning, etc.), transportation equipment fields (for example, ships, automobiles, etc.), furniture fields, various industrial fields other than optical fields such as miscellaneous goods fields, etc. Can also be used as

Claims (10)

A pressure-sensitive adhesive comprising a polyurethane resin (A) (except when it has a urea bond) 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,
The polyurethane resin (A) has a carbonate structure in the main chain and has no aromatic ring and has 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 a polyurethane resin (A).   The polyol (a1) unit comprises 80 to 99% by weight and the polyisocyanate (a2) comprises 1 to 20% by weight in 100% by weight of all monomers constituting the polyurethane resin (A). Pressure sensitive adhesive.   The pressure-sensitive adhesive according to claim 1, wherein the polyol (a1) includes a polycarbonate polyol (a1-5).   The pressure-sensitive adhesive according to any one of claims 1 to 3, which comprises 1 to 80% by weight of the polycarbonate polyol (a1-5) in 100% by weight of the polyol (a1).   The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the polyisocyanate (a2) contains an aliphatic diisocyanate or an alicyclic diisocyanate.   The pressure-sensitive adhesive according to any one of claims 1 to 5, wherein the reactive compound (B) contains a polyisocyanate (b1). The pressure-sensitive adhesive according to any one of claims 1 to 6, further comprising an ester compound (C) (excluding the polyurethane resin (A) and the reactive compound (B)).   The pressure-sensitive adhesive according to claim 1, further comprising an ionic compound (D).   A pressure-sensitive adhesive film comprising a substrate and an adhesive layer containing the pressure-sensitive adhesive according to claim 1.   An optical laminate comprising an optical film, an adhesive layer containing the pressure-sensitive adhesive according to any one of claims 1 to 8, and a glass plate.