KR20200007768A - Adhesive, adhesive sheet, manufacturing method of adhesive sheet, and image display apparatus - Google Patents

Abstract

Provided are an adhesive, a pressure-sensitive adhesive sheet, a manufacturing method of the pressure-sensitive adhesive sheet capable of satisfying re-peelability, wettability, adherend contamination under high temperature and high humidity, and an image display apparatus. The pressure-sensitive adhesive of the present invention is at least one selected from the group consisting of a polyurethane prepolymer (A), an organic acid (B-1), an acidic phosphate ester compound (B-2), and an organic acid anhydride (B-3). Wherein the acidic phosphate ester compound (B-2) is at least one selected from the group consisting of acidic phosphate ester compounds represented by the following formulas (I), (II) and (III), wherein the organic acid ( B-1) is an organic acid other than the acidic phosphoric acid ester compound (B-2), and the prepolymer (A) of the polyurethane is a prepolymer synthesized with a polyol and an isocyanate. In said general formula (I), R <^1> and R <^2> is a hydrogen atom, a hydrocarbon group, or an aryl group, respectively, R <^1> and R <^2> may be same or different, At least one of R <^1> and R <^2> is a hydrocarbon group Or an aryl group. In said Formula (II) and (III), R <^3> and R <^4> is a hydrogen atom, a hydrocarbon group, or an aryl group, respectively, R <^3> and R <^4> may be same or different, and at least one of R <^3> and R <^4> . Is a hydrocarbon group or an aryl group, AO is an alkylene oxide group, and each AO may be same or different, n represents an integer of 1 or more, and each n may be the same or different.

Description

Adhesive, adhesive sheet, manufacturing method of adhesive sheet, and image display apparatus

This invention relates to an adhesive, an adhesive sheet, the manufacturing method of an adhesive sheet, and an image display apparatus.

The adhesive and the adhesive sheet using the same are used extensively in various fields of the industry. As a specific use, the protective film etc. which stick and use on the surfaces, such as glass, are used, for example. As said glass, window glass, such as a mobile telephone, a smart phone, a car, a building, is mentioned, for example.

As an adhesive, an acrylic resin adhesive, a rubber adhesive, a urethane adhesive, etc. are mentioned, for example. Among them, the urethane pressure-sensitive adhesive has properties such as properties that can be peeled off after application (hereinafter referred to as re-peelability), and properties that make it difficult to draw bubbles or the like into the interface between the pressure-sensitive adhesive layer and the adherend (hereinafter referred to as wettability). Since it is excellent in, it is used widely (patent document 1 etc.).

Japanese Patent Application Laid-Open No. 2016-186064

In recent years, in addition to re-peelability and wettability, adhesives used for pressure-sensitive adhesive sheets for surface protection have required adherend contamination. This is because the product which the adhesive adhered to the surfaces, such as plastic and glass, may be transported and stored for a long time. Here, adherend contamination means that contamination of the adhesive originated on an adherend does not occur when peeling off an adhesive sheet, even if the product on which the adhesive sheet was affixed for a long time under high temperature, high humidity conditions. In addition, since the degree of contamination varies depending on the kind of the material (adhered body) to which the adhesive is applied and the environment in which the product is left for a long time, the required adherend contamination is also different. In addition, what is considered to be a cause of a contamination includes alteration contamination derived from the material of a to-be-adhered body other than the trace of the paste originating in an adhesive.

Then, an object of this invention is to provide the adhesive, adhesive sheet, the manufacturing method of an adhesive sheet which can satisfy re-peelability, wettability, and adherend contamination property under high temperature, high humidity, and an image display apparatus.

In order to achieve the above object, the pressure-sensitive adhesive of the present invention,

Polyurethane prepolymer (A),

At least one selected from the group consisting of an organic acid (B-1), an acidic phosphoric acid ester compound (B-2), and an organic acid anhydride (B-3),

The acidic phosphoric acid ester compound (B-2) is at least one selected from the group consisting of acidic phosphoric acid ester compounds represented by the following formulas (I), (II) and (III),

The organic acid (B-1) is an organic acid other than the acidic phosphoric acid ester compound (B-2),

The prepolymer (A) of the polyurethane is characterized by being a prepolymer synthesized with a polyol and an isocyanate.

[Formula I]

In the formula (I),

R ¹ and R ² are each a hydrogen atom, a hydrocarbon group or an aryl group,

R ¹ and R ² may be the same or different,

At least one of R ¹ and R ² is a hydrocarbon group or an aryl group.

[Formula II]

[Formula III]

In the above formulas (II) and (III),

R ³ and R ⁴ are each a hydrogen atom, a hydrocarbon group or an aryl group,

R ³ and R ⁴ may be the same or different,

At least one of R ³ and R ⁴ is a hydrocarbon group or an aryl group,

AO is an alkylene oxide group, and each AO may be same or different,

n represents an integer greater than or equal to 1, and each n may be same or different.

The adhesive sheet of this invention is an adhesive sheet in which the adhesive layer was formed in the at least single side | surface of a base material, The said adhesive layer is an adhesive layer formed using the adhesive of the said invention, It is characterized by the above-mentioned.

The manufacturing method of the adhesive sheet by this invention is a coating process of coating the adhesive and crosslinking agent of the said invention to the adhesion layer formation surface of the said base material in which the said adhesion layer is formed, and the said It is a manufacturing method of the adhesive sheet of the said invention including the heating process which heats the said adhesive and a crosslinking agent on the said adhesion layer formation surface after a coating process.

The image display device of the present invention is an image display device in which a protective sheet of an image display device is attached to an image display surface, wherein the protective sheet is the adhesive sheet of the present invention.

According to the present invention, it is possible to provide a pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, a manufacturing method of the pressure-sensitive adhesive sheet, and an image display device capable of satisfying re-peelability, wettability, and adherend contamination under high temperature and high humidity.

Hereinafter, the present invention will be described by way of example. However, this invention is not limited by the following description.

In the adhesive of this invention, the said organic acid (B-1) may be at least one of carboxylic acid and sulfonic acid, for example.

In the adhesive of this invention, the said organic acid anhydride (B-3) may be at least one of a carboxylic anhydride and a sulfonic anhydride, for example.

The pressure-sensitive adhesive of the present invention further contains a crosslinking agent (C), and the crosslinking agent may be a polyisocyanate or a polyol.

In the pressure-sensitive adhesive of the present invention, for example, the prepolymer (A) may be a polyurethane polyol synthesized from a polyol and a polyisocyanate and having a plurality of hydroxyl groups.

In the adhesive of the present invention, for example, the prepolymer (A) may be a polyurethane polyisocyanate having a plurality of isocyanate groups.

In the adhesive of this invention, the said crosslinking agent (C) may be polyisocyanate, for example. In addition, the crosslinking agent (C) may be a polyol, for example.

The pressure-sensitive adhesive of the present invention may be, for example, an pressure-sensitive adhesive for forming an adhesive layer on at least one side of the substrate to produce an adhesive sheet. In addition, the said base material may be a base material of polyethylene terephthalate and a polyolefin, for example.

In the present invention, "alkyl" includes, for example, linear or branched alkyl. Carbon number of the said alkyl is not specifically limited, For example, it is 1-30, Preferably, it is 1-18, 3-16, or 4-12. Although the said alkyl is not specifically limited, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert- butyl group, pentyl group, hexyl group , Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, isocyl group, etc. Can be mentioned. The same applies to groups derived from alkyl groups and atomic groups (alkoxy groups and the like). The same applies to groups containing alkyl groups in the structure (alkylamino groups, alkoxy groups, etc.), or groups derived from alkyl groups (haloalkyl groups, hydroxyalkyl groups, aminoalkyl groups, alkanol groups and the like).

In the present invention, "alkenyl" includes, for example, linear or branched alkenyl. Examples of the alkenyl include one or a plurality of double bonds in the alkyl. Carbon number of the said alkenyl is not specifically limited, For example, it is the same as that of the said alkyl, Preferably it is 2-12 or 2-8. The alkenyl is, for example, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 3-methyl-2-butenyl Etc. can be mentioned.

In the present invention, "alkynyl" includes, for example, linear or branched alkynyl. Examples of the alkynyl include those having one or a plurality of triple bonds in the alkyl. Carbon number of the said alkynyl is not specifically limited, For example, it is the same as that of the said alkyl, Preferably it is 2-12 or 2-8. Examples of the alkynyl include ethynyl, propynyl, butynyl and the like. The alkynyl may further have, for example, one or a plurality of double bonds.

In the present invention, the "aromatic ring" includes, for example, aryl, heteroaryl, and arylalkyl. In addition, a "cyclic structure" includes the said aromatic ring, cycloalkyl, a bridged cyclic hydrocarbon group, a spiro hydrocarbon group, and cycloalkenyl, for example.

In the present invention, "aryl" includes, for example, a monocyclic aromatic hydrocarbon group and a polycyclic aromatic hydrocarbon group. As said monocyclic aromatic hydrocarbon group, phenyl etc. are mentioned, for example. The polycyclic aromatic hydrocarbon group is, for example, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, etc. are mentioned. Preferably, naphthyl, such as phenyl, 1-naphthyl, and 2-naphthyl, etc. are mentioned, for example.

In the present invention, "heteroaryl" includes, for example, a monocyclic aromatic heterocyclic group and a condensed aromatic heterocyclic group. The heteroaryl is, for example, furyl (eg 2-furyl), thienyl (eg 2-thienyl), pyrrolyl (eg 1-pyrrolyl), imidazolyl (eg 1-imida) Zolyl), pyrazolyl (eg 1-pyrazolyl), triazolyl (eg 1,2,4-triazol-1-yl), tetrazolyl (eg 1-tetrazolyl), oxazolyl (eg 2 Oxazolyl), isoxazolyl (e.g. 3-isoxazolyl), thiazolyl (e.g. 2-thiazolyl), thiadiazolyl, isothiazolyl (e.g. 3-isothiazolyl), pyridyl (e.g. 2-pyridyl), pyridazinyl (e.g. 3-pyridazinyl), pyrimidinyl (e.g. 2-pyrimidinyl), furazanyl (e.g. 3-furazanyl), pyrazinyl (e.g. 2 Pyrazinyl), oxadiazolyl (eg 1,3,4-oxadiazol-2-yl), benzofuryl (eg 2-benzo [b] furyl), benzothienyl (eg 2-benzo [ b] thienyl), benzimidazolyl (eg 1-benzoimidazolyl), dibenzofuryl, benzooxazolyl, benzothiazolyl, quinoxalyl (eg 2-quinolsarinyl), cinnaolinyl (eg : 3-cinnolineyl), quinazolyl (E.g. 2-quinazolinyl), quinolyl (e.g. 2-quinolyl), phthalazinyl (e.g. 1-phthalazinyl), isoquinolyl (e.g. 1-isoquinolyl), furyl, Terridinyl (e.g. 2-phthridinyl), carbazolyl, phenanthridinyl, acridinyl (e.g. 1-acridinyl), indolyl (e.g. 1-indolyl), isoindolyl, phenazinyl (Eg 1-phenazinyl) or phenothiazineyl (eg 1-phenothiazineyl).

In this invention, "cycloalkyl" is a cyclic saturated hydrocarbon group, for example, Although carbon number is not specifically limited, For example, it is 3-24 or 3-15. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bridged cyclic hydrocarbon group, spiro hydrocarbon group, and the like, and preferably, cyclopropyl, cyclo Butyl, cyclopentyl, cyclohexyl, bridged cyclic hydrocarbon group, and the like.

In the present invention, the "crosslinked cyclic hydrocarbon group" is, for example, bicyclo [2.1.0] pentyl, bicyclo [2.2.1] heptyl, bicyclo [2.2.2] octyl and bicyclo [3.2.1 ] Octyl, tricyclo [2.2.1.0] heptyl, bicyclo [3.3.1] nonane, 1-adamantyl, 2-adamantyl and the like.

In the present invention, the "spirohydrocarbon group" includes, for example, spiro [3.4] octyl.

In this invention, "cycloalkenyl" contains a cyclic unsaturated aliphatic hydrocarbon group, for example, and carbon number is 3-24 or 3-7, for example. Examples of the group include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, and the like, and preferably cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl. Senil, etc. The cycloalkenyl includes, for example, a bridged cyclic hydrocarbon group and a spiro hydrocarbon group having an unsaturated bond in the ring.

In the present invention, "arylalkyl" includes, for example, benzyl, 2-phenethyl, naphthalenylmethyl and the like, and "cycloalkylalkyl" is, for example, cyclohexylmethyl, adamantylmethyl Etc., and "hydroxyalkyl" includes, for example, hydroxymethyl, 2-hydroxyethyl, and the like.

Also, as in the present invention, the "substituent" or "more substituents", is not particularly limited, for example, carboxy, halogen, halogenated alkyl _{(e: CF 3, CH 2 CF 3} , CH 2 CCl 3), nitro, Nitroso, cyano, alkyl (e.g. methyl, ethyl, isopropyl, tert-butyl), alkenyl (e.g. vinyl), alkynyl (e.g. ethynyl), cycloalkyl (e.g. cyclopropyl, adamantyl ), Cycloalkylalkyl (e.g. cyclohexylmethyl, adamantylmethyl), cycloalkenyl (e.g. cyclopropenyl), aryl (e.g. phenyl, naphthyl), arylalkyl (e.g. benzyl, phenethyl), Heteroaryl (e.g. pyridyl, furyl), heteroarylalkyl (e.g. pyridylmethyl), heterocyclyl (e.g. piperidyl), heterocyclylalkyl (e.g. morpholinylmethyl), alkoxy (e.g. , ethoxy, propoxy, butoxy), perfluoroalkyl (e.g., CF _3), halogenated alkoxy (e.g., OCF _3), acyl, alkene-yloxy (e.g., vinyloxy, allyloxy), aryloxy ( Phenyloxy), alkyloxycarbonyl (eg methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl), arylalkyloxy (eg benzyloxy), amino [alkylamino (eg methylamino, Ethylamino, dimethylamino), acylamino (e.g. acetylamino, benzoylamino), arylalkylamino (e.g. benzylamino, tritylamino), hydroxyamino), alkylaminoalkyl (e.g. diethylaminomethyl), Sulfamoyl, oxo and the like.

In this invention, "alkoxy" contains the said alkyl-O- group, for example, For example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, etc. are mentioned. In addition, methoxymethyl etc. are mentioned as "alkoxyalkyl", for example, 2-aminoethyl etc. are mentioned, for example "aminoalkyl".

In the present invention, "acyl" is not particularly limited, but for example, formyl, acetyl, propionyl, isobutylyl, valeryl, isovaleryl, pivaloyl, hexanoyl, cyclohexanoyl, benzoyl, Ethoxycarbonyl, etc. are mentioned. The same applies to groups containing an acyl group in the structure (acyloxy group, alkanoloxy group, etc.). In addition, in this invention, carbonyl of an acyl group contains carbonyl carbon, For example, a C1 alkanol group (acyl group) shall refer to a formyl group.

In the present invention, "halogen" refers to any halogen element, but examples thereof include fluorine, chlorine, bromine and iodine.

In the present invention, the "perfluoroalkyl" is not particularly limited, and examples thereof include a perfluoroalkyl group derived from a linear or branched alkyl group having 1 to 30 carbon atoms. More specifically, the "perfluoroalkyl" is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, pentyl, hexyl, heptyl, And perfluoroalkyl groups derived from groups such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and isocyl. The same applies to the group (perfluoroalkylsulfonyl group, perfluoroacyl group, etc.) containing a perfluoroalkyl group in the structure.

In addition, in this invention, when the various groups mentioned above are a heterocyclic ring or contain a heterocyclic ring, "carbon number" shall also include the hetero atom number which comprises the said heterocyclic ring.

In the present invention, when an isomer is present in a substituent or the like, any isomer may be used, unless otherwise specified. For example, in the case of a "naphthyl group", a 1-naphthyl group or a 2-naphthyl group may be sufficient, and in the case of a "propyl group", an n-propyl group or an isopropyl group may be sufficient as it.

Moreover, the adhesive sheet of this invention is an adhesive sheet in which the adhesive layer was formed in the at least single side | surface of a base material as mentioned above, The said adhesive layer is an adhesive layer formed using the adhesive of the said invention, It is characterized by the above-mentioned. It is preferable that the adhesive sheet of this invention is an adhesive sheet used as a protective sheet of the said image display surface by affixing on the image display surface of an image display apparatus.

As mentioned above, the manufacturing method of the adhesive sheet which concerns on this invention is a coating process of coating the adhesive of this invention to the adhesion layer formation surface in which the said adhesion layer is formed of the said base material, and after the said coating process, It is a manufacturing method of the adhesive sheet of the said invention containing the heating process of heating the said adhesive on the adhesion layer formation surface. In the said coating process, when the adhesive of this invention contains a prepolymer and does not contain a crosslinking agent, it is preferable to coat the adhesive of this invention with the said crosslinking agent.

Moreover, the image display apparatus of this invention is an image display apparatus by which the protective sheet of the said image display apparatus was affixed on the image display surface as mentioned above, The said protective sheet is the adhesive sheet of the said invention, It is characterized by the above-mentioned. do.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described more concretely. However, this invention is not limited to the following embodiment.

[1.Adhesive]

As described above, the pressure-sensitive adhesive of the present invention is a prepolymer (A) (hereinafter sometimes referred to as "component (A)") of a polyurethane, an organic acid (B-1), and an acidic phosphoric acid ester compound (B- 2) and at least one selected from the group consisting of organic acid anhydrides (B-3) (hereinafter may be referred to as "component (B)"), and the acidic phosphate ester compound (B-2) , At least one selected from the group consisting of acidic phosphoric acid ester compounds represented by the following formulas (I), (II) and (III), wherein the organic acid (B-1) is the acidic phosphoric acid ester compound (B- It is an organic acid other than 2), The prepolymer (A) of the said polyurethane is characterized by being a prepolymer synthesize | combined with a polyol and an isocyanate.

[1-1. Polyurethane Prepolymer (A)]

The prepolymer (A) of the polyurethane is a prepolymer synthesized from a polyol and an isocyanate as described above. The isocyanate may be, for example, polyisocyanate.

The prepolymer (A) of the polyurethane may be, for example, a polyurethane polyol synthesized with a polyol and a polyisocyanate. In the present invention, "polyurethane polyol" refers to a prepolymer having a plurality of hydroxyl groups as a prepolymer of polyurethane. In addition, in this invention, a "prepolymer" is a polymer in the state which superposed | polymerized or bridge | crosslinked to the middle, and means the polymer which can further polymerize or bridge | crosslink. In the present invention, the "prepolymer of polyurethane" is a polyurethane in a state where polymerization or crosslinking has progressed to the middle, and refers to a polyurethane which can be converted into a polyurethane which has undergone further polymerization or crosslinking. Said "polyurethane prepolymer" can be converted into the polyurethane which further advanced superposition | polymerization or crosslinking, for example, by having two or more hydroxyl groups or isocyanate groups. In the present invention, "polyurethane polyisocyanate" can be converted into a polyurethane further polymerized or crosslinked by having a plurality of isocyanate groups (for example, at the sock end of the molecule), unless otherwise specified. Refers to a prepolymer of polyurethane. In addition, in this invention, a "polyol" refers to the organic compound which has two or more (2 or 3 or more) hydroxyl groups (preferably at least one of an alcoholic hydroxyl group and a phenolic hydroxyl group) in 1 molecule.

Although the content rate of the said polyurethane polyol is not specifically limited, For example, 20-80 mass%, 30-70 mass%, or 40-60 mass% may be sufficient with respect to the total mass of the adhesive of this invention.

Or in the adhesive of this invention, the polyurethane prepolymer (A) may be polyurethane polyisocyanate which has two or more isocyanate groups. In the present invention, "polyisocyanate" refers to an organic compound (polyfunctional isocyanate) having a plurality (2 or 3 or more) of isocyanate groups (also referred to as isocyanate groups), that is, (-N = C = O) in one molecule. Say). Although the content rate of the polyurethane polyisocyanate which has two or more isocyanate groups is not specifically limited, Preferably it is 20-80 mass%, More preferably, it is 40-60 mass% with respect to the total mass of the adhesive of this invention. In addition, the kind of said polyol, polyisocyanate, etc. are described with the illustration of the manufacturing method of the adhesive of this invention in "2. Manufacturing method of an adhesive" mentioned later.

[1-2. Organic acid (B-1), acidic phosphoric acid ester compound (B-2), and organic acid anhydride (B-3)]

As described above, the pressure-sensitive adhesive of the present invention is at least one selected from the group consisting of an organic acid (B-1), an acidic phosphate ester compound (B-2), and an organic acid anhydride (B-3) as a component (B). It includes one. In the adhesive of this invention, the said organic acid (B-1) may be at least one of carboxylic acid and a sulfonic acid, as mentioned above, and may contain both.

In the organic acid (B-1), examples of the carboxylic acid include aromatic carboxylic acid and aliphatic carboxylic acid. Moreover, aromatic sulfonic acid, aliphatic sulfonic acid, etc. are mentioned as said sulfonic acid. From the viewpoint of suppressing or preventing corrosion of the coating device or the adhesion object of the pressure-sensitive adhesive of the present invention, it is preferable that the acidity of the component (B) (acid component) is not too strong. From this viewpoint, it is preferable that the said organic acid (B-1) is at least one of aromatic carboxylic acid and aromatic sulfonic acid. Although it does not specifically limit as said aromatic carboxylic acid and aromatic sulfonic acid, For example, aromatic carboxylic acid and aromatic sulfonic acid represented by general formula (IV) and (V) mentioned later are mentioned.

As said aliphatic carboxylic acid and said aliphatic sulfonic acid in the said organic acid (B-1), the aliphatic carboxylic acid or aliphatic sulfonic acid which the carboxy group or sulfo group couple | bonded with aliphatic saturated or unsaturated hydrocarbon group is mentioned, for example. The aliphatic saturated or unsaturated hydrocarbon group may be linear or branched, or may not contain. The aliphatic saturated or unsaturated hydrocarbon group may be, for example, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, bridged hydrocarbon group, spiro hydrocarbon group, cycloalkenyl group, and the like described above. From the viewpoint of suppressing or preventing corrosion of the application device or the adhesion object of the pressure-sensitive adhesive of the present invention, it is preferable that the acidity of the aliphatic carboxylic acid and the aliphatic sulfonic acid is not too strong. In view of this, the aliphatic saturated or unsaturated hydrocarbon group may have, for example, 3 or more, 6 or more, or 8 or more carbon atoms. It is preferable that the upper limit of carbon number of the said aliphatic saturated or unsaturated hydrocarbon group is 18 or less, 14 or less, 12 or less. As said aliphatic carboxylic acid and said aliphatic sulfonic acid, 1, such as propionic acid, n-hexanoic acid, 2-ethylhexanoic acid, n-nonanoic acid, n-nonadecanoic acid, 3,5,5-trimethylhexanoic acid, etc. Dibasic acids, such as a basic acid, hexane diacid, an octanoic acid, and a decane acid, 1-propanesulfonic acid, methanesulfonic acid, etc. are mentioned.

It is preferable that the said organic acid (B-1) contains an aromatic ring from a viewpoint of the solubility to the solvent (for example, toluene, etc.) at the time of adhesive manufacture, For example, at least one of the said aromatic carboxylic acid and aromatic sulfonic acid. Is preferably. The aromatic carboxylic acid and aromatic sulfonic acid can be represented by the following general formula (IV), for example.

[Formula IV]

In the above formula (IV),

Ar may be an aromatic ring (aryl) or a heteroaromatic ring (heteroaryl), monocyclic or condensed ring may be used,

R ¹⁰⁰ is a carboxy group or a sulfo group, and may be one or plural, or in the case of a plural number, may be the same or different,

Ar is good and which may have one or more arbitrary substituent other than R ^100, may need to have.

In said Formula (IV), Ar is a benzene ring, a naphthalene ring, anthracene ring, a pyridine ring, etc. are mentioned, for example. Further, as the arbitrary substituent other than R ^100, for example, there may be mentioned a saturated or unsaturated hydrocarbon. As said saturated or unsaturated hydrocarbon group, it is an aliphatic saturated or unsaturated hydrocarbon group, for example. The aliphatic saturated or unsaturated hydrocarbon group may be linear or branched, or may not contain. The aliphatic saturated or unsaturated hydrocarbon group may be, for example, 1 to 18 carbon atoms. The aliphatic saturated or unsaturated hydrocarbon group may be, for example, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, bridged hydrocarbon group, spiro hydrocarbon group, cycloalkenyl group, and the like described above.

In addition, the said organic acid (B-1) can be represented, for example by the following general formula (V).

[Formula V]

In said general formula (V), R <^100> is the same as said general formula (IV),

R ²⁰⁰ is an aliphatic saturated or unsaturated hydrocarbon group and may be one, two or more, the same or different. The said saturated or unsaturated hydrocarbon group is the same as that of the said General formula (IV), for example.

In the above general formulas (IV) and (V), the aromatic carboxylic acid and the aromatic sulfonic acid represented by the general formula (IV) or (V) from the viewpoint of suppressing or preventing corrosion of the coating device or the adhesion object of the pressure-sensitive adhesive of the present invention. It is desirable that the acid is not too strong. In view of this, and in view of the solubility of the aromatic carboxylic acid and the aromatic sulfonic acid represented by the formula (IV) or (V) in a solvent (for example, toluene, etc.), the carbon number of the aliphatic saturated or unsaturated hydrocarbon group It is preferable that they are 1 or more, 2 or more, and 4 or more. It is preferable that the upper limit of carbon number of the said aliphatic saturated or unsaturated hydrocarbon group is 18 or less and 14 or less. The said organic acid (B-1) can use together the organic acid represented by the said General formula (IV) and (V).

In the above formulas (IV) and (V), examples of the aromatic carboxylic acid include straight chain or branched alkylbenzene carboxylic acid (alkyl benzoic acid), and the like, for example, straight chain having 10 to 14 alkyl carbon atoms or Branched alkylbenzene carboxylic acid (alkyl benzoic acid) etc. are mentioned. Specifically as said aromatic carboxylic acid, benzoic acid, a phthalic acid, a pyromellitic acid, etc. are mentioned, for example. Moreover, as said aromatic sulfonic acid, a linear or branched alkylbenzene sulfonic acid etc. are mentioned, for example, For example, linear or branched alkylbenzene sulfonic acid of 10-14 alkyl carbon atoms is mentioned.

The acidic phosphoric acid ester compound (B-2) is at least one selected from the group consisting of acidic phosphoric acid ester compounds represented by the general formulas (I), (II) and (III) as described above. As the acidic phosphoric acid ester compound (B-2), as described above, the acidic phosphoric acid ester compound represented by the general formulas (I), (II) and (III) can be used in combination.

In said general formula (I), (II), and (III), R <^1> , R <^2> , R <^3> and R <^4> are a hydrogen atom, a hydrocarbon group, or an aryl group as mentioned above, respectively. As said hydrocarbon group, a saturated or unsaturated hydrocarbon group is mentioned, for example. As said saturated or unsaturated hydrocarbon group, it is an aliphatic saturated or unsaturated hydrocarbon group, for example. The aliphatic saturated or unsaturated hydrocarbon group may be linear or branched, or may not contain. The aliphatic saturated or unsaturated hydrocarbon group may be, for example, 4 to 18 carbon atoms, 4 to 14 carbon atoms, 4 to 10 carbon atoms, or 4 to 7 carbon atoms. The aliphatic saturated or unsaturated hydrocarbon group may be, for example, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, bridged hydrocarbon group, spiro hydrocarbon group, cycloalkenyl group, and the like described above. As said aryl group, each aryl group mentioned above is mentioned, for example.

In addition, in said general formula (I), (II), and (III), as above-mentioned, AO is an alkylene oxide group and each AO may be same or different. As AO, an ethylene oxide group, a propylene oxide group, etc. are mentioned, for example. As described above, n represents an integer of 1 or more, and each n may be the same or different. n may be 1-10 or 1-6, for example.

Although the said organic acid anhydride (B-3) is not specifically limited, For example, an aromatic carboxylic acid anhydride, an aliphatic carboxylic acid anhydride, an aromatic sulfonic acid anhydride, an aliphatic sulfonic acid anhydride, etc. are mentioned. In the aromatic carboxylic acid anhydride, the aliphatic carboxylic acid anhydride, the aromatic sulfonic acid anhydride and the aliphatic sulfonic acid anhydride, the aromatic carboxylic acid, the aliphatic carboxylic acid, the aromatic sulfonic acid and the aliphatic sulfonic acid are exemplified as the organic acid (B-1), for example. It may be the same as aliphatic carboxylic acid, aromatic carboxylic acid, aromatic sulfonic acid and aliphatic sulfonic acid.

It is preferable that the said organic acid anhydride (B-3) contains an aromatic ring from a viewpoint of the solubility in the solvent (for example, toluene, etc.) at the time of manufacture of an adhesive, For example, the said aromatic carboxylic anhydride and the said aromatic sulfonic acid It is preferable that it is at least one anhydride. The aromatic carboxylic acid anhydride and the aromatic sulfonic acid anhydride can be represented by the following general formula (VI) or (iii), for example.

[Formula VI]

[Formula Ⅶ]

In the formula (VI),

R ¹⁰⁰⁰ is a carboxylic acid anhydride group (-CO-O-CO-) or a sulfonic anhydride group (-SO ₂ -O-SO _2- ),

Ar may be an aromatic ring (aryl) or a heteroaromatic ring (heteroaryl), monocyclic or condensed ring may be sufficient, and each Ar may be same or different,

Each Ar may have, or may not have, arbitrary substituents,

Each Ar may also be connected by one or more carboxylic anhydride groups (-CO-O-CO-) or sulfonic anhydride groups (-SO ₂ -O-SO _2- ) other than R ¹⁰⁰⁰ , and are not connected. You don't have to.

In the formula (i),

R ¹⁰⁰⁰ is a carboxylic acid anhydride group (-CO-O-CO-) or a sulfonic anhydride group (-SO ₂ -O-SO _2- ),

Ar may be an aromatic ring (aryl) or a heteroaromatic ring (heteroaryl), monocyclic or condensed ring may be used,

Ar may or may not have arbitrary substituents, or may have one or more,

Ar is, also, R ¹⁰⁰⁰ except for one or a plurality of carboxylic acid anhydride group (-CO-O-CO-) or a sulfonic acid anhydride group _{(-SO 2 -O-SO 2 -} ) may optionally have, and does have.

In said Formula (VI) and (iii), Ar is the same as the said Formula (IV) illustrated by the said organic acid (B-1), For example, a benzene ring, a naphthalene ring, anthracene ring, a pyridine ring, etc. are mentioned. Can be. Moreover, as said arbitrary substituent, a saturated or unsaturated hydrocarbon group is mentioned like the said Formula (IV) illustrated by the said organic acid (B-1), for example. As said saturated or unsaturated hydrocarbon group, it is an aliphatic saturated or unsaturated hydrocarbon group, for example. The aliphatic saturated or unsaturated hydrocarbon group may be linear or branched, or may not contain. The aliphatic saturated or unsaturated hydrocarbon group may be, for example, 1 to 18 carbon atoms. The aliphatic saturated or unsaturated hydrocarbon group may be, for example, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, bridged hydrocarbon group, spiro hydrocarbon group, cycloalkenyl group, and the like described above.

In the above formula (VI), when R ¹⁰⁰⁰ is a carboxylic acid anhydride group (-CO-O-CO-), it is represented by the following formula (VI-1), and R ¹⁰⁰⁰ is a sulfonic anhydride group (-SO ₂ -O-SO _2- ) is represented by the following general formula (VI-2). In the following formulas (VI-1) and (VI-2), R ¹⁰⁰⁰ is a carboxylic anhydride group (-CO-O-CO-) or a sulfonic anhydride group (-SO ₂ -O-SO _2- ) as described below. Except phosphorus, it is the same as said General formula (VI).

[Formula VI-1]

[Formula VI-2]

In the above formula (VII), when R ¹⁰⁰⁰ is a carboxylic acid anhydride group (-CO-O-CO-), it is represented by the following formula (VII-1), and R ¹⁰⁰⁰ is a sulfonic anhydride group (-SO ₂ In the case of -O-SO _2- ), it is represented by the following chemical formula (VII-2). In the following formulas (VII-1) and (VII-2), R ¹⁰⁰⁰ is a carboxylic anhydride group (-CO-O-CO-) or a sulfonic anhydride group (-SO ₂ -O-SO _2- ) as described below. Except phosphorus, it is the same as said general formula (VII).

[Formula VII-1]

[Formula VII-2]

In addition, in the said organic acid anhydride (B-3), the said aromatic carboxylic acid anhydride and aromatic sulfonic acid anhydride can be represented, for example by the following general formula (i) or (i).

[Formula Ⅷ]

[Formula Ⅸ]

In the formula (i),

R ¹⁰⁰⁰ is a carboxylic acid anhydride group (-CO-O-CO-) or a sulfonic anhydride group (-SO ₂ -O-SO _2- ),

Each R ²⁰⁰ is an aliphatic saturated or unsaturated hydrocarbon group, each of R ²⁰⁰ bonded to each benzene ring may be one or a plurality, or each of R ²⁰⁰ may be the same or different,

Each benzene ring, and, R ¹⁰⁰⁰ except for one or a plurality of carboxylic acid anhydride group (-CO-O-CO-) or a sulfonic acid anhydride group _{(-SO 2 -O-SO 2 -} ) may optionally be connected to, be connected You don't have to.

Further, each of R ²⁰⁰ standing air, the saturated or unsaturated hydrocarbon group, for example, the same as in the general formula (Ⅳ) and (V).

In the formula (i),

R ¹⁰⁰⁰ is a carboxylic acid anhydride group (-CO-O-CO-) or a sulfonic anhydride group (-SO ₂ -O-SO _2- ),

R ²⁰⁰ is an aliphatic saturated or unsaturated hydrocarbon group, R ²⁰⁰ bonded to the benzene ring may be one or a plurality, or a plurality of R ²⁰⁰ may be the same or different,

The benzene ring may further have or may not have one or a plurality of carboxylic anhydride groups (-CO-O-CO-) or sulfonic anhydride groups (-SO ₂ -O-SO _2- ) other than R ¹⁰⁰⁰ .

In addition, a group in R ^200, the saturated or unsaturated hydrocarbon, for example, the same as in the general formula (Ⅳ) and (V).

In the above formula (VII), when R ¹⁰⁰⁰ is a carboxylic acid anhydride group (-CO-O-CO-), it is represented by the following formula (VII-1), and R ¹⁰⁰⁰ is a sulfonic anhydride group (-SO ₂ In the case of -O-SO _2- ), it is represented by the following chemical formula (VII-2). In the following formulas (VII-1) and (VII-2), R ¹⁰⁰⁰ is a carboxylic anhydride group (-CO-O-CO-) or a sulfonic anhydride group (-SO ₂ -O-SO _2- ) as described below. Except phosphorus, it is the same as said general formula (VII).

[Formula VII-1]

[Formula VII-2]

In the above formula (VII), when R ¹⁰⁰⁰ is a carboxylic acid anhydride group (-CO-O-CO-), it is represented by the following formula (VII-1), and R ¹⁰⁰⁰ is a sulfonic anhydride group (-SO ₂ In the case of -O-SO _2- ), it is represented by the following chemical formula (VII-2). In the following formulas (VII-1) and (VII-2), R ¹⁰⁰⁰ is a carboxylic anhydride group (-CO-O-CO-) or a sulfonic anhydride group (-SO ₂ -O-SO _2- ) as described below. Except phosphorus, it is the same as said general formula (VII).

[Formula VII-1]

[Formula VII-2]

In the above general formulas (VI) to (iii), from the viewpoint of suppressing or preventing corrosion of the coating device or the adhesion object of the pressure-sensitive adhesive of the present invention, the aromatic carboxylic acid and the aromatic sulfonic acid represented by the above general formulas (VI) to (iii) It is desirable that the acid is not too strong. From this point of view, and from the viewpoint of solubility in a solvent (for example, toluene) of the aromatic carboxylic acid anhydride or the aromatic sulfonic acid anhydride represented by the formulas (VI) to (iii), the aliphatic saturated or unsaturated hydrocarbon group It is preferable that carbon number is one or more, two or more, and four or more. It is preferable that the upper limit of carbon number of the said aliphatic saturated or unsaturated hydrocarbon group is 18 or less and 14 or less.

In the formulas (VI) to (iii), examples of the aromatic carboxylic acid include straight chain or branched alkylbenzene carboxylic acid (alkyl benzoic acid), and the like, for example, straight chain having 10 to 14 alkyl carbon atoms or Branched alkylbenzene carboxylic acid (alkyl benzoic acid) etc. are mentioned. Specific examples of the aromatic carboxylic acid anhydride include benzoic anhydride, phthalic anhydride, pyromellitic anhydride, and the like.

As mentioned above, it is preferable that the acidity of component (B) (acid component) is not too strong from a viewpoint which suppresses or prevents corrosion of the application | coating device of the adhesive of this invention, or an adhesion object. From this point of view, in the present invention, as the component (B) (acid component), as described above, the organic acid (B-1), the acidic phosphoric acid ester compound (B-2), and the organic acid anhydride (B-3) Although at least one selected from the group consisting of is used, it is more preferable that it is an acidic phosphate ester type compound (B-2) or an organic acid anhydride (B-3). In addition, the organic acid anhydride (B-3) is preferably a carboxylic acid anhydride from the viewpoint of suppressing or preventing corrosion of the coating device or the adhesion object of the pressure-sensitive adhesive of the present invention.

Although the content rate of component (B) (acid component) is not specifically limited, For example, even if it is 0.3-6 mass%, 0.6-6 mass%, or 3-6 mass% with respect to the total mass of the adhesive of this invention. good. In addition, the content rate of the said component (B) (acid component) is 0.5-10 mass%, 1-10 mass%, or 5 with respect to the total mass of the prepolymer (A) of a polyurethane, for example. 10 mass% may be sufficient. It is preferable that the content rate of component (B) (acid component) is not too small from a viewpoint of adherend contamination property at high temperature, high humidity. In addition, it is preferable that the content rate of component (B) (acid component) is not too high from a viewpoint of re-peelability, and a viewpoint of suppressing or preventing corrosion of an application | coating device or a sticking object.

[1-3. Cross-linking system (C)]

As described above, the pressure-sensitive adhesive of the present invention may further contain a crosslinking agent (C). Although a crosslinking agent (C) is not specifically limited, When a prepolymer (A) of polyurethane is a polyurethane polyol, it is preferable that one part or all part of a crosslinking agent (C) is polyisocyanate. In the present invention, as described above, the "polyisocyanate" is an organic having a plurality (2 or 3 or more) of isocyanate groups (also referred to as isocyanato groups), that is, (-N = C = O) in one molecule. It refers to a compound (polyfunctional isocyanate).

When the adhesive of this invention contains the said polyisocyanate as a crosslinking agent (C), although the content is not specifically limited, For example, with respect to the molar amount of the hydroxyl group of the said polyurethane polyol, the isocyanate group of the said polyisocyanate is 0.5-. 5 times or 1-4 times molar amount may be sufficient.

When a crosslinking agent (C) contains polyisocyanate (polyfunctional isocyanate), it does not specifically limit as said polyisocyanate. The said polyisocyanate may be the same as the polyisocyanate used for the synthesis | combination of the prepolymer (A) of polyurethane illustrated in "2. The manufacturing method of an adhesive agent" mentioned later, for example, For example, trimethylol The propane adduct body, the burette body reacting with water, the trimer which has isocyanurate ring, etc. may be sufficient, and may use only one type or may use multiple types together.

Or in the adhesive of this invention, the polyurethane prepolymer (A) of polyurethane may be polyurethane polyisocyanate which has two or more isocyanate groups as mentioned above. In this case, it is preferable that one part or all part of the said crosslinking agent (C) is a polyol. When the adhesive of this invention contains the said polyol as a crosslinking agent (C), although the content is not specifically limited, The hydroxyl value of the said polyol is 0.5 to 5 times with respect to the molar amount of the isocyanate group of the said polyurethane polyisocyanate, or 1 to 4 times the molar amount may be sufficient.

When a crosslinking agent (C) contains a polyol, it does not specifically limit as said polyol. The said polyol may be the same as the polyol used for the synthesis | combination of the prepolymer (A) of polyurethane illustrated by "2. The manufacturing method of an adhesive agent" mentioned later, for example, even if it uses only one type and uses multiple types together Also good.

[1-4. Other Ingredients]

The adhesive of this invention contains the said component (A) and (B) as mentioned above. As mentioned above, the said component (C) (crosslinking agent (C)) may be included and does not need to be included. In addition, the adhesive of this invention may contain other components other than the said component (A)-(C), and does not need to contain it. For example, the pressure-sensitive adhesive of the present invention may or may not contain a solvent, an antioxidant, a crosslinking agent, a filler, a colorant, an ultraviolet absorber, an antifoaming agent, a light stabilizer, an antistatic agent, or the like as the other components. . Although these types etc. are not specifically limited, For example, you may be the same as or similar to a general adhesive. Although it does not specifically limit as said ultraviolet absorber, For example, ultraviolet absorbers, such as a benzophenone type, a benzotriazole type, a triazine type, are mentioned. Although it does not specifically limit as said antifoamer, For example, antifoamers, such as a silicone type and mineral oil type, are mentioned. Although it does not specifically limit as said light stabilizer, For example, light stabilizers, such as a hindered amine type, are mentioned. Examples of the antistatic agent include ionic compounds such as inorganic salts and organic salts, and nonionic compounds such as nonionic surfactants. Although it does not specifically limit about the said solvent, the said antioxidant, and the said crosslinking inhibitor, For example, it is as having demonstrated with the illustration of the manufacturing method of the adhesive of this invention in "2. .

As said other component, carboxylic acid ester etc. may be included, for example. Although it does not specifically limit as said carboxylic acid ester, For example, the carboxylic acid ester of Unexamined-Japanese-Patent No. 2011-190420, Unexamined-Japanese-Patent No. 2015-151429, Unexamined-Japanese-Patent No. 2016-186029, etc. may be sufficient. The carboxylic acid ester may be, for example, carboxylic acid ester in Examples described later.

[2.Method of Manufacturing Adhesive]

The manufacturing method of the adhesive of this invention is not specifically limited except using the said component (A) and (B), For example, you may refer to the manufacturing method of a general adhesive, for example, the said You may refer to patent document 1 etc. Hereinafter, the manufacturing method in the case where the prepolymer (A) of polyurethane is a polyurethane polyol (prepolymer of polyurethane) synthesize | combined with a polyol and polyisocyanate is demonstrated mainly, for example.

First, a polyol, a polyisocyanate, a solvent, and a catalyst are put into a reaction container as needed, and reaction is performed, heating and stirring. Although the usage-amount of the said polyol is not specifically limited, For example, it is 20-80 mass% or 40-60 mass% with respect to the mass of the adhesive after manufacture. Although the usage-amount of the said polyisocyanate is not specifically limited, For example, it is 0.5-10 mass% or 1-5 mass% with respect to the mass of the adhesive after manufacture. Although the usage-amount of the said solvent is not specifically limited, It is 10-50 mass% or 20-40 mass% with respect to the mass of the adhesive after manufacture, for example. Although it is not necessary to use the said catalyst, it is preferable to use from a viewpoint of the smooth progress of reaction. When using the said catalyst, the usage-amount is not specifically limited, For example, it is 0.001-0.1 mass% with respect to the mass of the adhesive after manufacture. Although the reaction temperature of the said reaction is not specifically limited, For example, it is 30-80 degreeC or 40-60 degreeC. Although reaction time of the said reaction is not specifically limited, For example, it is 0.5-15 hrs, 0.5-4 hrs, or 1-3 hrs. In this way, a polyurethane polyol (a prepolymer (A) of polyurethane) -containing composition can be synthesized.

In addition, in the synthesis | combination of the said polyurethane polyol containing composition, (1) the method of putting a polyester polyol, a polyether polyol, a catalyst, and a polyisocyanate into a flask whole quantity, and (2) polyester polyol and a polyether polyol, for example. The method of adding a catalyst to a flask and adding dropwise polyisocyanate is possible. Although the side of (1) is simple, since side of (2) is easy to control reaction, it is possible to remark as needed.

In addition, component (B) is added to the synthesized polyurethane polyol-containing composition and stirred until uniform. At this time, you may add a component (C) (crosslinking agent (C)) as needed. Moreover, you may add other components other than components (A)-(C) as needed. The said other component may contain the solvent, for example, and may also contain antioxidant, crosslinking inhibitor, carboxylic acid ester, etc. as mentioned above. In this way, the adhesive of this invention can be obtained.

It is preferable that a crosslinking agent (C) contains polyisocyanate (polyfunctional isocyanate), for example. Although it does not specifically limit as said polyisocyanate, It may be the same as that of the polyisocyanate used for the synthesis | combination of the polyurethane polyol (prepolymer (A) of polyurethane) containing composition illustrated below, For example, trimethylol propane The adduct body, the burette body which reacts with water, and the trimer which has isocyanurate ring may be sufficient, You may use only one type or may use multiple types together. Although the usage-amount of the said polyisocyanate in a crosslinking agent (C) is not specifically limited, For example, the molar amount of the isocyanate group of the said polyisocyanate is 0.5 to 5 times or 1 to 4 times with respect to the molar amount of the hydroxyl group of the said polyurethane polyol. Or the molar amount of the hydroxyl group of the said polyol is 0.5 to 5 times or 1 to 4 times with respect to the molar amount of the isocyanate group of the said polyurethane polyisocyanate.

Although it is not necessary to use the said solvent, it is preferable to use from a viewpoint of the smooth mixing of each component which comprises the adhesive of this invention. Although the usage-amount is not specifically limited when using the said catalyst, For example, it is 0.001-0.1 mass% or 0.01-0.05 mass% with respect to the mass of the adhesive after manufacture. Although the said antioxidant does not need to be used, it is preferable to use it. Although the usage-amount is not specifically limited when using the said antioxidant, For example, it is 0.05-1 mass% or 0.1-0.6 mass% with respect to the mass of the adhesive after manufacture. When using the said fatty acid ester, the usage-amount is not specifically limited, For example, it is 5-50 mass% or 10-30 mass% with respect to the mass of the adhesive after manufacture.

Hereinafter, the synthesis of the polyurethane polyol (the prepolymer (A) of polyurethane) -containing composition will be described in more detail.

Although the said polyol is not specifically limited, For example, although bifunctional (having two hydroxyl groups in 1 molecule) or trifunctional or more (having 3 or more hydroxyl groups in 1 molecule) may be sufficient, it is preferable that it is trifunctional or more, It is especially preferable that it is trifunctional. In addition, only one type may be used for the said polyol, or it may use it together multiple types. Although the said polyol is not specifically limited, For example, one or both of a polyester polyol and a polyether polyol may be sufficient.

It does not specifically limit as said polyester polyol, For example, well-known polyester polyol may be sufficient. As an acid component of the said polyester polyol, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, etc. are mentioned, for example. As the glycol component of the polyester polyol, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1 5-pentanediol, 3,3'-dimethyl Allheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentylglycol, butylethylpentanediol and the like. As a polyol component of the said polyester polyol, glycerin, trimethylol propane, pentaerythritol, etc. are mentioned, for example. In addition, polyester polyol etc. which are obtained by ring-opening-polymerizing lactones, such as polycaprolactone, poly ((beta) -methyl- (gamma) -valerolactone), and polyvalerolactone, are mentioned.

The molecular weight of the said polyester polyol is not specifically limited, It can use from low molecular weight to high molecular weight. Preferably a polyester polyol having a number average molecular weight of 500 to 5,000 is used. If the number average molecular weight is 500 or more, the reactivity is too high to prevent gelation. Moreover, when number average molecular weight is 5,000 or less, it is easy to prevent the fall of reactivity and the fall of the cohesion force of a polyurethane polyol itself. Although it is not necessary to use even if it uses the said polyester polyol, the usage-amount in the case of using may be 10-90 mol% or 10-50 mol% in the polyol which comprises the said polyurethane polyol, for example.

In addition, the said polyether polyol is not specifically limited, For example, a well-known polyether polyol may be sufficient. Specifically, the polyether polyol may be a low molecular weight polyol such as water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, or the like, and may be used as an initiator, for example, ethylene oxide, propylene oxide, The polyether polyol obtained by superposing | polymerizing oxirane compounds, such as butylene oxide and tetrahydrofuran, may be sufficient. More specifically, the polyether polyol may be two or more functional groups such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, or the like. The molecular weight of the said polyether polyol is not specifically limited, It can use from low molecular weight to high molecular weight. For example, polyether polyols having a number average molecular weight of 1,000 to 15,000 may be used. If the number average molecular weight is 1,000 or more, the reactivity is too high to prevent gelation. Moreover, when molecular weight is 15,000 or less, it is easy to prevent the fall of reactivity and the fall of the cohesion force of a polyurethane polyol itself. Although the said polyether polyol does not need to be used even if it is used, the usage-amount when using it may be 20-100 mol% or 20-80 mol% in the polyol which comprises the said polyurethane polyol, for example.

As for the said polyether polyol, a part thereof is glycol, such as ethylene glycol, 1, 4- butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerin, trimethylol propane, pentaerythritol, ethylenediamine, N- You may substitute and use together polyhydric amines, such as aminoethyl ethanolamine, isophorone diamine, and xylene diamine.

As mentioned above, although the polyol may be a bifunctional polyether polyol (having two hydroxyl groups in one molecule), it is preferable that it is trifunctional or more (having three or more hydroxyl groups in one molecule). In particular, the number average molecular weight is 1,000 to 15,000, and by using some or all of the trifunctional or higher polyols, the balance between adhesion and re-peelability can be further easily achieved. If the number average molecular weight is 1,000 or more, the reactivity of the trifunctional or higher polyol is too high to prevent gelation. Moreover, when a number average molecular weight is 15,000 or less, it is easy to prevent the fall of the reactivity of trifunctional or more than trifunctional polyol, and the fall of the cohesion force of polyurethane polyol itself. For example, a polyol having a number average molecular weight of 2,500 to 3,500 and at least trifunctional may be used in part or in whole.

Although it does not specifically limit as said polyisocyanate (organic polyisocyanate compound), For example, well-known aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, etc. are mentioned. In addition, only one type of polyisocyanate may be used or it may use it together in multiple types.

As said aromatic polyisocyanate, it is 1, 3- phenylene diisocyanate, 4,4'- diphenyl diisocyanate, 1, 4- phenylene diisocyanate, 4,4'- diphenylmethane diisocyanate, 2,4, for example. -Triylene diisocyanate, 2,6-triylene 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, etc. are mentioned.

Examples of the aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. are mentioned.

Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1 , 4-die benzene, 1, 4- tetramethyl xylene diisocyanate, 1, 3- tetramethyl xylene diisocyanate, etc. are mentioned.

As said alicyclic polyisocyanate, 3-isocyanate methyl-3,5,5-trimethyl cyclohexyl isocyanate, 1, 3- cyclopentane diisocyanate, 1, 3- cyclohexane diisocyanate, 1, 4- cyclo, for example Hexane diisocyanate, methyl-2 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1, 4-bis (isocyanate methyl) cyclohexane etc. are mentioned.

Moreover, the trimethylolpropane adduct of the said polyisocyanate, the biuret reacting with water, and the trimer which has an isocyanurate ring can also be used together.

As said polyisocyanate, 4,4'- diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), etc. are preferable.

It does not specifically limit as said catalyst, For example, a well-known catalyst can be used. As said catalyst, a tertiary amine compound, an organometallic compound, etc. are mentioned, for example.

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

Examples of the organometallic compound 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, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloro Low acetate, 2-ethylhexanoic acid tin, etc. are mentioned. As the non-tin compound, for example, titanium such as dibutyl titanium dichloride, tetrabutyl titanate, butoxy titanium trichloride, lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate and the like ( Iron), iron such as 2-ethylhexanoate and iron acetylacetonate, cobalt such as cobalt benzoate and cobalt benzoate, zinc-based zinc such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate Etc. can be mentioned.

In the case of using these catalysts, for example, in a system in which two kinds of polyols, such as polyester polyols and polyether polyols exist, gelation occurs in a single catalyst system due to the difference in reactivity, or the reaction solution is turbid. It's easy to get into trouble. In such a case, by using two or more types of catalysts together, reaction rate, selectivity of a catalyst, etc. can be controlled, and these problems can be solved. As the combination, for example, tertiary amines / organic metals, tins / non-tins, tins / tins, etc. are used, preferably tins / tins, more preferably dibutyltin dilaurate And tin 2-ethylhexanoate. Although the compounding ratio is not specifically limited, For example, 2-ethylhexanoic acid tin / dibutyltin dilaurate is less than 1 by mass, for example, 0.2-0.6 may be sufficient. If the blending ratio is less than 1, it is easy to prevent gelation due to the balance of catalyst activity. Although the usage-amount of these catalysts is not specifically limited, For example, they are 0.01-1.0 mass% or 0.01-0.2 mass% with respect to the total amount of a polyol and organic polyisocyanate.

When using the said catalyst, reaction temperature of the said polyurethane polyol synthesis | combination may be less than 100 degreeC, or 40 to 60 degreeC, for example. If it is less than 100 degreeC, it is easy to control reaction rate and a crosslinked structure, and the polyurethane polyol which has a predetermined molecular weight is easy to be obtained.

In addition, when the said catalyst is not used (no catalyst), the reaction temperature of the said polyurethane polyol synthesis | combination may be 100 degreeC or more, or 110 degreeC or more, for example. In the absence of a catalyst, the reaction time of the polyurethane polyol synthesis is, for example, 3 hours or more.

The said solvent used for the said polyurethane polyol synthesis | combination is not specifically limited, For example, a well-known solvent can be used. As said solvent, ketones, such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, ester, such as ethyl acetate, n-butyl acetate, and isobutyl acetate, hydrocarbons, such as toluene and xylene, etc. are mentioned, for example. Toluene is particularly preferable at the point of solubility of a polyurethane polyol, the boiling point of a solvent, etc.

Moreover, it does not specifically limit as said antioxidant, For example, antioxidant, such as a phenol type and a sulfur type, is mentioned.

Moreover, in the adhesive of this invention, it does not specifically limit about the manufacturing method in the case where the prepolymer (A) of polyurethane contains the polyurethane polyisocyanate which has two or more isocyanate groups. Specifically, for example, except that the amount of polyisocyanate used is relatively high to leave an isocyanate group in the prepolymer (the pressure-sensitive adhesive of the present invention is synthesized from the carboxylic acid ester, polyol and polyisocyanate). And a polyurethane polyol (a production method in the case of containing a prepolymer of polyurethane). In this case, although the usage-amount of the said polyol is not specifically limited, It is 30-70 mass% or 40-60 mass% with respect to the mass of the adhesive after manufacture, for example. Although the usage-amount of the said polyisocyanate is not specifically limited, For example, it is 3-20 mass% or 5-15 mass% with respect to the mass of the adhesive after manufacture. The usage-amount of other components (solvent, a catalyst, antioxidant, a crosslinking agent, etc.) may be the same as the manufacturing method mentioned above, for example. In addition, in this case, it is preferable that a crosslinking agent (C) contains a polyol as mentioned above. Although the usage-amount of the said polyol in a crosslinking agent (C) is not specifically limited, For example, the molar amount of the hydroxyl group of the said polyol is 0.5-5 times or 1-4 times with respect to the molar amount of the isocyanate group of the said polyurethane polyisocyanate. Or the molar amount of the hydroxyl group of the said polyol is 0.5 to 5 times or 1 to 4 times with respect to the molar amount of the isocyanate group of the said polyurethane polyisocyanate.

In addition, in this invention, the molecular weight, molecular weight dispersion degree, etc. of the prepolymer (A) of a polyurethane are not specifically limited. The number average molecular weight of the prepolymer of polyurethane is theoretical if the molecular weight of each of the polyisocyanate and polyol used as a raw material for the preparation of the prepolymer of polyurethane and the reaction ratio (NCO / OH equivalent ratio) of the polyisocyanate and the polyol are determined. It can be computed by (Japanese Patent Laid-Open No. 2017-025147).

[3. Adhesive Sheet, Manufacturing Method and Use thereof]

Next, the adhesive sheet of this invention, its manufacturing method, use, etc. are demonstrated, for example.

The adhesive sheet of this invention is an adhesive sheet in which the adhesive layer was formed in the at least single side | surface of a base material as mentioned above, The said adhesive layer is an adhesive layer formed using the adhesive of the said invention, It is characterized by the above-mentioned. Although the manufacturing method is not specifically limited, For example, it can manufacture by the manufacturing method of the said invention (manufacturing method of the adhesive sheet by this invention).

As mentioned above, the manufacturing method of the said invention (manufacturing method of the adhesive sheet by this invention) is a coating process of coating the adhesive of this invention to the adhesion layer formation surface in which the said adhesion layer is formed of the said base material. And a heating step of heating the pressure-sensitive adhesive on the pressure-sensitive adhesive layer-forming surface after the coating step. Hereinafter, the manufacturing method of the adhesive sheet by this invention mainly when the prepolymer (A) of polyurethane contains the polyurethane polyol synthesize | combined with a polyol and polyisocyanate is demonstrated, for example.

That is, first, the adhesive of the said invention is coated on the adhesion layer formation surface in which the said adhesion layer is formed of the said base material (coating process). The said base material is not specifically limited, For example, although plastics, a polyurethane, paper, metal foil, etc. are mentioned, Plastic is preferable. As said plastics, PET (polyethylene terephthalate), PE (polyethylene), PP (polypropylene), PC (polycarbonate), etc. are mentioned, for example.

The shape of the said base material is not specifically limited, For example, a sheet, a film, a foam, etc. are mentioned. It is preferable that the said base material is the elongate tape shape which can be wound from a viewpoint of the ease of handling of the adhesive sheet after manufacture, the ease of preservation, etc., for example.

In addition, the said base material may be a base material which performed the easily adhesive process on the adhesive layer formation surface of the said base material as needed, for example. Although the said easily bonding process is not specifically limited, For example, the method of processing corona discharge, the method of apply | coating an anchor coat agent, etc. are mentioned, for example.

When the adhesive of this invention does not contain a crosslinking agent (C), it is preferable to mix a crosslinking agent (C), for example, before the said coating process. In the case where the crosslinking agent (C) contains a polyisocyanate, the polyisocyanate is not particularly limited, but the polyisocyanate exemplified in the above `` 2.Method for producing an adhesive '' and the trimethylolpropane adduct and water react with The trimer which has a biuret body, an isocyanurate ring, etc. are mentioned, You may use only one type or may use multiple types together. When a crosslinking agent (C) contains a polyol, it does not specifically limit as said polyol. The said polyol may be the same as the polyol used for the synthesis | combination of the prepolymer (A) of polyurethane illustrated by the above-mentioned "2. Manufacturing method of an adhesive agent", for example, even if it uses only one type and uses multiple types together Also good. In addition, the usage-amount of a crosslinking agent (C) is as above-mentioned, for example. Moreover, you may mix a solvent further before the said coating process for the purpose of making it easy to mix the adhesive of the said invention and the said crosslinking agent, or the purpose of making it easy to coat on the said base material. Although the kind etc. of the said solvent are not specifically limited, For example, it is the same as the solvent illustrated by said "2. manufacturing method of an adhesive", You may use only one type or may use multiple types together.

The coating method in the said coating process is not specifically limited, A well-known method may be sufficient. As said coating method, the roll coater method, the comma coater method, the die coater method, the reverse coater method, the silkscreen method, the gravure coater method etc. are mentioned, for example.

In addition, although the coating amount (coating amount) of the said adhesive in the said coating process is not specifically limited, The thickness of the adhesion layer in the manufactured adhesive sheet is 1-50 micrometers, 5-30 micrometers, 7-, for example. 20 micrometers or 10-15 micrometers.

Moreover, the said adhesive is heated on the said adhesion layer formation surface after the said coating process (heating process). In addition, in order to distinguish the said heating process from the 2nd heating process mentioned later, you may say "a 1st heating process." Although the heating temperature in the said heating process (1st heating process) is not specifically limited, For example, it is 60 degreeC or more, temperature exceeding 60 degreeC, 90 degreeC or more, or temperature exceeding 90 degreeC, or 100 degreeC or more, or 130 degreeC or more. Although the upper limit of the said heating temperature is not specifically limited, For example, it is 150 degrees C or less.

In order to prevent the adhesive layer from protruding from the edge of the base material at the time of storage of the adhesive sheet or during handling, it is preferable to increase the heating temperature in the heating step as high as possible. By making the said heating temperature as high as possible, for example, since the crosslinking (hardening) reaction of the adhesive of this invention and the said crosslinking agent is easy to fully advance, it is guessed that the said protruding can be prevented. However, this mechanism is a guess and does not limit this invention at all.

As mentioned above, in the general adhesive, when the heating temperature after apply | coating an adhesive to a base material is too high, there exists a possibility that the adhesiveness with respect to the said base material of the said adhesion layer may fall. However, according to the adhesive of this invention, even if it heats at high temperature, adhesiveness with respect to the said base material is favorable and, as mentioned above, it can prevent the flipping and protruding to the said base material.

In addition, the heating time in the said heating process (1st heating process) is although it does not specifically limit, For example, drying of the coated adhesive (removal of a solvent) is enough, and the said base material is damaged by heat Time that is not enough is desirable. Although the said specific heating time is based also on the kind of the said solvent, the said base material, etc., it is 30 to 240 second or 60 to 180 second, for example.

Moreover, in the manufacturing method of the adhesive sheet by this invention, it is preferable to include the 2nd heating process which heats at temperature lower than the said heating process after the said heating process (1st heating process). Although the said 2nd heating process does not need to be performed, it can prevent more protruding of the adhesion layer from the edge of the said base material by doing this. Although the phenomenon which arises in the said 2nd heating process is not clear, it is guessed that hardening (crosslinking) of an adhesion layer further advances, for example. However, this conjecture does not limit this invention at all. Although the heating temperature in a said 2nd heating process is not specifically limited, For example, it is 30-50 degreeC or 35-45 degreeC. In addition, the heat time in a said 2nd heating process is although it does not specifically limit, For example, it is 24-120 hours or 48-96 hours.

Although the use of the adhesive sheet of this invention is not specifically limited, As mentioned above, it is preferable to use as a protective sheet of the said image display surface by affixing on the image display surface of an image display apparatus. Moreover, when using for this use, it is more preferable that the said base material is transparent, for example.

As described above, the image display device of the present invention is an image display device in which a protective sheet of the image display device is attached to an image display surface, wherein the protective sheet is the adhesive sheet of the present invention. Although it does not specifically limit as said image display apparatus, For example, a mobile telephone, a smart phone, a tablet type computer etc. are mentioned. However, the use of the adhesive sheet of this invention is not limited to an image display apparatus, For example, it can be used also as a protective sheet of window glass, such as an automobile and a building. In addition, the adhesive sheet of this invention is not limited to glass, for example, It can be used also as a protective sheet for ITO (Indium Tin Oxide) processed on the glass substrate as a transparent conductive film. In addition, the use of the adhesive sheet of this invention is not limited to these, For example, it can be widely used for uses, such as a general adhesive sheet, an adhesive film, and an adhesive tape. Moreover, the use of the adhesive of this invention is not limited only to the adhesive sheet of this invention especially, For example, it can be widely used for uses, such as an adhesive.

Although the form of the adhesive sheet of this invention is not specifically limited, For example, at the time of storage, a separator is affixed on the said adhesion layer, and the said adhesion layer is protected and just before use (for example, attachment to an image display apparatus etc.). It is preferable to peel the separator at. For example, it is preferable that the adhesive sheet of this invention is a long tape shape which can be wound, and is wound up and stored. According to the adhesive tape of this invention, it can prevent that the said adhesion layer protrudes from the edge of an adhesive tape at the time of winding-up, storage time, etc ..

Example

EMBODIMENT OF THE INVENTION Hereinafter, the Example of this invention is described. In addition, this invention is not limited to these Examples.

The raw material name (compound name) used by the following example and the comparative example, the product name (brand name), and the manufacturer are shown in following Table 1.

TABLE 1

Synthesis Example 1

According to the following procedure, the prepolymer (A) of polyurethane was synthesize | combined.

Glycerin PO.EO, hexamethylene diisocyanate, toluene, and DBTDL were put into the separable flask provided with the stirrer, the reflux cooling tube, and the thermometer, and reaction was performed at 60 degreeC for 3 hours, stirring. When the NCO group of the content was measured using the infrared spectrophotometer (IR), the residue of the NCO group was not able to be confirmed. Next, the content was cooled to 40 degrees C or less, and antioxidant and ethyl acetate were added. In addition, "glycerine PO.EO" shows the propylene oxide and ethylene oxide addition product of glycerin, and "DBTDL" shows dibutyltin dilaurate.

Synthesis Example 2

A polyurethane prepolymer (A) was synthesized in the same manner as in Synthesis Example 1 except that glycerin PO and EO in Synthesis Example 1 were used as glycerin PO. In addition, "glycerol PO" shows the propylene oxide addition product of glycerin.

Synthesis Example 3

A polyurethane prepolymer (A) was synthesized in the same manner as in Synthesis Example 1 except that glycerin PO.EO of Synthesis Example 1 was used in combination with a pluronic polyol. In addition, a "pluronic polyol" shows the ethylene oxide adduct of polypropylene glycol.

Synthesis Example 4

A polyurethane prepolymer (A) was synthesized in the same manner as in Synthesis Example 1 except that glycerin PO.EO and Synthetic Polypropylene glycol of Synthesis Example 1 were used in combination.

Synthesis Example 5

A polyurethane prepolymer (A) was synthesized in the same manner as in Synthesis Example 1 except that hexamethylene diisocyanate in Synthesis Example 1 was used as 4,4'-diphenylmethane diisocyanate.

The component amount (mass part) of each component used by the synthesis | combination of the prepolymer (A) of the polyurethane in the said synthesis examples 1-5 is put together in Table 2, and is shown. That is, in the synthesis examples 1-5, the solution containing the prepolymer (A) of polyurethane was obtained.

TABLE 2

Example 1

1 mass part of linear alkylbenzenesulfonic acid of organic acid, and 8 mass parts of crosslinking agents N (polyisocyanate polyisocyanate crosslinking agent made from Lion Specialty Chemicals) of 100 mass parts (60 mass parts as solid content) of the polyurethane of the synthesis example 1, solid content 75 mass parts %) Was mix | blended and what was stirred well was made into the adhesive (coating liquid) of Example 1.

Example 2

An adhesive was prepared in the same manner as in Example 1 except that Polyol of Polyurethane was used as Synthesis Example 2.

Example 3

An adhesive was prepared in the same manner as in Example 1 except that Polyol of Polyurethane was used as Synthesis Example 3.

Example 4

An adhesive was prepared in the same manner as in Example 1 except that Polyol of Polyurethane was used as Synthesis Example 4.

Example 5

An adhesive was prepared in the same manner as in Example 1 except that the polyol of polyurethane was used as Synthesis Example 5.

Example 6

An adhesive was prepared in the same manner as in Example 1 except that the organic acid was used as the branched alkylbenzene sulfonic acid.

Example 7

An adhesive was prepared in the same manner as in Example 1 except that the acidic phosphoric acid ester compound JP-508 (manufactured by Johoku Chemical Co., Ltd.) was used instead of the organic acid.

Example 8

An adhesive was prepared in the same manner as in Example 1 except that the acidic phosphoric acid ester compound AP-8 (manufactured by Daihachi Chemical Co., Ltd.) was used instead of the organic acid.

Example 9

An adhesive was prepared in the same manner as in Example 1 except that the acidic phosphoric acid ester compound phosphpanol P-700 (manufactured by Toho Chemical Co., Ltd.) was used instead of the organic acid.

Example 10

An adhesive was produced in the same manner as in Example 1 except that 30 parts by mass of a carboxylic acid ester represented by the general formula (1001) (n is an average of 12) was further blended.

[Formula 1001]

Example 11

An adhesive was produced in the same manner as in Example 1 except that 30 parts by mass of a carboxylic acid ester represented by the formula (1010) (n is an average of 10) was further blended.

[Formula 1010]

Example 12

An adhesive was produced in the same manner as in Example 1 except that 0.6 parts by mass of the linear alkylbenzenesulfonic acid was used.

Example 13

An adhesive was prepared in the same manner as in Example 1 except that 3.0 parts by mass of linear alkylbenzenesulfonic acid was used.

Example 14

An adhesive was prepared in the same manner as in Example 9 except that phosphanol P-700 (manufactured by Toho Chemical Co., Ltd.) was 2.0 parts by mass.

Example 15

An adhesive was prepared in the same manner as in Example 9 except that phosphanol P-700 (manufactured by Toho Chemical Co., Ltd.) was 4.0 parts by mass.

Example 16

An adhesive was prepared in the same manner as in Example 1 except that 2 parts by mass of the acidic phosphoric acid ester compound JP-504 (manufactured by Johoku Chemical Co., Ltd.) was used in place of the organic acid.

Example 17

An adhesive was prepared in the same manner as in Example 1 except that the organic acid was used as propionic acid.

Example 18

An adhesive was prepared in the same manner as in Example 1 except that the organic acid was used as n-nonadecanoic acid.

Example 19

An adhesive was prepared in the same manner as in Example 1 except that 2 parts by mass of the acidic phosphoric acid ester compound phosphpanol B-410 (manufactured by Toho Chemical Co., Ltd.) was used in place of the organic acid.

Example 20

An adhesive was prepared in the same manner as in Example 1 except that 4 parts by mass of an anhydrous benzoic acid of an organic acid anhydride was passed in place of the organic acid, and 12 parts by mass of the crosslinking agent N was used.

Example 21

An adhesive was prepared in the same manner as in Example 1 except that phthalic anhydride of an organic acid anhydride was used instead of the organic acid.

Example 22

An adhesive was prepared in the same manner as in Example 1 except that 0.3 parts by mass of linear alkylbenzenesulfonic acid was used.

Example 23

A pressure-sensitive adhesive was produced in the same manner as in Example 1 except that the crosslinking agent N was 4 parts by mass.

Example 24

An adhesive was produced in the same manner as in Example 1 except that the crosslinking agent N was 12 parts by mass.

Example 25

An adhesive was prepared in the same manner as in Example 1 except that 2 parts by mass of the acidic phosphoric acid ester compound AP-4 (manufactured by Daihachi Chemical Co., Ltd.) was used in place of the organic acid, and 12 parts by mass of the crosslinking agent N was used.

Example 26

An adhesive was prepared in the same manner as in Example 1 except that 2 parts by mass of the acidic phosphoric acid ester compound AP-10 (manufactured by Daihachi Chemical Co., Ltd.) was used instead of 12 parts by mass of the organic acid.

Example 27

An adhesive was prepared in the same manner as in Example 1 except that 2 parts by mass of the acidic phosphoric acid ester compound phosphpanol L-220 (manufactured by Toho Chemical Co., Ltd.) was used and 12 parts by mass of the crosslinking agent N was used instead of the organic acid.

Example 28

An adhesive was prepared in the same manner as in Example 1 except that 2 parts by mass of the acidic phosphoric acid ester compound phosphpanol S-710 (manufactured by Toho Chemical Co., Ltd.) was used and 12 parts by mass of the crosslinking agent N was used instead of the organic acid.

Example 29

An adhesive was prepared in the same manner as in Example 1 except that the organic acid was used as 1 part by mass of 2-ethylhexanoic acid.

Example 30

An adhesive was produced in the same manner as in Example 1 except that the organic acid was 0.6 parts by mass of linear alkylbenzenesulfonic acid and 1 part by mass of 2-ethylhexanoic acid.

[Comparative Example 1]

An adhesive was prepared in the same manner as in Example 1 except that the organic acid and the acidic phosphoric acid ester compound were not blended.

[Comparative Example 2]

A pressure-sensitive adhesive was produced in the same manner as in Comparative Example 1 except that 1 part by mass of carboxylic acid ester represented by the formula (1010) (n is an average of 10) was further blended.

[Comparative Example 3]

A pressure-sensitive adhesive was produced in the same manner as in Comparative Example 1 except that 30 parts by mass of a carboxylic acid ester represented by the formula (1010) (n is an average of 10) was further blended.

About the adhesive of the Example and comparative example which were manufactured as mentioned above, adhesive force (peel force), wettability, and adherend contamination were evaluated by the following method. The results are summarized in Table 2 below.

1. Adhesion

For evaluation of the adhesive force, an adhesive sheet produced by coating a coating liquid (adhesive) on a 50 μm-thick PET film was used as a sample. In an environment of 23 ° C x 50% RH, the sample was cut to a width of 25 mm, and bonded to the adherend (glass plate) with a load of 3 kg of 2 kg rollers. After 1 hour of curing, the peeling force (N / 25 mm) when one end of the sample was pulled off at a speed of 300 mm / min in the 180 ° direction with an autograph was used as the adhesive force. It is preferable that this adhesive force (peel force) is not excessively large, and, as for the peeling force as an adhesive sheet from a re peelable viewpoint, it is preferable that it is 0.1 N / 25 mm or less.

2. wettability

In the evaluation of wettability, the pressure-sensitive adhesive sheet prepared by coating the coating liquid on a 50 μm-thick PET film was used as a sample. The sample was cut into 5 cm x 10 cm, and only one side of a width of 5 cm of the sample was brought into contact with the glass plate in a state of tilting at 45 °. Then, hands were removed and the time (seconds) required for the entire surface of the sample to come into contact with the glass plate (wet the glass plate) was set as the wettability evaluation. The shorter the time (second), the higher the wettability (adhesiveness) to the glass plate. The higher the wettability, the faster the bonding to the adherend (the glass plate in this example). The wettability is preferably 10 seconds / 10 cm or less.

3. Adherent contamination

For evaluation of adherend contamination resistance, an adhesive sheet prepared by coating a coating liquid on a 50 μm-thick PET film was used as a sample. The sample was cut into 4 cm x 10 cm, and the adhesive sheet was bonded to the glass plate or PET film. This was allowed to stand for 72 hours in a constant temperature and humidity chamber at 80 ° C. × 80% RH, and then left for 1 hour under an environment of 23 ° C. × 50% RH. Next, the adhesive sheet was peeled off from the glass plate or PET film, and the state of white contamination of the glass surface of the part where the adhesive sheet was bonded was visually evaluated, and this was made into the evaluation result of adherend contamination. In addition, the state of white contamination was evaluated by irradiating white light in a dark room.

(Evaluation result of adherend contamination)

(Double-circle): White contaminants were not seen at all on the glass surface.

(Circle): A pointy white contaminant was seen in a part of glass surface.

(Triangle | delta): The white dirt was seen in the shape of a stain on the glass surface.

X: White contaminants were seen on the entire surface of the glass surface.

TABLE 3

Table 4

As shown in Table 3, 4, the adhesive of Examples 1-30 containing all the components (A)-(C) had the favorable adhesive force (repeelability), wettability, and adherend contamination. That is, the adhesive of Examples 1-30 was able to satisfy all the re-peelability, wettability, and adherend contamination simultaneously. On the other hand, although the adhesive of Comparative Examples 1-3 which does not contain the component (B) (acid component) had favorable adhesive force (re-peelability) and wettability, adherend contamination was inferior compared with an Example. .

Industrial availability

As described above, according to the present invention, it is possible to provide a pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, a method for producing a pressure-sensitive adhesive sheet, and an image display apparatus capable of satisfying re-peelability, wettability, and adherend contamination under high temperature and high humidity. The manufacturing method of the adhesive, the adhesive sheet, and the adhesive sheet of this invention can be used as a protective sheet of window glass, such as a mobile telephone, a smart phone, a car, and a building, for example. In addition, this invention is not limited to this, It can use widely in various uses, For example, it is widely applicable to the field where the manufacturing method of a general adhesive, an adhesive sheet, and an adhesive sheet is used.

This application claims priority based on Japanese Patent Application No. 2017-095993 for which it applied on May 12, 2017, and blows in all that the specification.

Claims (7)

Polyurethane prepolymer (A),
At least one selected from the group consisting of an organic acid (B-1), an acidic phosphoric acid ester compound (B-2), and an organic acid anhydride (B-3),
The acidic phosphoric acid ester compound (B-2) is at least one selected from the group consisting of acidic phosphoric acid ester compounds represented by the following formulas (I), (II) and (III),
The organic acid (B-1) is an organic acid other than the acidic phosphoric acid ester compound (B-2),
The prepolymer (A) of the polyurethane is a pressure-sensitive adhesive, characterized in that the prepolymer synthesized from a polyol and an isocyanate.
[Formula I]

In the formula (I),
R ¹ and R ² are each a hydrogen atom, a hydrocarbon group or an aryl group,
R ¹ and R ² may be the same or different,
At least one of R ¹ and R ² is a hydrocarbon group or an aryl group.
[Formula II]

[Formula III]

In the above formulas (II) and (III),
R ³ and R ⁴ are each a hydrogen atom, a hydrocarbon group or an aryl group,
R ³ and R ⁴ may be the same or different,
At least one of R ³ and R ⁴ is a hydrocarbon group or an aryl group,
AO is an alkylene oxide group, and each AO may be same or different,
n represents an integer greater than or equal to 1, and each n may be same or different. The method of claim 1,
The organic acid (B-1) is at least one of carboxylic acid and sulfonic acid. The method according to claim 1 or 2,
Said organic acid anhydride (B-3) is at least one of a carboxylic anhydride and a sulfonic anhydride. The method according to any one of claims 1 to 3,
Moreover, the crosslinking agent (C) is included, The said adhesive is an adhesive characterized by the polyisocyanate or polyol. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed on at least one side of the substrate, wherein the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer formed by using the pressure-sensitive adhesive according to any one of claims 1 to 4. A coating step of coating the pressure-sensitive adhesive according to any one of claims 1 to 4 on the pressure-sensitive adhesive layer forming surface on which the pressure-sensitive adhesive layer is formed;
The manufacturing method of the adhesive sheet of Claim 5 including the process of heating the said adhesive on the said adhesion layer formation surface after the said coating process. As an image display apparatus in which a protective sheet of an image display apparatus is attached to an image display surface,
The said protective sheet is the adhesive sheet of Claim 5, The image display apparatus characterized by the above-mentioned.