JP2016003300A - Adhesive composition, surface protective film and transparent conductive film with surface protective film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition capable of exhibiting light peelablity to metal, having excellent wettability to an entire surface of a metal mesh film, exhibiting low contamination property to the metal mesh film, and efficiently preventing corrosion of the metal, and also to provide a surface protective film having an adhesive layer made from such an adhesive composition, and a transparent conductive film with a surface protective film having such a surface protective film.SOLUTION: An adhesive composition includes a resin and an azole compound. The resin is at least one selected from a polyurethane resin and a polyester resin. The azole compound is other than azole compounds having 1,2,3-triazole structure and having a phenyl ring structure connected at the position 2.

Description

  The present invention relates to an adhesive composition. Moreover, this invention relates to the surface protection film which has an adhesive layer formed from the adhesive composition of this invention. Furthermore, this invention relates to the transparent conductive film with a surface protection film which has the surface protection film of this invention.

  In recent years, in the field of precision electronic devices such as touch panels, metal mesh films having metal electrodes and metal circuits provided on a substrate have been used. As a typical example of such a metal mesh film, for example, a copper wiring having a width of about 3 μm to 10 μm is provided on a resin substrate.

  It is preferable to attach a surface protective film to such a metal mesh film in order to protect the surface (see, for example, Patent Documents 1 to 4).

  However, when the throwing force between the metal and the substrate is low, or the metal wiring after etching is slightly scratched, the metal mesh film has a A problem arises in that the metal is removed from the adhesive layer of the protective film, resulting in disconnection.

  In order to prevent the disconnection as described above, the surface protective film is required to have light peelability. However, surface protection films using ordinary acrylic adhesives (see, for example, Patent Documents 1 to 4) have a limit to light release to some extent, and when light release exceeds that, The wettability to the whole surface of a mesh film is bad, the problem that it does not fully stick to a metal mesh film, and the problem that a bubble entraps between a metal mesh film and a surface protection film arise. This is because, in the metal mesh film, the metal wiring exists on the substrate, and the ratio of the area of the metal portion in the area of the entire surface is small, while the ratio of the area of the substrate exposed portion in the area of the entire surface is large. Because.

  Accordingly, there is a demand for a pressure-sensitive adhesive layer design that can exhibit light releasability with respect to metal and is excellent in wettability to the entire surface of the metal mesh film.

  In addition, strict low contamination is required for metal mesh films used in the field of precision electronic equipment and the like. For this reason, it is calculated | required that the adhesive component of an adhesive layer does not contaminate the metal mesh film surface by adhesive residue etc.

  Furthermore, the metal provided in the metal mesh film is easily corroded. For example, when stored under high humidity, the metal is easily corroded even if the surface protective film is adhered, and there is a problem that a change in color and a change in resistance value occur. Such a problem is particularly remarkable when the metal is, for example, copper.

JP-A-7-242863 JP 2001-19915 A JP 2004-99805 A JP 2006-45315 A

  The problem of the present invention is that it can exhibit light releasability to metal, has excellent wettability to the entire surface of the metal mesh film, can exhibit low contamination to the metal mesh film, and effectively corrodes metal An object of the present invention is to provide a pressure-sensitive adhesive composition that can be prevented. Moreover, it is providing the surface protection film which has an adhesive layer formed from such an adhesive composition. Furthermore, it is providing the transparent conductive film with a surface protective film which has such a surface protective film.

The pressure-sensitive adhesive composition of the present invention is
A pressure-sensitive adhesive composition comprising a resin and an azole compound,
The resin is at least one selected from polyurethane resins and polyester resins,
The azole compound is an azole compound other than an azole compound having a 1,2,3-triazole structure and having a phenyl ring structure bonded to the 2-position.

  In a preferred embodiment, the azole compound is an imidazole compound, an isomer of an imidazole compound, a benzotriazole compound having a 1,2,3-triazole structure and having no phenyl ring structure bonded to the 2-position. Is at least one selected from

  In preferable embodiment, the content rate of the said azole compound with respect to 100 weight part of said resin is 0.05 weight part-5 weight part.

  In a preferred embodiment, the resin is a polyurethane resin.

  In a preferred embodiment, the polyurethane resin is a polyurethane resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).

  The surface protective film of this invention has the adhesive layer and base material layer which are formed from the adhesive composition of this invention.

  The transparent conductive film with a surface protective film of the present invention has a metal thin film on at least one surface of a transparent resin substrate, and has the surface protective film of the present invention on the surface of the metal thin film.

  According to the present invention, it is possible to express light releasability with respect to a metal, excellent wettability to the entire surface of the metal mesh film, exhibit low contamination with respect to the metal mesh film, and effectively corrode metal. The pressure-sensitive adhesive composition can be provided. Moreover, the surface protection film which has an adhesive layer formed from such an adhesive composition can be provided. Furthermore, the transparent conductive film with a surface protective film which has such a surface protective film can be provided.

It is a schematic sectional drawing of the surface protection film by preferable embodiment of this invention.

≪≪Adhesive composition≫≫
The pressure-sensitive adhesive composition of the present invention contains a resin and an azole compound.

≪Resin≫
The resin contained in the pressure-sensitive adhesive composition of the present invention is at least one selected from polyurethane resins and polyester resins. By adopting at least one selected from polyurethane-based resins and polyester-based resins as the resin contained in the pressure-sensitive adhesive composition of the present invention, light releasability can be expressed with respect to the metal, and the entire surface of the metal mesh film It is possible to provide a pressure-sensitive adhesive composition that has excellent wettability and can exhibit low contamination to a metal mesh film.

  The resin contained in the pressure-sensitive adhesive composition of the present invention is preferably a polyurethane resin. By adopting a polyurethane-based resin as the resin contained in the pressure-sensitive adhesive composition of the present invention, it is possible to more easily exhibit light releasability with respect to metal, and it is more excellent in wettability to the entire surface of the metal mesh film. It is possible to provide a pressure-sensitive adhesive composition that can further exhibit low contamination to the film.

<Polyester resin>
Any appropriate polyester resin can be adopted as the polyester resin as long as the effects of the present invention are not impaired.

  The polyester resin is preferably a polyester obtained by polycondensation of a dicarboxylic acid having a side chain and a diol, or a derivative thereof. Any appropriate polymerization method can be used as the polyester synthesis method.

  The dicarboxylic acid preferably has a side chain and has two carboxyl groups as functional groups, and more preferably the side chain is an alkyl group. The dicarboxylic acid having a side chain is preferable because the flexibility of the polyester can be increased. Since the side chain is an alkyl group, hydrolysis of the polyester is less likely to occur, which is preferable.

  Examples of the dicarboxylic acid include plant-derived dicarboxylic acid. Examples of such dicarboxylic acids include dimer acids derived from castor oil-derived sebacic acid, oleic acid, erucic acid, and the like, and others include adipic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dodecenyl succinic anhydride, fumaric acid, succinic acid, dodecanedioic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, maleic acid, maleic anhydride, itaconic acid, citracone Aliphatic and alicyclic dicarboxylic acids such as acids, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 2, 2'-diphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid And the like. Among these, dimer acid and the like are particularly preferable from the viewpoint of being derived from plants and being friendly to the global environment. These can be used alone or in combination of two or more.

  Any appropriate diol can be adopted as the diol as long as it does not impair the characteristics of the present invention. Examples of such a diol include those having two hydroxyl groups as functional groups. Preferably, the diol has a side chain, and more preferably, the side chain is an alkyl group. The diol having a side chain is preferable because the flexibility of the polyester can be increased. Since the side chain is an alkyl group, hydrolysis of the polyester is less likely to occur, which is preferable.

  Examples of the diol include plant-derived diols. Examples of such diols include fatty acid esters derived from castor oil, dimer diols derived from oleic acid, erucic acid, and the like, glycerol monostearate, and the like. 2-propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, 2-ethyl-2- Butylpropanediol, 1,9-nonanediol, 2-methyloctyl Diols, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and other aliphatic glycols, and ethylene oxide adducts and propylene oxides of bisphenol A Examples include adducts, ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, polytetramethylene glycol, polypropylene glycol, polyethylene glycol, polycarbonate glycol, and the like. These can be used alone or in combination of two or more.

  The molar ratio of dicarboxylic acid and diol is preferably 1: 1.08 to 2.10, more preferably 1: 1.09 to 2.05, and still more preferably 1: 1.10 to 2.00. When the molar ratio of the diol to the dicarboxylic acid 1 is smaller than 1.08, the molecular weight of the resulting polyester is increased, the number of hydroxyl groups serving as functional groups is decreased, and a crosslinking agent (for example, polyfunctional isocyanate) is used. Further, it becomes difficult to promote the crosslinking reaction, and there is a possibility that a pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) having a desired gel fraction cannot be obtained. When the molar ratio of the diol to the dicarboxylic acid 1 exceeds 2.10, there is a tendency that only a polyester having a molecular weight smaller than the desired molecular weight is obtained, and even if a crosslinking agent is used, gelation cannot be promoted. There is a possibility that a pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) having a gel fraction cannot be obtained. In addition, when the number of moles of dicarboxylic acid and diol is close and the molar ratio is closer to 1: 1, the molecular weight of the resulting polyester increases, and as a result, the adhesive force (peeling force) increases and light peeling can be realized. Since it disappears, it is not preferable as an adhesive film for surface protection.

  The weight average molecular weight (Mw) of polyester becomes like this. Preferably it is 5000-50000, More preferably, it is 5500-45000, More preferably, it is 6000-40000. When the weight average molecular weight of the polyester is less than 5,000, the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) using the polyester may cause a decrease in the adhesive strength. There is a possibility that the adhesive layer) itself cannot be fixed. On the other hand, when the weight average molecular weight exceeds 50000, it may cause a decrease in cohesive force and a decrease in holding power.

  As long as the properties of the polyester are not impaired, other components can be polymerized or added after the polymerization when the polyester is produced. For example, a polyhydric hydroxyl group-containing compound such as trimethylolpropane, pentaerythritol, dipentaerythritol, or other trifunctional hydroxyl group-containing compounds, polycarboxylic acid trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, etc. Trifunctional or higher carboxylic acid compounds, and compounds having both a hydroxyl group and a carboxyl group, such as glycolic acid, hydroxypivalic acid, 3-hydroxy-2-methylpropionic acid, lactic acid, glyceric acid, malic acid, citric acid, etc. Is mentioned. These can be used alone or in combination of two or more.

  The polymerization (condensation polymerization) reaction between the dicarboxylic acid and the diol may be performed using a solvent, may be performed without a solvent, or any other suitable method may be used.

  As a method of removing water generated by polymerization (condensation polymerization) reaction of dicarboxylic acid and diol, azeotropic dehydration using toluene or xylene, or blowing an inert gas into the reaction system, together with the inert gas And a method of discharging generated water and monoalcohol out of the reaction system, a method of distilling under reduced pressure, and the like.

  As a polymerization catalyst used in the polymerization (condensation polymerization) reaction between a dicarboxylic acid and a diol, any appropriate polymerization catalyst used as a polymerization catalyst in the usual polyester production can be used. Examples of such a polymerization catalyst include various metal compounds such as titanium, tin, antimony, zinc, and germanium, and strong acid compounds such as p-toluenesulfonic acid and sulfuric acid.

  The polyester resin preferably contains a polyether polyol. The polyether polyol can be inserted into the pressure-sensitive adhesive composition by crosslinking the polyester and the polyether polyol with a crosslinking agent. In particular, by blending a polyether polyol, it is possible to obtain a pressure-sensitive adhesive layer (or a surface protective film having the same) having good wettability and suppressing air bubble biting.

  Any appropriate polyether polyol can be adopted as the polyether polyol as long as the effects of the present invention are not impaired. Examples of such polyether polyols include bifunctional polyether polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol, and trifunctional polyether polyols such as trimethylolpropane tripolyoxyethylene ether. , Tetrafunctional polyether polyols such as pentaerythritol polyoxyethylene ether, polyoxyalkylene glycols such as polytrimethylene ether glycol, 1 to 20 mol% of a copolymer polyether polyol of 3-methyltetrahydrofuran and tetrahydrofuran (for example, Hodogaya Chemical) “PTG-L1000”, “PTG-L2000”, “PTG-L3000”, etc.), neopentyl glycol and tetrahydrofuran Copolymerized polyether glycol, polyoxypropylene glycol, and the like. In addition, plant-derived polyether polyol is preferable from the viewpoint of being friendly to the global environment. These can be used alone or in combination of two or more.

  As the polyether polyol, a block copolymer type such as polyoxyethylene polyoxypropylene glycol or a random copolymer type can also be used. In addition, aliphatic hydrocarbon groups such as methyl group, ethyl group, allyl group, propyl group, butyl group, 2-ethylhexyl group, phenyl group, methylphenyl group, nonylphenyl group, benzyl group, etc. The terminal hydroxyl group may be modified with the aromatic hydrocarbon group, so that the reactivity may be eliminated. However, if all the functional groups are modified, the reactivity is completely lost, so that the crosslinking reaction with the polyester cannot be performed, and the polyether polyol itself causes bleeding out to the pressure-sensitive adhesive surface, which is not preferable. In order to obtain particularly good adhesive properties, it is preferable to use one having a structure having a branched chain in the molecular skeleton such as polypropylene glycol or polybutylene glycol. This is because it is presumed that the polymer chain has high mobility and the contribution in the vicinity of the pressure-sensitive adhesive surface is increased. A type in which a part of these all terminal hydroxyl groups (terminal functional groups) is modified is further useful. This is because the molecular chain that has become denatured and has no reactivity is free, so that the molecular mobility is further increased and it is easy to adjust to the desired adhesive property.

  The number average molecular weight (Mn) of the polyether polyol is preferably from 100 to 5000, more preferably from 200 to 4000, and even more preferably 300 for those in which all terminal hydroxyl groups (terminal functional groups) are unmodified. ~ 3000. When the number average molecular weight (Mn) of the polyether polyol is less than 100, the effect of improving the adhesive property may be reduced. If the number average molecular weight (Mn) of the polyether polyol is larger than 5000, the polyether polyol itself tends to bleed out, which may cause contamination. Also, by adjusting the number average molecular weight (Mn) of the polyether polyol within the above range, effects such as good wettability and suppression of bubble biting can be obtained, and compatibility with polyester is also good. It is preferable that the cause of occurrence of bleed-out or the like can be suppressed without causing appearance defects and the adherend is not contaminated.

  The number average molecular weight (Mn) of those in which a part of all terminal hydroxyl groups (terminal functional groups) is modified is preferably 100 to 1500, more preferably 200 to 1200, and still more preferably 300 to 1000. . If the number average molecular weight (Mn) of a modified part of all terminal hydroxyl groups (terminal functional groups) is less than 100, the adhesive property improving effect may be reduced. When the number average molecular weight (Mn) is larger than 1,500, although some of the terminal hydroxyl groups (terminal functional groups) have been modified, the polyether polyol itself tends to bleed out, which may cause contamination.

  The blending amount of the polyether polyol is preferably 1 part by weight to 400 parts by weight, more preferably 3 parts by weight with respect to 100 parts by weight of the polyester when the terminal hydroxyl groups (terminal functional groups) are unmodified. Part to 300 parts by weight, more preferably 5 parts to 200 parts by weight. If the blending amount of the polyether polyol in which all terminal hydroxyl groups (terminal functional groups) are unmodified is less than 1 part by weight with respect to 100 parts by weight of the polyester, the effect of improving the adhesive properties may not be obtained. If the blending amount of the polyether polyol having all terminal hydroxyl groups (terminal functional groups) unmodified is more than 400 parts by weight with respect to 100 parts by weight of the polyester, the polyether polyol itself tends to bleed out, causing contamination. There is a risk of becoming. By adjusting the blending amount of the polyether polyol in which all terminal hydroxyl groups (terminal functional groups) are unmodified within the above range, effects such as good wettability and suppression of bubble entrapment can be obtained. The compatibility with the polyester is also good, the appearance is not poor, the occurrence of bleeding out and the like can be suppressed, and the adherend is not contaminated, which is preferable.

  The blending amount of the polyether polyol is preferably 1 part by weight to 35 parts by weight with respect to 100 parts by weight of the polyester, and more preferably about those in which a part of all terminal hydroxyl groups (terminal functional groups) are modified. Is 3 to 32 parts by weight, more preferably 5 to 28 parts by weight. If the blending amount of the polyether polyol in which a part of all terminal hydroxyl groups (terminal functional groups) is modified is less than 1 part by weight with respect to 100 parts by weight of the polyester, there is a possibility that the effect of improving the adhesive property cannot be obtained. is there. When the blending amount of the polyether polyol in which a part of all terminal hydroxyl groups (terminal functional groups) is modified is more than 35 parts by weight with respect to 100 parts by weight of the polyester, the polyether polyol itself tends to bleed out, May cause contamination. By adjusting the blending amount of the polyether polyol in which a part of all terminal hydroxyl groups (terminal functional groups) is modified within the above range, effects such as good wettability and suppression of bubble entrapment are obtained. In addition, the compatibility with the polyester is good, the appearance is not deteriorated, the cause of bleed-out and the like can be suppressed, and the adherend is not contaminated.

  Any appropriate crosslinking agent can be adopted as the crosslinking agent as long as the effects of the present invention are not impaired. Examples of such crosslinking agents include polyvalent isocyanurates, polyfunctional isocyanates, polyfunctional melamine compounds, polyfunctional epoxy compounds, polyfunctional oxazoline compounds, polyfunctional aziridine compounds, metal chelate compounds, and the like. In particular, from the viewpoint of obtaining transparency of the obtained pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) and obtaining a pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) having a high gel fraction, polyisocyanurate and polyfunctionality Isocyanate compounds are preferred. These can be used alone or in combination of two or more.

  Examples of polyvalent isocyanurates include polyisocyanurates of hexamethylene diisocyanate. By using these, it is possible to achieve the purpose of obtaining the transparency of the obtained pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) and the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) having a high gel fraction. It is.

  Commercially available products can be used as the polyvalent isocyanurate. Specifically, the trade name “Duranate TPA-100” (manufactured by Asahi Kasei Chemicals), trade names “Coronate HK”, “Coronate HX”, “Coronate”. 2096 "(manufactured by Nippon Polyurethane Industry Co., Ltd.).

  The polyfunctional isocyanate compound is, for example, preferably a compound having at least two isocyanate groups in the molecule, more preferably a compound having at least three isocyanate groups in the molecule. Specifically, aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates and the like can be mentioned.

  Examples of the aliphatic polyisocyanates include 1,2-ethylene diisocyanate, tetramethylene diisocyanate such as 1,2-tetramethylene diisocyanate, 1,3-tetramethylene diisocyanate, 1,4-tetramethylene diisocyanate, and 1,2. -Hexamethylene diisocyanate such as hexamethylene diisocyanate, 1,3-hexamethylene diisocyanate, 1,4-hexamethylene diisocyanate, 1,5-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,5-hexamethylene diisocyanate; Examples include 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, and lysine diisocyanate.

  Examples of the alicyclic polyisocyanates include isophorone diisocyanate, cyclohexyl diisocyanate such as 1,2-cyclohexyl diisocyanate, 1,3-cyclohexyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,2-cyclopentyl diisocyanate, 1,3. -Cyclopentyl diisocyanate such as cyclopentyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and the like.

  Examples of aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4′-diisocyanate, 2,2′-diphenylpropane-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxy Diphenyl-4,4'-diisocyanate, xylylene-1,4-diisocyanate, and the like xylylene-1,3-diisocyanate.

  In addition to aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates, difunctional or trimer based on araliphatic polyisocyanates can be used as the polyfunctional isocyanate compound. , Diphenylmethane diisocyanate dimer and trimer, reaction product of trimethylolpropane and tolylene diisocyanate, reaction product of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate And polymers such as polyester polyisocyanate.

  Commercially available products can also be used as the polyfunctional isocyanate compound. Specifically, as a trimer adduct of trimethylolpropane and tolylene diisocyanate, the product name “Coronate L” (manufactured by Nippon Polyurethane Industry Co., Ltd.) As a trimer adduct of trimethylolpropane and hexamethylene diisocyanate, a trade name “Coronate HL” (manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like can be mentioned.

  Examples of the polyfunctional melamine compound include methylated methylol melamine and butylated hexamethylol melamine, and examples of the polyfunctional epoxy compound include diglycidyl aniline and glycerin diglycidyl ether.

  As a compounding quantity of a crosslinking agent, it is preferable to mix | blend so that the gel fraction of an adhesive composition (or adhesive layer) may be 40 weight%-95 weight%, for example, More preferably, 45 weight%-93 It mix | blends so that it may become weight%, More preferably, it mix | blends so that it may become 50 to 92 weight%. When the gel fraction of the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) is less than 40% by weight, a large amount of unreacted polyether polyol remains, which may contaminate the adherend, and is inferior in handling properties. There is a fear. Moreover, when the gel fraction of the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) is less than 40% by weight, the pressure-sensitive adhesive force (peeling force) increases with time, or a surface protective film (specifically, it has) When the pressure-sensitive adhesive layer) is peeled off, the adherend may be contaminated, and the light peelability (removability) may be poor. When the gel fraction of the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) exceeds 95% by weight, the polyether polyol is constrained and may not come out on the surface of the pressure-sensitive adhesive layer, and wettability to the adherend. Or the adhesive strength becomes too low and the surface protection film itself may not be fixed to the adherend, and may not be used for surface protection.

  As a compounding quantity of a crosslinking agent, Preferably it is 2 to 30 weight part with respect to 100 weight part of polyester, More preferably, it is 3 to 28 weight part, More preferably, it is 4 to 26 weight part Part. When the blending amount of the crosslinking agent with respect to 100 parts by weight of the polyester is less than 2 parts by weight, the cohesive force may not be improved when the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) is used. A large amount of the polyether polyol in the reaction may be present, which may cause contamination of the adherend. If the blending amount of the cross-linking agent with respect to 100 parts by weight of the polyester exceeds 30 parts by weight, the cross-linking agent becomes excessive. Therefore, after bonding, the adhesive strength increases with time or the adherend is contaminated. May occur.

  The blending amount of the crosslinking agent is, for example, preferably 2 to 50 parts by weight, more preferably 3 to 40 parts by weight, with respect to 100 parts by weight of the total of the polyester and the polyether polyol. The amount is preferably 4 to 30 parts by weight. When the blending amount of the crosslinking agent with respect to 100 parts by weight of the total of the polyester and the polyether polyol is less than 2 parts by weight, the cohesive force may not be improved when the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer) is used. In addition, a large amount of unreacted polyether polyol may be present, which may cause contamination of the adherend. If the blending amount of the cross-linking agent with respect to 100 parts by weight of the total of polyester and polyether polyol exceeds 50 parts by weight, the cross-linking agent becomes excessive. There is a risk of malfunctions such as

  In order to efficiently adjust the gel fraction of the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer), a crosslinking catalyst can be appropriately used. Examples of such a crosslinking catalyst include tetra-n-butyl titanate, tetraisopropyl titanate, butyl tin oxide, dioctyl tin diurarate, and the like. These can be used alone or in combination of two or more.

  As a compounding quantity of a crosslinking catalyst, for example with respect to 100 weight part of polyester, Preferably it is 0.01 weight part-1 weight part, More preferably, it is 0.05 weight part-0.5 weight part. If the blending amount of the crosslinking catalyst with respect to 100 parts by weight of the polyester is less than 0.01 part by weight, the effect of adding the catalyst may not be obtained, and if the blending amount of the crosslinking catalyst with respect to 100 parts by weight of the polyester exceeds 1 part by weight. The shelf life is remarkably shortened, and the coating stability may be lowered.

  In order to extend the shelf life, acetylacetone, methanol, methyl orthoacetate, or the like can be appropriately blended as a retarder.

  In order to impart desired properties to the pressure-sensitive adhesive composition (or pressure-sensitive adhesive layer), a polyester may be combined with a tackifier resin together with a crosslinking agent.

  Any appropriate tackifying resin can be adopted as the tackifying resin as long as the effects of the present invention are not impaired. Examples of such tackifier resins include terpene tackifier resins, phenol tackifier resins, rosin tackifier resins, aliphatic petroleum resins, aromatic petroleum resins, copolymer petroleum resins, and alicyclics. Petroleum-based petroleum resins, xylene resins, epoxy-based tackifying resins, polyamide-based tackifying resins, ketone-based tackifying resins, elastomer-based tackifying resins, etc. It is preferable to use a rosin-based or terpene-based tackifier resin. These can be used alone or in combination of two or more. In addition, a biomass degree means what computed the ratio of the plant-derived use raw material from the weight of the plant-derived use raw material with respect to the weight of the whole use raw material which comprises the said polyester-type adhesive composition.

  Examples of terpene-based tackifier resins include terpene resins, terpene phenol resins, and aromatic-modified terpene resins. Specifically, α-pinene polymers, β-pinene polymers, dipentene polymers, and the like These include terpene resins obtained by phenol modification, aromatic modification, hydrogenation modification, and hydrocarbon modification.

  Examples of the phenolic tackifier resin include condensates of various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, and formaldehyde. Also, resole obtained by addition reaction of the above phenols and formaldehyde under an alkali catalyst, novolak, unmodified or modified rosin obtained by condensation reaction of the above phenols and formaldehyde under an acid catalyst, and these Examples thereof include rosin-modified phenol resins obtained by adding phenol to an rosin such as a derivative in the presence of an acid catalyst and performing thermal polymerization.

  Examples of the rosin-based tackifying resin include rosin resin, polymerized rosin resin, hydrogenated rosin resin, rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, and the like. Specifically, gum rosin, wood rosin, and tall Examples thereof include unmodified rosin such as oil rosin (raw rosin), hydrogenated, disproportionated, polymerized, and other chemically modified modified rosins and derivatives thereof.

  The compounding amount of the tackifying resin is preferably 0 to 50 parts by weight, more preferably 2 to 30 parts by weight, and particularly preferably 5 to 20 parts by weight with respect to 100 parts by weight of the polyester. Part. When the compounding amount of the tackifying resin with respect to 100 parts by weight of the polyester exceeds 50 parts by weight, the pressure-sensitive adhesive composition (or the pressure-sensitive adhesive layer) has high adhesive strength, and re-peeling after exposure to a high temperature environment becomes difficult. There is a fear.

  In the polyester resin, an ultraviolet absorber, a light stabilizer, a release adjusting agent, a plasticizer, a softening agent, a filler, a colorant such as a pigment or a dye, an anti-aging agent, an interface, as long as the effects of the present invention are not impaired. General additives such as activators may be included.

<Polyurethane resin>
Any appropriate polyurethane resin can be adopted as the polyurethane resin as long as the effects of the present invention are not impaired. The polyurethane resin is preferably a polyurethane resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), or a polyurethane obtained from a composition containing a urethane prepolymer (C). Resin. By adopting the above-mentioned polyurethane-based resin, it is possible to further develop light releasability with respect to the metal, further improve wettability to the entire surface of the metal mesh film, and lower with respect to the metal mesh film. It is possible to provide a pressure-sensitive adhesive composition capable of further expressing the contamination.

<Polyurethane resin obtained from composition containing polyol (A) and polyfunctional isocyanate compound (B)>
Specifically, the polyurethane resin obtained from the composition containing the polyol (A) and the polyfunctional isocyanate compound (B) is preferably a composition containing the polyol (A) and the polyfunctional isocyanate compound (B). Is a polyurethane-based resin obtained by curing. The polyol (A) may be one kind or two or more kinds. Only one type of polyfunctional isocyanate compound (B) may be used, or two or more types may be used.

  Examples of the polyol (A) include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, castor oil-based polyol, and the like.

  The polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.

  Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-1. , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl Examples include -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, and polypropylene glycol. Examples of the acid component include succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid , And these acid anhydrides.

  Examples of polyether polyols include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcin, hydroquinone, etc.), etc. And polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

  Examples of the polycaprolactone polyol include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

  Examples of the polycarbonate polyol include a polycarbonate polyol obtained by polycondensation reaction of the polyol component and phosgene; the polyol component, dimethyl carbonate, diethyl carbonate, diprovir carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; Polycarbonate polyol obtained by esterification reaction with a compound; the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound A polycarbonate polyol obtained by a reaction of tellurization; a polycarbonate polyol obtained by a transesterification reaction between the above various polycarbonate polyols and an ester compound; a polycarbonate polyol obtained by a transesterification reaction between the various polycarbonate polyols and a hydroxyl group-containing compound; And polyester polycarbonate polyols obtained by polycondensation reaction of the various polycarbonate polyols with dicarboxylic acid compounds; copolymer polyether polycarbonate polyols obtained by copolymerizing the various polycarbonate polyols and alkylene oxides;

  An example of the castor oil-based polyol is a castor oil-based polyol obtained by reacting a castor oil fatty acid with the polyol component. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.

  The polyol (A) preferably contains a polyol (A1) having three OH groups and a number average molecular weight Mn of 8000 to 20000. The polyol (A1) may be only one kind or two or more kinds. When the polyol (A) contains the polyol (A1) having three OH groups and a number average molecular weight Mn of 8000 to 20000, the light releasability can be further exhibited with respect to the metal, and the surface of the metal mesh film It is possible to provide a pressure-sensitive adhesive composition that is more excellent in wettability to the whole and that can further exhibit low contamination to the metal mesh film.

  The content ratio of the polyol (A1) to 100 parts by weight of the polyol (A) is preferably 70 parts by weight or more, more preferably 70 parts by weight to 100 parts by weight, and further preferably 70 parts by weight to 90 parts by weight. is there. By adjusting the content ratio of the polyol (A1) with respect to 100 parts by weight of the polyol (A) within the above range, light releasability can be further expressed with respect to the metal, and wettability to the entire surface of the metal mesh film It is possible to provide a pressure-sensitive adhesive composition that is more excellent and can further exhibit low contamination to the metal mesh film.

  The number average molecular weight Mn of the polyol (A1) is 8000 to 20000, preferably 8000 to 18000, more preferably 8500 to 17000, still more preferably 9000 to 16000, and particularly preferably 9500 to 15500. Most preferably, it is 10000-15000. By adjusting the number average molecular weight Mn of the polyol (A1) within the above range, it is possible to further exhibit light releasability with respect to the metal, and more excellent wettability to the entire surface of the metal mesh film. Therefore, it is possible to provide a pressure-sensitive adhesive composition that can further exhibit low contamination.

  The polyol (A) may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 5000 or less. The polyol (A2) may be only one kind or two or more kinds. The number average molecular weight Mn of the polyol (A2) is preferably 500 to 5000, more preferably 800 to 4500, still more preferably 1000 to 4000, particularly preferably 1000 to 3500, and most preferably 1000. ~ 3000. When the number average molecular weight Mn of the polyol (A2) is out of the above range, there is a possibility that the adhesive strength with time is particularly increased. The polyol (A2) preferably has a polyol (triol) having 3 OH groups, a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and 6 OH groups. Polyol (hexaol).

  As the polyol (A2), a total amount of at least one of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) is: The content ratio in the polyol (A) is preferably 10% by weight or less, more preferably 7% by weight or less, still more preferably 6% by weight or less, and particularly preferably 5% by weight or less. In the polyol (A), as the polyol (A2), at least of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) By adjusting 1 type to the said range, the urethane type adhesive which was further excellent in transparency can be provided.

  The content ratio of the polyol (A2) to 100 parts by weight of the polyol (A) is preferably 30 parts by weight or less, more preferably 0 to 30 parts by weight. By adjusting the content ratio of the polyol (A2) with respect to 100 parts by weight of the polyol (A) within the above range, the light releasability can be further expressed with respect to the metal, and the wettability to the entire surface of the metal mesh film It is possible to provide a pressure-sensitive adhesive composition that is more excellent and can further exhibit low contamination to the metal mesh film.

  In the polyol (A2), the content ratio of the polyol having 4 or more OH groups therein and a number average molecular weight Mn of 5000 or less is preferably less than 10 parts by weight with respect to 100 parts by weight of the polyol (A). More preferably, it is 8 parts by weight or less, more preferably 7 parts by weight or less, particularly preferably 6 parts by weight or less, and most preferably 5 parts by weight or less. When the content ratio of the polyol having 4 or more OH groups in the polyol (A2) and having a number average molecular weight Mn of 5000 or less is 10 parts by weight or more with respect to 100 parts by weight of the polyol (A), the urethane-based pressure-sensitive adhesive May be easily whitened and transparency may be lowered.

  Only one type of polyfunctional isocyanate compound (B) may be used, or two or more types may be used.

  As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound that can be used in the urethanization reaction can be adopted. Examples of such a polyfunctional isocyanate compound (B) include polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanate compounds, polyfunctional aromatic isocyanate compounds, and the like.

  Examples of the polyfunctional aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4 Examples include 4-trimethylhexamethylene diisocyanate.

  Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Examples include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.

  Examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-didiphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like.

  Examples of the polyfunctional isocyanate compound (B) include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, burettes reacted with water, and trimers having an isocyanurate ring. These may be used in combination.

  Specifically, the polyurethane-based resin is preferably obtained by curing a composition containing the polyol (A) and the polyfunctional isocyanate compound (B). Such a composition may contain any appropriate other component other than the polyol (A) and the polyfunctional isocyanate compound (B) as long as the effects of the present invention are not impaired. Examples of such other components include catalysts, other resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, Examples thereof include an antioxidant, a conductive agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, and a solvent.

  The polyurethane-based resin preferably contains a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, and a light stabilizer. When the polyurethane-based resin contains a deterioration preventing agent, the adhesive residue can be prevented from remaining on the adherend, for example, even when the polyurethane resin is attached to the adherend and stored in a heated state, and thus the adhesive residue hardly occurs on the adherend. Therefore, in the surface protective film of the present invention having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention, contamination on the adherend can be further reduced. Only one type of deterioration preventing agent may be used, or two or more types may be used. As the deterioration preventing agent, an antioxidant is particularly preferable.

  The content ratio of the deterioration inhibitor is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.05 parts by weight to 7 parts by weight, further preferably 100 parts by weight of the polyol (A). Is 0.1 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight, and most preferably 0.1 to 1 part by weight. By adjusting the content ratio of the deterioration preventive agent within the above range, adhesive residue is less likely to remain on the adherend even if it is stored in a heated state after being attached to the adherend. Can become better. Therefore, in the surface protective film of the present invention having the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention, contamination on the adherend can be further reduced. If the content ratio of the deterioration inhibitor is too small, there is a possibility that the adhesive residue preventing property cannot be sufficiently exhibited. If the content of the deterioration inhibitor is too large, there may be a problem that the cost is disadvantageous, a problem that the adhesive property cannot be maintained, or a problem that the adherend is contaminated may occur. .

  Examples of the antioxidant include a radical chain inhibitor and a peroxide decomposer.

  Examples of the radical chain inhibitor include phenolic antioxidants and amine antioxidants.

  Examples of the peroxide decomposer include a sulfur-based antioxidant and a phosphorus-based antioxidant.

  Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, and high-molecular 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- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like.

  Examples of the bisphenol antioxidant include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4 ′. -Thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-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.

  Examples of the polymeric phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4, 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl) -4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like.

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

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, and phenyl diisodecyl phosphite.

  Examples of UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid UV absorbers, oxalic anilide UV absorbers, cyanoacrylate UV absorbers, and triazine UV absorbers. It is done.

  Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ′. -Dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) ) Methane.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′-(3 ', 4' ', 5' ', 6' ',-tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], [2 (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole, and the like.

  Examples of salicylic acid-based ultraviolet absorbers include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.

  Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and the like.

  Examples of the light stabilizer include hindered amine light stabilizers and ultraviolet light stabilizers.

  Examples of the hindered amine light stabilizer include [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate], bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate and the like.

  Examples of the ultraviolet stabilizer include nickel bis (octylphenyl) sulfide, [2,2′-thiobis (4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-tert- Examples thereof include butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type quencher, and nickel-dibutyldithiocarbamate.

  The polyurethane-based resin preferably contains a fatty acid ester. When the polyurethane resin contains a fatty acid ester, the wetting speed can be further improved. Only one type of fatty acid ester may be used, or two or more types may be used.

  The content ratio of the fatty acid ester is preferably 5 parts by weight to 50 parts by weight, more preferably 7 parts by weight to 40 parts by weight, and still more preferably 8 parts by weight to 100 parts by weight of the polyol (A). 35 parts by weight, particularly preferably 9 parts by weight to 30 parts by weight, and most preferably 10 parts by weight to 20 parts by weight. By adjusting the content ratio of the fatty acid ester within the above range, the wetting speed can be further improved. If the content of the fatty acid ester is too small, the wetting speed may not be sufficiently improved. When the content ratio of the fatty acid ester is too large, there may be a problem that the cost becomes disadvantageous, a problem that the adhesive property cannot be maintained, or a problem that the adherend is contaminated.

  The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, still more preferably 230 to 380, particularly preferably 240 to 360, and most preferably 270 to 340. It is. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting speed can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, the wetting speed may not be improved even if the number of added parts is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curability of the pressure-sensitive adhesive at the time of drying deteriorates, and there is a possibility that it may not only affect the wettability but also adversely affect other adhesive properties.

  As the fatty acid ester, any appropriate fatty acid ester can be adopted as long as the effects of the present invention are not impaired. Examples of such fatty acid esters include polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, myristic acid Isopropyl, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, coconut fatty acid methyl, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate , Pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, triglycera 2-ethylhexanoate De, butyl laurate, and the like octyl oleate.

  The polyurethane-based resin preferably contains a compound that causes keto-enol tautomerism. Keto-enol tautomerism is also known as so-called enolization in which a hydrogen atom bonded to an α-carbon atom of a carbonyl compound is transferred to an oxygen atom of a carbonyl group, as is generally well known. Isomerization. By including a compound that causes keto-enol tautomerism, the polyurethane resin can sufficiently increase the pot life in the storage stage of the composition used to form the polyurethane resin by the action with the catalyst, When a polyurethane-based resin is formed using the composition (preferably cured), the crosslinking reaction of the polyol (A) and the polyfunctional isocyanate compound (B) proceeds rapidly.

  Examples of the compound causing keto-enol tautomerism include acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, and 5-methylhexane-2,4-dione. , Octane-2,4-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane-3,5-dione, nonane-2,4-dione, nonane-4,6-dione, 2 , 2,6,6-tetramethylheptane-3,5-dione, tridecane-6,8-dione, 1-phenylbutane-1,3-dione, hexafluoroacetylacetone, β-diketones such as ascorbic acid; Methyl acetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, acetoacetic acid ert-butyl, methyl propionyl acetate, ethyl propionyl acetate, n-propyl propionyl acetate, isopropyl propionyl acetate, n-butyl propionyl acetate, sec-butyl propionyl acetate, tert-butyl propionyl acetate, benzyl acetoacetate, dimethyl malonate, malonic acid Β-ketoesters such as diethyl; acid anhydrides such as acetic anhydride; ketones such as acetone, methylethylketone, methyl-n-butylketone, methylisobutylketone, methyl-tert-butylketone, methylphenylketone, and cyclohexanone; It is done.

  As a compound which causes keto-enol tautomerism, β-diketones are preferable, and acetylacetone is more preferable. By adopting such a compound as a compound that causes keto-enol tautomerism, the pot life in the storage stage of the composition used to form the polyurethane resin can be sufficiently extended by the action with the catalyst. On the other hand, when the polyurethane resin is formed using the composition (preferably cured), the crosslinking reaction of the polyol (A) and the polyfunctional isocyanate compound (B) proceeds more rapidly.

  The compound / catalyst causing keto-enol tautomerism is preferably 0.006 to 300, more preferably 0.007, in terms of molar ratio of the compound / catalyst causing keto-enol tautomerism. To 100, more preferably 0.008 to 20, more preferably 0.009 to 1.1, still more preferably 0.010 to 1.0, and still more preferably 0.010 to 0. 0.9, particularly preferably 0.010 to 0.8, and most preferably 0.010 to 0.7. By adjusting the content ratio of the compound causing the keto-enol tautomerism and the catalyst within the above range, the pot life in the storage stage of the composition used for forming the polyurethane resin by the action of the catalyst is further increased. On the other hand, when the polyurethane resin is formed using the composition (preferably cured), the crosslinking reaction of the polyol (A) and the polyfunctional isocyanate compound (B) proceeds more rapidly. . In particular, if the compound / catalyst molar ratio causing the keto-enol tautomerism is within the range of 0.006 to 0.7, the surface protection film of the present invention can effectively suppress whitening, Can provide very high transparency.

  The polyurethane-based resin preferably contains an ionic liquid containing a fluoro organic anion. When the polyurethane resin contains an ionic liquid containing a fluoro organic anion, a polyurethane resin having excellent antistatic properties can be provided. The ionic liquid contained in the polyurethane resin may be only one kind or two or more kinds.

  In the present invention, the ionic liquid means a molten salt (ionic compound) that is liquid at 25 ° C.

  As long as the ionic liquid is an ionic liquid containing a fluoro organic anion, any appropriate ionic liquid can be adopted as long as the effects of the present invention are not impaired. Such an ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By adopting an ionic liquid composed of a fluoro organic anion and an onium cation as the ionic liquid, it is possible to provide a polyurethane-based resin having extremely excellent antistatic properties.

  Any appropriate onium cation can be adopted as the onium cation capable of constituting the ionic liquid as long as the effects of the present invention are not impaired. Such an onium cation is preferably at least one selected from a nitrogen-containing onium cation, a sulfur-containing onium cation, and a phosphorus-containing onium cation. By selecting these onium cations, it is possible to provide a polyurethane resin that is extremely excellent in antistatic properties.

The onium cation capable of constituting the ionic liquid is preferably at least one selected from cations having a structure represented by the general formulas (1) to (5).

  In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a hetero atom, and Rb and Rc may be the same or different, and hydrogen or a carbon atom having 1 to 16 carbon atoms. Represents a hydrogen group and may contain a hetero atom. However, there is no Rc when the nitrogen atom contains a double bond.

  In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms, and may contain a hetero atom, and Re, Rf, and Rg are the same or different and each represents hydrogen or 1 to carbon atoms. Represents 16 hydrocarbon groups and may contain heteroatoms.

  In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and Ri, Rj, and Rk may be the same or different, and may be hydrogen or 1 carbon atom. Represents 16 hydrocarbon groups and may contain heteroatoms.

  In the general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, Rl, Rm, Rn, and Ro are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms, It may contain atoms. However, when Z is a sulfur atom, there is no Ro.

  In the general formula (5), X represents a Li atom, a Na atom, or a K atom.

  Examples of the cation represented by the general formula (1) include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton.

  Specific examples of the cation represented by the general formula (1) include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, and 1-butyl. -3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, Pyridinium cations such as 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidini Cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1- Ethyl piperidinium cation, 1-methyl-1-propyl piperidinium cation 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1- Ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpi Piperidinium cations such as peridinium cations; 2-methyl-1-pyrroline cations; Til-2-phenylindole cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation;

  Among these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, and 1 are preferable because the effects of the present invention can be further exhibited. -Pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- Methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyrrolidinium cation, 1-methyl-1-he Tylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexyl Pyrrolidinium cations such as pyrrolidinium cation and 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1- Methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl -1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cut 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation And more preferably, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methyl, and the like. Pyridinium cation, 1-methyl-1-propylpyrrolidinium cation, and 1-methyl-1-propylpiperidinium cation.

  Examples of the cation represented by the general formula (2) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.

  Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl. -3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazole 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazole Lilium cation, 1-hexyl-2,3-dimethylimidazo Imidazolium cations such as um cation; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1 , 2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, etc. Tetrahydropyrimidinium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4- Dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1 4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium dihydropyrimidinium cation, such as cations; and the like.

  Among these, from the viewpoint that the effects of the present invention can be further exhibited, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1 -Butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3- Imidazolium cations such as methylimidazolium cation and 1-tetradecyl-3-methylimidazolium cation, more preferably 1-ethyl-3-methylimidazolium cation and 1-hexyl-3-methylimidazolium cation is there.

  Examples of the cation represented by the general formula (3) include a pyrazolium cation and a pyrazolinium cation.

  Specific examples of the cation represented by the general formula (3) include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl- Pyrazolium cations such as 2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation; Pilas such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation Zolinium cation; and the like.

  Examples of the cation represented by the general formula (4) include, for example, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a part of the alkyl group substituted with an alkenyl group, an alkoxyl group, or an epoxy group. And the like.

  Specific examples of the cation represented by the general formula (4) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium. Cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation , Tributylsulfonium cation, trihexylsulfonium cation , Diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, Examples include trimethyldecylphosphonium cation and diallyldimethylammonium cation.

  Among these, the triethylmethyl ammonium cation, tributyl ethyl ammonium cation, trimethyl decyl ammonium cation, diethyl methyl sulfonium cation, dibutyl ethyl sulfonium cation, dimethyl decyl sulfonium cation, Asymmetric tetraalkylammonium cations such as triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N, N-diethyl-N-methyl-N- (2-methoxy) Ethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammoni Cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl-N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N-dipropylammonium cation, N, N-diethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N, N-dimethyl -N-propyl-N-hexylammonium cation, N, N-dimethyl- -Propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N-hexylammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl-N-pentyl -N-hexylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl-N- Methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium Cation, triethylheptylammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N, N-dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N-butyl-N -Hexylammonium cation, N, N-dipropyl-N, N-dihexylammonium cation, N, N-dibutyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N-hexylammonium cation , Trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and the like, more preferably trimethylpropylammonium cation.

  Any appropriate fluoroorganic anion can be adopted as the fluoroorganic anion capable of constituting the ionic liquid as long as the effects of the present invention are not impaired. Such a fluoroorganic anion may be completely fluorinated (perfluorinated) or partially fluorinated.

  Examples of such fluoroorganic anions include fluorinated aryl sulfonates, perfluoroalkane sulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonylamides, and bis (cyano). Perfluoroalkanesulfonylmethide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetate, perfluoroalchelate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkane) Sulfonyl) trifluoroacetamide and the like.

  Among these fluoro organic anions, more preferred are perfluoroalkylsulfonate, bis (fluorosulfonyl) imide, bis (perfluoroalkanesulfonyl) imide, and more specifically, for example, trifluoromethanesulfonate, pentafluoroethane. Sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide.

As a specific example of the ionic liquid contained in the polyurethane-based resin, it can be appropriately selected from a combination of the cation component and the anion component. Specific examples of such ionic liquids include, for example, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethane Sulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imi 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) ) Imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis ( Trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Propyl pyro Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1 -Propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfone) Nyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) Imido, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoro) Romethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperi Nitrobis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoro Tansulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidi Nitrobis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1- Methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis ( Pentafluoroethane Sulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexyl Pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide , 1- Ntilpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1 -Methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (penta Fluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl- 1-propi Piperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (Pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3- Methyl imidazolium Mutrifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3 -Methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazole Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazole Bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1,2-dimethyl-3-propylimidazolium Bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoro) Methanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl- 2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2,3 5-trimethylpyrazolium (trifluoromethyl Tansulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-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 (tri Fluoromethanesulfonyl) 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-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N -Propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptyla Monium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, Trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoro) Romethanesulfonyl) imide, N, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammo Ni-bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl -N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoro) Romethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (Trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium (Trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammoni Umbis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis (pentafluoroethanetanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) Examples thereof include imide and lithium bis (fluorosulfonyl) imide.

  Among these ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) Imido, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imi 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) ) Imido, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl -3-methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, Chiumubisu (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

  A commercially available ionic liquid may be used, but it can also be synthesized as follows. The method of synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained. In general, the document “ionic liquids—the forefront and future of development” (CMC Publishing Co., Ltd.). The halide method, the hydroxide method, the acid ester method, the complex formation method, the neutralization method, and the like are used.

  The synthesis method for the halide method, hydroxide method, acid ester method, complex formation method, and neutralization method will be described below using nitrogen-containing onium salts as examples. Other sulfur-containing onium salts and phosphorus-containing onium salts Other ionic liquids can be obtained by the same method.

  The halide method is a method performed by reactions as shown in reaction formulas (1) to (3). First, a tertiary amine and an alkyl halide are reacted to obtain a halide (reaction formula (1), and chlorine, bromine, and iodine are used as the halogen).

Acid (HA) or salt having the anionic structure (A ⁻ ) of the ionic liquid intended for the obtained halide (MA and M are cations that form a salt with the intended anion such as ammonium, lithium, sodium, potassium, etc.) ) To obtain the desired ionic liquid (R ₄ NA).

The hydroxide method is a method performed by reactions as shown in reaction formulas (4) to (8). First, halide (R ₄ NX) is subjected to ion exchange membrane electrolysis (reaction formula (4)), OH type ion exchange resin method (reaction formula (5)) or reaction with silver oxide (Ag ₂ O) (reaction formula ( 6)) to obtain a hydroxide (R ₄ NOH) (chlorine, bromine and iodine are used as the halogen).

The target ionic liquid (R ₄ NA) can be obtained by using the reaction of the reaction formulas (7) to (8) in the same manner as the halogenation method for the obtained hydroxide.

The acid ester method is a method performed by reactions as shown in reaction formulas (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester product (Reaction Formula (9)). As the acid ester, inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid are used. And esters of organic acids such as esters, methanesulfonic acid, methylphosphonic acid, formic acid, etc.).

The target ionic liquid (R ₄ NA) can be obtained by using the reaction of the reaction formulas (10) to (11) in the same manner as the halogenation method for the obtained acid ester. Further, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as the acid ester, an ionic liquid can be directly obtained.

The neutralization method is a method performed by a reaction as shown in the reaction formula (12). A tertiary amine is reacted with an organic acid such as CF ₃ COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, and (C ₂ F ₅ SO ₂ ) ₂ NH. Can be obtained.

  R described in the above reaction formulas (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom.

  The blending amount of the ionic liquid varies depending on the compatibility of the polymer to be used and the ionic liquid, and thus cannot be defined unconditionally. However, in general, the amount is preferably 0.1% with respect to 100 parts by weight of the polyurethane resin. 001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, still more preferably 0.01 to 30 parts by weight, and particularly preferably 0.01 to 20 parts by weight. Parts by weight, most preferably 0.01 parts by weight to 10 parts by weight. By adjusting the blending amount of the ionic liquid within the above range, it is possible to provide a polyurethane resin having excellent antistatic properties. If the amount of the ionic liquid is less than 0.01 parts by weight, sufficient antistatic properties may not be obtained. When the amount of the ionic liquid exceeds 50 parts by weight, contamination of the adherend tends to increase.

  The composition containing the polyol (A) and the polyfunctional isocyanate compound (B) preferably contains any appropriate solvent.

  The content ratio of the polyfunctional isocyanate compound (B) is preferably 5 parts by weight to 60 parts by weight, more preferably 8 parts by weight with respect to 100 parts by weight of the polyol (A). -60 parts by weight, more preferably 10-60 parts by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, it is possible to further develop light releasability with respect to the metal, and more excellent wettability to the entire surface of the metal mesh film. It is possible to provide a pressure-sensitive adhesive composition that can further exhibit low contamination to the film.

  In the polyol (A) and the polyfunctional isocyanate compound (B), the equivalent ratio of the NCO group to the OH group is preferably 1.0 to 5.0, more preferably 1.2 to NCO group / OH group. It is 4.0, More preferably, it is 1.5-3.5, Most preferably, it is 1.8-3.0. By adjusting the equivalent ratio of NCO group / OH group within the above range, it is possible to further develop light release properties for metals, and further improve the wettability to the entire surface of the metal mesh film. On the other hand, it is possible to provide a pressure-sensitive adhesive composition that can further exhibit low contamination.

  As a method for obtaining a polyurethane resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), the effects of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization, are used. Any appropriate method can be adopted as long as it is not impaired.

  In order to cure the composition containing the polyol (A) and the polyfunctional isocyanate compound (B), a catalyst is preferably used. Examples of such a catalyst include organometallic compounds and tertiary amine compounds.

  Examples of organometallic compounds include iron compounds, tin compounds, titanium compounds, zirconium compounds, lead compounds, cobalt compounds, zinc compounds, and the like. Among these, iron-based compounds and tin-based compounds are preferable in terms of reaction rate and pot life of the pressure-sensitive adhesive layer.

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

  Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, Examples include tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Examples of titanium compounds include dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and the like.

  Examples of the zirconium-based compound include zirconium naphthenate and zirconium acetylacetonate.

  Examples of the lead-based compound include lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, and the like.

  Examples of the cobalt-based compound include cobalt 2-ethylhexanoate and cobalt benzoate.

  Examples of the zinc-based compound include zinc naphthenate and zinc 2-ethylhexanoate.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabixic mouth- (5,4,0) -undecene-7, and the like.

  Only one type of catalyst may be used, or two or more types of catalysts may be used. Further, a catalyst and a crosslinking retarder may be used in combination. The amount of the catalyst is preferably 0.02 parts by weight to 0.10 parts by weight, more preferably 0.02 parts by weight to 0.08 parts by weight, with respect to 100 parts by weight of the polyol (A). Preferably it is 0.02 weight part-0.06 weight part, Most preferably, it is 0.02 weight part-0.05 weight part. By adjusting the amount of the catalyst within the above range, light releasability can be further exhibited with respect to the metal, it is more excellent in wettability to the entire surface of the metal mesh film, and low contamination with respect to the metal mesh film. Can be provided, and a pressure-sensitive adhesive composition can be provided.

<Polyurethane resin obtained from composition containing urethane prepolymer (C)>
Any appropriate polyurethane-based resin can be adopted as the polyurethane-based resin obtained from the composition containing the urethane prepolymer (C) as long as it is a polyurethane-based resin obtained using a so-called “urethane prepolymer” as a raw material. .

  The polyurethane resin obtained from the composition containing the urethane prepolymer (C) is, for example, a polyurethane resin obtained from the composition containing the polyurethane polyol as the urethane prepolymer (C) and the polyfunctional isocyanate compound (B). Is mentioned. Only one type of urethane prepolymer (C) may be used, or two or more types may be used. Only one type of polyfunctional isocyanate compound (B) may be used, or two or more types may be used.

  The polyurethane polyol as the urethane prepolymer (C) preferably reacts the polyester polyol (a1) and the polyether polyol (a2) with the organic polyisocyanate compound (a3) in the presence or absence of a catalyst. It is something to be made.

  Any appropriate polyester polyol can be used as the polyester polyol (a1). Examples of such polyester polyol (a1) include polyester polyols obtained by reacting an acid component and a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and the like. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, Examples of the polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol component include glycerin, trimethylolpropane, and pentaerythritol. Other examples of the polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone.

  The molecular weight of the polyester polyol (a1) can be used from a low molecular weight to a high molecular weight. The molecular weight of the polyester polyol (a1) is preferably a number average molecular weight of 500 to 5,000. When the number average molecular weight is less than 500, the reactivity becomes high and the gelation tends to occur. When the number average molecular weight exceeds 5000, the reactivity is lowered, and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyester polyol (a1) used is preferably 10 to 90 parts by weight with respect to 100 parts by weight of the polyol constituting the polyurethane polyol.

  Any appropriate polyether polyol can be used as the polyether polyol (a2). As such a polyether polyol (a2), for example, a low molecular weight polyol such as water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane or the like is used as an initiator, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran or the like is used. The polyether polyol obtained by polymerizing an oxirane compound is mentioned. Specific examples of such polyether polyol (a2) include polyether polyols having 2 or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

  The molecular weight of the polyether polyol (a2) can be used from a low molecular weight to a high molecular weight. As a molecular weight of polyether polyol (a2), a number average molecular weight becomes like this. Preferably it is 1000-5000. When the number average molecular weight is less than 1000, the reactivity is high and the gelation tends to occur. When the number average molecular weight exceeds 5000, the reactivity is lowered, and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyether polyol (a2) used is preferably 20 to 80 parts by weight in 100 parts by weight of the polyol constituting the polyurethane polyol.

  A part of the polyether polyol (a2), if necessary, may be glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, They can be used in combination with polyamines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.

  As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule. A part or all of the polyol may be used. When polyether polyol (a2) having an average molecular weight of 1000 to 5000 and having part or all of polyether polyol having at least 3 hydroxyl groups in one molecule is used, the balance between adhesive force and light peelability Can be good. In such a polyether polyol, if the number average molecular weight is less than 1000, the reactivity becomes high and there is a possibility that gelation tends to occur. Further, in such a polyether polyol, when the number average molecular weight exceeds 5000, the reactivity is lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such a polyether polyol is more preferably 2500 to 3500.

  Any appropriate organic polyisocyanate compound can be used as the organic polyisocyanate compound (a3). Examples of such an organic polyisocyanate compound (a3) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, Examples include 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene. 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl-2. , 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, etc. It is done.

  As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a burette reacted with water, a trimer having an isocyanurate ring, and the like can be used in combination.

  Any appropriate catalyst can be used as the catalyst that can be used in obtaining the polyurethane polyol. Examples of such a catalyst include tertiary amine compounds and organometallic compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU), and the like.

  Examples of organometallic compounds include tin compounds and non-tin compounds.

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

  Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; And zirconium-based compounds such as zirconium naphthenate.

  When a catalyst is used in obtaining a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, are present, due to the difference in reactivity, in a single catalyst system, gelation or a reaction solution is caused. The problem of becoming cloudy is likely to occur. Therefore, by using two kinds of catalysts when obtaining the polyurethane polyol, the reaction rate, the selectivity of the catalyst and the like can be easily controlled, and these problems can be solved. Examples of such a combination of two types of catalysts include tertiary amine / organometallic, tin / non-tin, and tin / tin, preferably tin / tin, more preferably Is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The blending ratio is, by weight ratio, 2-ethylhexanoic acid tin / dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. If the blending ratio is 1 or more, gelation tends to occur due to the balance of catalytic activity.

  When a catalyst is used in obtaining the polyurethane polyol, the amount of the catalyst used is preferably 100 parts by weight based on the total amount of the polyester polyol (a1), the polyether polyol (a2), and the organic polyisocyanate compound (a3). 0.01 parts by weight to 1.0 part by weight.

  When using a catalyst in obtaining a polyurethane polyol, the reaction temperature is preferably less than 100 ° C, more preferably 85 ° C to 95 ° C. If it is 100 ° C. or higher, it may be difficult to control the reaction rate and the crosslinked structure, and it may be difficult to obtain a polyurethane polyol having a predetermined molecular weight.

  When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, reaction temperature becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 110 degreeC or more. Moreover, when obtaining a polyurethane polyol without a catalyst, it is preferable to make it react for 3 hours or more.

  For example, 1) polyester polyol, polyether polyol, catalyst, and organic polyisocyanate are charged in a flask. 2) polyester polyol, polyether polyol, and catalyst are charged in a flask, and organic polyisocyanate is obtained. The method of adding by dripping is mentioned. As a method for obtaining the polyurethane polyol, the method 2) is preferable in controlling the reaction.

  Any suitable solvent can be used to obtain the polyurethane polyol. Examples of such a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Among these solvents, toluene is preferable.

  What was mentioned above can be used as a polyfunctional isocyanate compound (B).

  The composition containing the urethane prepolymer (C) may contain any appropriate other component as long as the effects of the present invention are not impaired. What was mentioned above can be used as such other components.

  As a method for producing a polyurethane-based resin obtained from the composition containing the urethane prepolymer (C), any appropriate method can be used as long as it is a method for producing a polyurethane-based resin using a so-called “urethane prepolymer” as a raw material. A manufacturing method may be adopted.

≪Azole compounds≫
The azole compound contained in the pressure-sensitive adhesive composition of the present invention is an azole compound other than an azole compound having a 1,2,3-triazole structure and having a phenyl ring structure bonded to the 2-position. Here, the azole compound is a general term for compounds having a hetero 5-membered ring structure containing one or more nitrogen atoms.

  By adopting an azole compound other than an azole compound having a 1,2,3-triazole structure and having a phenyl ring structure bonded to the 2-position as an azole compound contained in the pressure-sensitive adhesive composition of the present invention, a metal Thus, it is possible to provide a pressure-sensitive adhesive composition that can effectively prevent corrosion.

  The azole compound contained in the pressure-sensitive adhesive composition of the present invention preferably has an imidazole compound, an isomer of an imidazole compound, a 1,2,3-triazole structure, and a phenyl ring structure bonded to the 2-position. It is at least one selected from benzotriazole-based compounds that are not present.

  Examples of the imidazole compound include imidazole, pyrazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2,5-dihydro-1H-imidazole, 4,5-dihydro- Examples include 1H-pyrazole.

  Examples of the benzotriazole compounds having a 1,2,3-triazole structure and having no phenyl ring structure bonded to the 2-position include 1,2,3-benzotriazole, 1- [N, N-bis (2-Ethylhexyl) aminomethyl] benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, 5-methylbenzotriazole, carboxybenzotriazole, 2,2 ′-[[methyl- 1H-benzotriazol-1-yl] methyl] imino] bisethanol, 1,2,3-benzotriazole sodium salt and the like.

  The content of the azole compound with respect to 100 parts by weight of the resin contained in the pressure-sensitive adhesive composition of the present invention is preferably 0.05 to 5 parts by weight, more preferably 0.06 to 4 parts by weight. More preferably, it is 0.07 parts by weight to 3 parts by weight, particularly preferably 0.08 parts by weight to 2 parts by weight, and most preferably 0.1 parts by weight to 1 part by weight. To provide a pressure-sensitive adhesive composition capable of more effectively preventing metal corrosion by adjusting the content ratio of the azole compound to 100 parts by weight of the resin contained in the pressure-sensitive adhesive composition of the present invention within the above range. Can do.

≪≪Surface protection film≫≫
The surface protective film of this invention has the adhesive layer and base material layer which are formed from the adhesive composition of this invention.

  Only one layer may be sufficient as a base material layer, and two or more layers may be sufficient as it. In addition to the base material layer and the pressure-sensitive adhesive layer, the surface protective film of the present invention may have any other appropriate layer as long as the effects of the present invention are not impaired.

  FIG. 1 is a schematic cross-sectional view of a surface protective film according to a preferred embodiment of the present invention. The surface protective film 10 includes a base material layer 1 and an adhesive layer 2. The surface protective film of the present invention may further have any appropriate other layer as required (not shown).

  For the purpose of forming a wound body that can be easily rewound on the surface of the base material layer 1 that is not provided with the pressure-sensitive adhesive layer 2, for example, the base material layer includes a fatty acid amide, polyethyleneimine, and a long-chain alkyl series. A release treatment can be performed by adding an additive or the like, or a coating layer made of any appropriate release agent such as silicone, long-chain alkyl, or fluorine can be provided.

  The surface protective film of the present invention may be bonded with a release liner having releasability.

  The thickness of the surface protective film of the present invention can be set to any appropriate thickness depending on the application. From the viewpoint of sufficiently expressing the effects of the present invention, the thickness is preferably 5 μm to 250 μm, more preferably 10 μm to 200 μm, still more preferably 15 μm to 175 μm, and particularly preferably 20 μm to 150 μm.

  In the surface protective film of the present invention, the change in reflectance at 550 nm with respect to copper is preferably 50% or less, more preferably 30% or less, still more preferably 20% or less, and particularly preferably 10% or less. . Provided is a surface protective film having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition capable of effectively preventing metal corrosion by adjusting the 550 nm reflectance change of copper of the surface protective film of the present invention within the above range. can do. Note that the change in reflectance at 550 nm with respect to copper is obtained by the following equation, and details thereof will be described later.

  550 nm reflectivity change with respect to copper (%) = [1-{(550 nm reflectivity after storage for 120 hours at 60 ° C. × 90% RH) / (550 nm reflectivity before storage for 120 hours at 60 ° C. × 90% RH)} ] × 100

  The surface protective film of the present invention has an adhesive strength to an acrylic plate at 23 ° C. × 50% RH of preferably 0.001 N / 25 mm to 0.06 N / 25 mm, more preferably 0.003 N / 25 mm to 0.00. 05N / 25mm, more preferably 0.005N / 25mm to 0.04N / 25mm, and particularly preferably 0.007N / 25mm to 0.03N / 25mm. By adjusting the adhesive strength of the surface protective film of the present invention to an acrylic plate at 23 ° C. × 50% RH within the above range, it is formed from an adhesive composition having moderately excellent adhesiveness to the entire surface of the metal mesh film. A surface protective film having a pressure-sensitive adhesive layer can be provided. In addition, the detail of the adhesive force with respect to an acrylic board in 23 degreeC x 50% RH is mentioned later.

  In the surface protective film of the present invention, the adhesive force to copper at 23 ° C. × 50% RH is preferably 0.001 N / 25 mm to 0.07 N / 25 mm, more preferably 0.003 N / 25 mm to 0.06 N. / 25 mm, more preferably 0.005 N / 25 mm to 0.05 N / 25 mm, and particularly preferably 0.007 N / 25 mm to 0.04 N / 25 mm. The pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition that can exhibit light releasability with respect to metal by adjusting the pressure-sensitive adhesive force to copper at 23 ° C. × 50% RH of the surface protective film of the present invention. The surface protection film which has can be provided. In addition, the detail of the adhesive force with respect to copper in 23 degreeC x 50% RH is mentioned later.

  In the surface protective film of the present invention, the wetting speed at 23 ° C. × 50% RH is preferably 15 seconds or less, more preferably 13 seconds or less, and further preferably 10 seconds or less. By adjusting the wetting speed of the surface protective film of the present invention at 23 ° C. × 50% RH within the above range, a surface protective film excellent in wettability to the entire surface of the metal mesh film can be provided. Details of the wetting speed at 23 ° C. × 50% RH will be described later.

  The surface protective film of the present invention has a residual adhesive force after pasting of 60 ° C. × 90% RH for 48 hours, preferably 90% or more, more preferably 92% or more, further preferably 94% or more, Especially preferably, it is 96% or more, Most preferably, it is 97% or more. By adjusting the residual adhesive strength of the surface protective film of the present invention after pasting at 60 ° C. × 90% RH for 48 hours within the above range, it is formed from a pressure-sensitive adhesive composition that can exhibit low contamination to the metal mesh film. A surface protective film having a pressure-sensitive adhesive layer can be provided. The details of the residual adhesive strength after pasting for 60 hours at 60 ° C. × 90% RH will be described later.

≪Adhesive layer≫
The pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition of the present invention.

  As the thickness of the pressure-sensitive adhesive layer, any appropriate thickness can be adopted depending on the application. The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 100 μm, more preferably 2 μm to 90 μm, further preferably 3 μm to 80 μm, particularly preferably 4 μm to 60 μm, and most preferably 5 μm to 30 μm. . When the thickness of the pressure-sensitive adhesive layer is less than 1 μm, it is difficult to obtain a sufficient adhesive force, and the surface protective film (specifically, the pressure-sensitive adhesive layer) itself cannot be fixed to the adherend and is easily peeled off. If the thickness exceeds 100 μm, the adhesive strength may increase with time and it may be difficult to peel off. In addition, as an adhesive layer, any form of a single layer and a laminated body may be sufficient.

  The pressure-sensitive adhesive layer can be produced by any appropriate production method. Examples of such a production method include a method of applying the pressure-sensitive adhesive composition of the present invention, which is a material for forming the pressure-sensitive adhesive layer, onto the base material layer and forming the pressure-sensitive adhesive layer on the base material layer. Examples of such coating methods include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.

  In addition to the pressure-sensitive adhesive composition of the present invention, the pressure-sensitive adhesive layer can contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than urethane adhesives, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, and anti-aging agents. , Conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, corrosion inhibitor, heat stabilizer, polymerization inhibitor, lubricant, solvent, and the like.

≪Base material layer≫
Any appropriate thickness can be adopted as the thickness of the base material layer depending on the application. The thickness of the base material layer is preferably 5 μm to 250 μm, more preferably 7 μm to 200 μm, still more preferably 10 μm to 175 μm, and particularly preferably 15 μm to 150 μm.

  The base material layer may be a single layer or a laminate of two or more layers. The base material layer may be stretched.

  Any appropriate material can be adopted as the material of the base material layer depending on the application. For example, a plastic, paper, a metal film, a nonwoven fabric, etc. are mentioned. Preferably, it is a plastic. The base material layer may be composed of one kind of material, or may be composed of two or more kinds of materials. For example, you may be comprised from 2 or more types of plastics.

  Examples of the plastic include a polyester resin, a polyamide resin, and a polyolefin resin. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin resin include olefin monomer homopolymers, olefin monomer copolymers, and the like. Specific examples of polyolefin resins include homopolypropylene; block-type, random-type, and graft-type propylene copolymers having an ethylene component as a copolymer component; reactor TPO; low density, high density, linear Low density, ultra-low density, etc. ethylene polymers; ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid And ethylene copolymers such as butyl copolymer, ethylene / methacrylic acid copolymer, and ethylene / methyl methacrylate copolymer.

  The base material layer may contain any appropriate additive as required. Examples of the additive that can be contained in the base material layer include an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, and a pigment. The kind, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration. From the viewpoint of improving weather resistance and the like, particularly preferred additives include antioxidants, ultraviolet absorbers, light stabilizers, and fillers.

  Any appropriate antioxidant can be adopted as the antioxidant. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, phenol-phosphorus-based antioxidants, and the like. The content of the antioxidant is preferably 1 part by weight or less with respect to 100 parts by weight of the base resin of the base layer (when the base layer is a blend, the blend is the base resin), More preferably, it is 0.5 weight part or less, More preferably, it is 0.01 weight part-0.2 weight part.

  Arbitrary appropriate ultraviolet absorbers can be employ | adopted as a ultraviolet absorber. Examples of such UV absorbers include benzotriazole UV absorbers, triazine UV absorbers, and benzophenone UV absorbers. The content of the ultraviolet absorber is preferably 2 parts by weight or less with respect to 100 parts by weight of the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). More preferably 1 part by weight or less, still more preferably 0.01 part by weight to 0.5 part by weight.

  Any appropriate light stabilizer can be adopted as the light stabilizer. Examples of such light stabilizers include hindered amine light stabilizers and benzoate light stabilizers. The content ratio of the light stabilizer is preferably 2 parts by weight or less with respect to 100 parts by weight of the base resin forming the base layer (in the case where the base layer is a blend, the blend is the base resin). More preferably 1 part by weight or less, still more preferably 0.01 part by weight to 0.5 part by weight.

  Any appropriate filler can be adopted as the filler. Examples of such fillers include inorganic fillers. Specific examples of the inorganic filler include carbon black, titanium oxide, and zinc oxide. The content of the filler is preferably 20 parts by weight or less with respect to 100 parts by weight of the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). The amount is more preferably 10 parts by weight or less, and still more preferably 0.01 parts by weight to 10 parts by weight.

  Furthermore, as the additive, for the purpose of imparting antistatic properties, inorganic, low molecular weight and high molecular weight antistatic agents such as surfactants, inorganic salts, polyhydric alcohols, metal compounds, carbon and the like are also preferred. In particular, a high molecular weight antistatic agent and carbon are preferable from the viewpoint of contamination and adhesiveness maintenance.

≪Method for producing surface protective film≫
The surface protective film of the present invention can be produced by any appropriate method. As such a manufacturing method, for example,
(1) A method of applying a solution or a hot melt of the pressure-sensitive adhesive composition of the present invention, which is a material for forming a pressure-sensitive adhesive layer, onto a base material layer,
(2) A method of transferring the pressure-sensitive adhesive layer applied and formed in the form of a separator onto the base material layer according to that,
(3) A method of forming and applying the pressure-sensitive adhesive composition of the present invention, which is a material for forming the pressure-sensitive adhesive layer, onto the base material layer,
(4) A method of extruding a base material layer and an adhesive layer in two layers or multiple layers,
(5) A method of laminating a pressure-sensitive adhesive layer on a base material layer, or a method of laminating two pressure-sensitive adhesive layers together with a laminate layer,
(6) A method of laminating a pressure-sensitive adhesive layer and a base material layer forming material such as a film or a laminate layer in two or multiple layers,
It can be performed according to any appropriate production method.

  As a coating method, for example, a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, a gravure coater method, or the like can be used.

≪≪Transparent conductive film with surface protective film≫≫
The transparent conductive film with a surface protective film of the present invention has a metal thin film on at least one surface of a transparent resin substrate, and has the surface protective film of the present invention on the surface of the metal thin film.

  The transparent resin base material preferably has transparency in the visible region and has a total light transmittance of 90% or more. Moreover, since the resin film which has flexibility is excellent in handleability, it is preferable as a transparent resin base material.

  Specific examples of the resin film used for the transparent resin substrate include, for example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins, epoxy resins, fluorine resins, silicone resins, polycarbonate resins, Single layer film made of diacetate resin, triacetate resin, polyarylate resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, polyimide resin, polyamide resin, polyolefin resin, cyclic polyolefin resin, etc. or multiple layers made of these resins The composite film is mentioned.

  The transparent conductive film with a surface protective film of the present invention has a metal thin film on at least one surface of a transparent resin substrate. This metal thin film is preferably formed by forming a film on at least one surface of the transparent resin substrate.

  Any appropriate method can be adopted as a method for forming the metal thin film. Examples of such a method include vapor deposition, sputtering, plating, coating, printing, and ion plate method.

  Arbitrary appropriate metals can be employ | adopted as a metal used as the material of a metal thin film. Examples of such metals include gold, silver, copper, nickel, aluminum, tin, chromium, titanium, stainless steel, zinc, and composite materials thereof. The metal used as the material of the metal thin film may be only one type or two or more types.

  The surface of the metal thin film may be subjected to surface treatment such as blackening treatment or coating treatment.

  The metal thin film may be patterned. Any appropriate method can be adopted as a method of forming such a metal pattern. As such a method, for example, a method using a silver salt photosensitive material, a method of applying electroless plating or electrolytic plating to a silver image further obtained by using the same method, and a conductive material such as a silver paste using a screen printing method. A method of printing a conductive ink, a method of printing a conductive ink such as silver ink by an ink jet method, a conductive layer is formed by vapor deposition or sputtering, a resist film is formed thereon, exposure, development, etching, resist Examples thereof include a method obtained by removing a layer, a method in which a metal foil such as a copper foil is attached, a resist film is further formed thereon, exposure, development, etching, and removal of the resist layer are performed.

  The pattern shape when the metal thin film is patterned is preferably a mesh pattern. Examples of the mesh pattern include a lattice mesh pattern made up of squares, rectangles, rhombuses, etc., a mesh pattern made up of triangles, pentagons or more polygons, a mesh pattern made up of circles and ellipses, and a mesh pattern made up of these combined shapes. And a random mesh pattern.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. In addition, the test and evaluation method in an Example etc. are as follows. Note that “parts” means “parts by weight” unless otherwise noted, and “%” means “% by weight” unless otherwise noted.

<Corrosive>
The surface protective film was bonded to the copper side of a film obtained by vapor-depositing copper on a PET film, cut to 50 mm × 50 mm, and used as a sample for evaluation. The sample for evaluation was stored for 120 hours in an atmosphere of a temperature of 60 ° C. and a humidity of 90% RH, and the corrosivity was evaluated.
A: When the surface protective film is peeled off from the sample for evaluation, there is no discoloration of the copper surface.
○: When the surface of the surface protection film was peeled off from the sample for evaluation taken out, the copper surface was slightly discolored.
X: When discoloration of the copper surface is remarkable when the surface protective film is peeled off from the sample for evaluation taken out.

<550 nm reflectance change with respect to copper>
As an adherend for evaluation, the PET side of a film in which copper was vapor-deposited on a PET film was bonded to a glass with a double-sided tape, and an evaluation adherend was prepared in which the copper side of the film on which copper was vapor-deposited became the surface. . The reflectance of 550 nm (SCI measurement value) was measured on the copper surface of the evaluation adherend using a spectrocolorimeter “CM-2600d” manufactured by Konica Minolta, and the surface protective film was cut into 25 mm × 100 mm. Then, they were bonded to the copper surface of the adherend for evaluation to obtain a sample for evaluation. The sample for evaluation was stored for 120 hours in an atmosphere at a temperature of 60 ° C. and a humidity of 90% RH, and after the surface protective film was peeled off, the reflectance (SCI measured value) at 550 nm was measured again.
The change in reflectance at 550 nm with respect to copper was determined by the following formula.
550 nm reflectivity change with respect to copper (%) = [1-{(550 nm reflectivity after storage for 120 hours at 60 ° C. × 90% RH) / (550 nm reflectivity before storage for 120 hours at 60 ° C. × 90% RH)} ] × 100

<Adhesive strength to acrylic plate at 23 ° C. × 50% RH>
The surface protective film was cut into a width of 25 mm and a length of 150 mm to obtain a sample for evaluation. In an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH, the pressure-sensitive adhesive layer surface of the sample for evaluation was attached to an acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite L # 001) by one reciprocating 2.0 kg roller. . After curing for 30 minutes in an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH, using a universal tensile tester (product name: TCM-1kNB, manufactured by Minebea Co., Ltd.) at a peeling angle of 180 ° and a pulling speed of 300 mm / min. It peeled and the adhesive force was measured.

<Adhesive strength to copper at 23 ° C. × 50% RH>
As an adherend for evaluation, the PET side of a film in which copper was vapor-deposited on a PET film was bonded to a glass with a double-sided tape, and an evaluation adherend was prepared in which the copper side of the film on which copper was vapor-deposited became the surface. . The surface protective film was cut into a width of 25 mm and a length of 150 mm to obtain a sample for evaluation. Under an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH, the pressure-sensitive adhesive layer surface of the evaluation sample was attached to the copper surface of the evaluation adherend by one reciprocating 2.0 kg roller. After curing for 30 minutes in an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH, using a universal tensile tester (product name: TCM-1kNB, manufactured by Minebea Co., Ltd.) at a peeling angle of 180 ° and a pulling speed of 300 mm / min. It peeled and the adhesive force was measured.

<Wetting speed at 23 ° C. × 50% RH>
The surface protective film was cut into a width of 25 mm and a length of 100 mm to obtain an evaluation sample. Using an acrylic plate (trade name: Acrylite L # 001, manufactured by Mitsubishi Rayon Co., Ltd.) as the adherend, peel off the separator of the evaluation sample, fix one end of the width side, and end the width side that is not fixed The time (unit: s / 25 mm × 10 mm) from lifting the part and releasing the hand until wetting and spreading by 100 mm was measured.
○: Wetting spread time is less than 10 seconds.
×: Wetting and spreading time is 10 seconds or more or wetting and spreading does not occur.

<Residual adhesive strength after application at 60 ° C. × 90% RH for 48 hours>
A surface protective film was bonded to the entire surface with an acrylic plate (Mitsubishi Rayon Co., Ltd., trade name: Acrylite L # 001) with a hand roller, and stored for 48 hours in an atmosphere of temperature 60 ° C. and humidity 90% RH. The surface protective film was peeled off at a speed of 0.3 m / min and cut into a length of 150 mm and a 19 mm wide No. A 31B tape (manufactured by Nitto Denko Corporation, substrate thickness: 25 μm) was attached by reciprocating 2.0 kg roller in an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH. After curing for 30 minutes in an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH, using a universal tensile tester (product name: TCM-1kNB, manufactured by Minebea Co., Ltd.) at a peeling angle of 180 ° and a pulling speed of 300 mm / min. It peeled and the adhesive force was measured.
Separately, for an acrylic plate not subjected to the above-described treatment, a 19 mm wide No. The adhesive strength of the 31B tape was measured, and the residual adhesive strength was calculated by the following formula.
Residual adhesive strength (%) = (No. 31B adhesive strength to acrylic plate after surface protective film peeling / No. 31B adhesive strength to acrylic plate) × 100
This residual adhesive force is an index of how much the adhesive component of the surface protective film is transferred and contaminated on the surface of the adherend. The higher the value of the residual adhesive force, the better the surface protection film without contaminating the adherend, and the lower the value of the residual adhesive force, the more contaminated the surface of the adherend with an adhesive component or the like. .

<Contamination>
○: Residual adhesive strength is 90% or more.
X: Residual adhesive strength is less than 90%.

[Comparative Example 1]
(Adhesive composition)
As a polyol, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) which is a polyol having 3 OH groups: Sanix GP-3000 (manufactured by Sanyo Chemical Co., Ltd.) which is a polyol having 3 OH groups Mn = 3000): 13 parts by weight, a polyol having 3 OH groups, Sanniks GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000): 2 parts by weight, and trimethylolpropane / Tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX): 17.7 parts by weight (in terms of solid content), Nersem ferric acid (manufactured by Nippon Chemical Industry Co., Ltd.): 0.04 parts by weight, Irganox 1010 (manufactured by BASF) as a deterioration inhibitor: 0.50 part by weight, blended with solid content As a 35 wt% it was diluted with ethyl acetate, and stirred with a disper to obtain a pressure-sensitive adhesive composition comprising a polyurethane-based resin (C1).
(Surface protection film)
The pressure-sensitive adhesive composition (C1) was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain coater was 10 μm, a drying temperature 130 ° C., and a drying time 2 Cure and dry under conditions of minutes. Thus, the adhesive layer was produced on the base material. Next, a silicone treatment of a 38 μm thick polyester resin (Mitsubishi Resin Co., Ltd., thickness: 38 μm, trade name “Diafoil MRF # 38”) having a silicone treatment on one surface on the surface of the adhesive layer The surfaces were bonded together and further allowed to stand at 50 ° C. for 3 days to obtain a surface protective film (C1).
The results are shown in Table 1.

[Example 1]
(Adhesive composition)
Further, Comparative Example 1 except that BT-120 solution dissolved in ethyl acetate was added so that 0.1 part by weight of 1,2,3-benzotriazole (BT-120, manufactured by Johoku Chemical Co., Ltd.) was added as a solid content. It carried out similarly and obtained the adhesive composition (1) containing a polyurethane-type resin.
(Surface protection film)
A surface protective film (1) was obtained in the same manner as in Comparative Example 1, except that the pressure-sensitive adhesive composition (1) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

[Example 2]
(Adhesive composition)
Further, Comparative Example 1 except that BT-120 solution dissolved in ethyl acetate was added so that 0.5 part by weight of 1,2,3-benzotriazole (BT-120, manufactured by Johoku Chemical Co., Ltd.) was added as a solid content. It carried out similarly and obtained the adhesive composition (2) containing a polyurethane-type resin.
(Surface protection film)
A surface protective film (2) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (2) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

Example 3
(Adhesive composition)
Further, fatty acid ester (isopropyl palmitate, manufactured by Kao, trade name: Exepal IPP, Mn = 299): 30 parts by weight, 1,2,3-benzotriazole (BT-120, manufactured by Johoku Chemical Industry Co., Ltd.) with a solid content of 0 A pressure-sensitive adhesive composition (3) containing a polyurethane resin was obtained in the same manner as in Comparative Example 1 except that a BT-120 solution dissolved in ethyl acetate was added so as to add 5 parts by weight.
(Surface protection film)
A surface protective film (3) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (3) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

Example 4
(Adhesive composition)
Furthermore, fatty acid ester (isopropyl palmitate, manufactured by Kao, trade name: Exepal IPP, Mn = 299): 30 parts by weight, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., AS210): 1.5 parts by weight, polyether-modified silicone (PEG-32 methyl ether dimethicone, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.01 parts by weight, 1,2,3-benzotriazole (BT-120, Johoku Chemical Industry) Manufactured in the same manner as in Comparative Example 1 except that a BT-120 solution dissolved in ethyl acetate was added so that 0.5 part by weight of the solid content was added to obtain a pressure-sensitive adhesive composition (4) containing a polyurethane resin. It was.
(Surface protection film)
A surface protective film (4) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (4) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

Example 5
(Adhesive composition)
Further, Comparative Example 1 except that BT-120 solution dissolved in ethyl acetate was added so that 1.0 part by weight of 1,2,3-benzotriazole (BT-120, manufactured by Johoku Chemical Co., Ltd.) was added as a solid content. It carried out similarly and obtained the adhesive composition (5) containing a polyurethane-type resin.
(Surface protection film)
A surface protective film (5) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (5) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

Example 6
(Adhesive composition)
Further, TT-LX dissolved in ethyl acetate so that 0.5 part by weight of 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole (TT-LX, manufactured by Johoku Chemical Co., Ltd.) is added as a solid content. A pressure-sensitive adhesive composition (6) containing a polyurethane resin was obtained in the same manner as in Comparative Example 1 except that the solution was blended.
(Surface protection film)
A surface protective film (6) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (6) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

Example 7
(Adhesive composition)
Furthermore, it carried out similarly to the comparative example 1 except having mix | blended 5M-BTA solution which melt | dissolved with ethyl acetate so that 0.5 weight part of 5-methylbenzotriazole (5M-BTA, Johoku Chemical Industry Co., Ltd.) might be added by solid content. An adhesive composition (7) containing a polyurethane resin was obtained.
(Surface protection film)
A surface protective film (7) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (7) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

Example 8
(Adhesive composition)
Further, except that an imidazole solution dissolved in ethyl acetate was added so that 0.5 part by weight of imidazole (manufactured by Kanto Chemical Co., Inc.) was added, a pressure-sensitive adhesive composition containing a polyurethane resin was carried out in the same manner as in Comparative Example 1. (8) was obtained.
(Surface protection film)
A surface protective film (8) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (8) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

[Comparative Example 2]
(Adhesive composition)
Further, a Tinuvin PS solution dissolved in ethyl acetate was added so that 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole (Tinvin PS, manufactured by BASF) was added in an amount of 0.5 parts by weight as a solid content. Except that, it carried out similarly to the comparative example 1, and obtained the adhesive composition (C2) containing a polyurethane-type resin.
(Surface protection film)
A surface protective film (C2) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (C2) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

[Comparative Example 3]
(Adhesive composition)
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 100 parts by weight, 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) ): 10 parts by weight, acrylic acid (manufactured by Toa Gosei Co., Ltd.): 0.02 parts by weight, 2,2′-azobisisobutyronitrile as a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 Part by weight, ethyl acetate: 192 parts by weight, nitrogen gas was introduced with gentle stirring, and the polymerization temperature was kept at around 60 ° C. for 8 hours to conduct an acrylic polymer solution (solid content 36 % By weight) was prepared. The weight average molecular weight of the acrylic polymer in the obtained acrylic polymer solution was 650,000.
In the obtained acrylic polymer solution, trimethylolpropane / tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate HX) as a cross-linking agent with respect to 100 parts by weight of the solid content of the acrylic polymer in terms of solid content. 5 parts by weight, dioctyltin dilaurate (manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst is added in 0.02 part by weight in terms of solid content, diluted with ethyl acetate so that the solid content is 25% by weight, and stirred with a disper. A pressure-sensitive adhesive composition (C3) containing an acrylic resin was obtained.
(Surface protection film)
A surface protective film (C3) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (C3) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

[Comparative Example 4]
(Adhesive composition)
Further, Comparative Example 3 except that BT-120 solution dissolved in ethyl acetate was added so that 0.5 part by weight of 1,2,3-benzotriazole (BT-120, manufactured by Johoku Chemical Co., Ltd.) was added as a solid content. It carried out similarly and obtained the adhesive composition (C4) containing acrylic resin.
(Surface protection film)
A surface protective film (C4) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (C4) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

[Comparative Example 5]
(Adhesive composition)
Trimethylolpropane / tolylene diisocyanate (crosslinker) was added as a crosslinking agent to the urethane prepolymer solution for pressure-sensitive adhesive (SH-109, manufactured by Toyochem Co., Ltd.) with respect to 100 parts by weight of the solid content of the urethane prepolymer for pressure-sensitive adhesive. Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd. was added in 6 parts by weight in terms of solid content, and ethyl acetate was added and mixed and stirred so that the solid content of the prepared solution was 25%. A pressure-sensitive adhesive composition (C5) containing a resin was obtained.
(Surface protection film)
A surface protective film (C5) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (C5) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

Example 9
(Adhesive composition)
Further, Comparative Example 5 except that BT-120 solution dissolved in ethyl acetate was added so that 1,2,3-benzotriazole (BT-120, manufactured by Johoku Chemical Industry Co., Ltd.) was added in an amount of 0.5 parts by weight as a solid content. It carried out similarly and obtained the adhesive composition (9) containing a prepolymer type polyurethane-type resin.
(Surface protection film)
A surface protective film (9) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive composition (9) was used instead of the pressure-sensitive adhesive composition (C1).
The results are shown in Table 1.

Example 10
(Adhesive composition)
A four-necked separable flask was equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a condenser tube with a trap, and the molar ratio of dimer acid as dicarboxylic acid to propylene glycol as diol was 1.00. : Dimer acid (trade name “Pripol 1009”, manufactured by Croda, weight average molecular weight: 567): 619 parts by weight, propylene glycol (trade name “propylene glycol”, manufactured by Wako Pure Chemical Industries, Ltd.) , Weight average molecular weight: 76): 100 parts by weight, dibutyltin oxide (IV) (manufactured by Kishida Chemical Co., Ltd.): 0.1 part by weight as a catalyst, and the temperature was raised to 160 ° C. while stirring at normal pressure. Retained. The reaction was continued for about 14 hours while removing the reaction product water through the cooling tube. Further, the nitrogen introduction tube and the cooling tube with a trap were removed, a vacuum pump was attached, and the temperature was maintained at 160 ° C. while stirring in a reduced pressure atmosphere (0.002 MPa). The reaction was continued for about 4 hours to obtain a polyester polymer.
Polyester polyol (trade name “Smack MP-70”, manufactured by Kao Corporation, one-end methyl ether type polypropylene glycol): 20 parts by weight, an isocyanurate type poly as a crosslinking agent with respect to 100 parts by weight of the obtained polyester polymer Hexamethylene diisocyanate (trade name “Desmodur N3600”, manufactured by Sumika Bayer Co., Ltd.): 30 parts by weight is blended, and 1,2,3-benzotriazole (BT-120, manufactured by Johoku Chemical Co., Ltd.) has a solid content of 0.001. Add BT-120 solution dissolved in ethyl acetate to add 5 parts by weight, and add ethyl acetate as a solvent so that the viscosity after adjustment is 10 Pa · s to obtain a pressure-sensitive adhesive composition (10) containing a polyester resin. It was.
(Surface protection film)
A pressure-sensitive adhesive composition (10) was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain coater would be 10 μm, drying temperature 100 ° C., drying time 3 Cure and dry under conditions of minutes. Thus, the adhesive layer was produced on the base material. Next, a silicone treatment of a 38 μm thick polyester resin (Mitsubishi Resin Co., Ltd., thickness: 38 μm, trade name “Diafoil MRF # 38”) having a silicone treatment on one surface on the surface of the adhesive layer The surfaces were bonded together and further allowed to stand at 40 ° C. for 7 days to obtain a surface protective film (10).
The results are shown in Table 1.

[Comparative Example 6]
(Adhesive composition)
Addition reaction type silicone pressure sensitive adhesive (trade name “X-40-3306”, manufactured by Shin-Etsu Chemical Co., Ltd.): 100 parts by weight and platinum-based catalyst (trade name “CAT-PL-50T”, manufactured by Shin-Etsu Chemical Co., Ltd.) ): 0.2 parts by weight were mixed to obtain a pressure-sensitive adhesive composition (C6) containing a silicone resin.
(Surface protection film)
Silicone-treated polyester resin (Mitsubishi Resin Co., Ltd., thickness: 38 μm, product name “Diafoil MRF # 38”) with a silicone treatment on one side, the thickness after drying with a fountain coater The pressure-sensitive adhesive composition (C6) was applied so as to be 10 μm, and was cured and dried under the conditions of a drying temperature of 140 ° C. and a drying time of 3 minutes. Thus, the adhesive layer was produced on the base material. Subsequently, a 25 μm thick polyester resin (“Lumirror S10” (thickness 25 μm, manufactured by Toray Industries, Inc.) was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (C6).
The results are shown in Table 1.

[Comparative Example 7]
(Adhesive composition)
Further, Comparative Example 6 except that BT-120 solution dissolved in ethyl acetate was added so that 1,2,3-benzotriazole (BT-120, manufactured by Johoku Chemical Industry Co., Ltd.) was added in an amount of 0.5 parts by weight as a solid content. It carried out similarly and obtained the adhesive composition (C7) containing a silicone type resin.
(Surface protection film)
A surface protective film (C7) was obtained in the same manner as in Comparative Example 6 except that the pressure-sensitive adhesive composition (C6) was replaced with the pressure-sensitive adhesive composition (C7).
The results are shown in Table 1.

  According to the present invention, it is possible to express light releasability with respect to a metal, excellent wettability to the entire surface of the metal mesh film, exhibit low contamination with respect to the metal mesh film, and effectively corrode metal. A surface protective film having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition that can be prevented can be provided. Such a surface protective film is, for example, a metal electrode on a substrate in the field of precision electronic equipment such as a touch panel. It is useful as a surface protective film for metal mesh films provided with metal circuits.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 10 Surface protection film

Claims (7)

A pressure-sensitive adhesive composition comprising a resin and an azole compound,
The resin is at least one selected from polyurethane resins and polyester resins,
The azole compound is an azole compound other than an azole compound having a 1,2,3-triazole structure and having a phenyl ring structure bonded to the 2-position.
Adhesive composition.   The azole compound is at least one selected from imidazole compounds, isomers of imidazole compounds, and benzotriazole compounds having a 1,2,3-triazole structure and having no phenyl ring structure bonded to the 2-position. The pressure-sensitive adhesive composition according to claim 1, wherein   The pressure-sensitive adhesive composition according to claim 1 or 2, wherein a content ratio of the azole compound with respect to 100 parts by weight of the resin is 0.05 part by weight to 5 parts by weight.   The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the resin is a polyurethane resin.   The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the polyurethane-based resin is a polyurethane-based resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).   A surface protective film comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to claim 1 and a base material layer.   The transparent conductive film with a surface protective film which has a metal thin film in the at least one surface of a transparent resin base material, and has the surface protective film of Claim 6 on the surface of this metal thin film.

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