JP2001192636A - Adhesive and adhesive tape using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane urea resin adhesive that has a moderate adhesion power which the conventional polyurethane adhesives could never attain, by improving the defect, the poor removableness, of an acrylic resin adhesive. SOLUTION: The objective adhesive comprises the Michel's addition type urethane-urea resin bearing isocyanate groups on the chain terminals that is obtained by allowing (B) an amine prepared by the Michel's addition of (c) a polyamine to (d) an unsaturated compound to react with (A) the polyurethane- urea resultant from the reaction between (a) a polyol and (b) a polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane urea resin pressure-sensitive adhesive used for laminates such as pressure-sensitive adhesive tapes, labels, seals, decorative sheets, non-slip sheets and double-sided pressure-sensitive adhesive tapes.

[0002]

2. Description of the Related Art Adhesives can be broadly classified into acrylic resin-based and rubber-based adhesives according to their constituent materials, but both have drawbacks in performance. Acrylic resin-based pressure-sensitive adhesives have excellent pressure-sensitive adhesive properties, but their removability is not sufficient for general industrial use, and further improvement in odor and skin irritation is desired for medical use. Since the performance of the rubber system cannot be ensured unless it contains a low molecular weight material, addition of a low molecular weight material such as a plasticizer is indispensable, but after a long period of time, the low molecular weight material bleeds, causing a significant decrease in performance. .

In recent years, acrylic resin-based pressure-sensitive adhesives whose performance can be relatively easily controlled have become mainstream, but problems such as removability, odor, and skin irritation have not been solved. Regarding removability, after the acrylic resin-based pressure-sensitive adhesive is applied to the adherend, several days later, when the adhesive is peeled off again from the adherend, the adhesive strength increases and the resin migrates to the adherend. The reality is that you cannot avoid ".

On the other hand, various improvements have been made, and one of the most promising means is to make the pressure-sensitive adhesive slightly adhesive having an adhesive force of 100 g / inch width or less to exhibit removability. It is very difficult for a resin-based pressure-sensitive adhesive to exhibit slight tackiness with extremely low tackiness, resulting in insufficient holding power and large variations in tackiness depending on the amount of a curing agent added.
When sticking a sheet coated with an adhesive on a window glass or the like, fine adhesion is indispensable in order to stick cleanly without bubbles, and it has been difficult with an acrylic resin-based adhesive.
Further, the market is most expected to develop a pressure-sensitive adhesive having a removability in a medium pressure-sensitive adhesive region of 800 to 1500 g / inch width, but an acrylic resin pressure-sensitive adhesive cannot remove adhesive residue, and is thus re-peelable. There was no adhesive in the middle adhesive region having the property. In addition, acrylic resin-based pressure-sensitive adhesives have fundamental problems in odor, skin irritation, and the like, and it has been difficult to improve their performance as long as acrylic resin is the main component.

As a solution to this problem, studies are being made to impart adhesiveness to urethane resins to obtain properties that cannot be obtained with acrylic resins. There have been attempts to make adhesives using the high cohesive force of urethane resins, but the range of physical properties of urethane resin-based adhesives made only by urethanization reaction with polyol and diisocyanate is in the weakly adhesive range. Was. In order to increase the adhesive strength of polyurethane-based pressure-sensitive adhesives, there was a method of reducing the amount of curing agent, but due to the reduced cross-linking structure and insufficient cohesion, good removability was not exhibited, and polyurethane-based pressure-sensitive adhesives were not developed. It was difficult to improve the adhesive strength more than the medium adhesive.

[0006]

SUMMARY OF THE INVENTION The present invention solves the drawback of insufficient removability of an acrylic resin-based pressure-sensitive adhesive, and has a Michael-attached urethane having a medium tackiness that cannot be achieved by a conventional polyurethane resin-based pressure-sensitive adhesive. An object of the present invention is to provide a pressure-sensitive adhesive containing a urea resin.

[0007]

As a result of various studies on the resin composition and reaction method of the polyurethane resin, various functional groups were introduced into the polyamine compound by the Michael addition reaction, and a Michael addition type urethane urea resin having a higher molecular weight was obtained. It has been found that by using this, a pressure-sensitive adhesive having good removability and exhibiting moderate adhesive strength can be obtained.

According to the present invention, a polyamine (c) and an unsaturated compound (d) are subjected to a Michael addition reaction with a urethane prepolymer (A) obtained by reacting a polyol (a) with a polyisocyanate (b). Pressure-sensitive adhesive comprising a Michael addition type urethane urea resin having an isocyanate group at the end by reacting an amine compound (B).

Further, the present invention provides a urethane prepolymer (A) obtained by reacting a polyol (a) and a polyisocyanate (b) with a Michael addition reaction of a polyamine (c) with an unsaturated compound (d). Pressure-sensitive adhesive comprising a Michael addition type urethane urea resin obtained by reacting an amine compound (B) with a reaction terminator (f).

Further, the present invention relates to the above-mentioned pressure-sensitive adhesive, wherein the reaction terminator (f) is a monoamine compound having a hydroxyl group.

Further, the present invention relates to the above-mentioned pressure-sensitive adhesive, further comprising a curing agent (D).

The present invention further relates to the above-mentioned pressure-sensitive adhesive, wherein the polyamine (c) is isophoronediamine or 2,2,4-trimethylhexamethylenediamine.

Further, the present invention provides a urethane prepolymer (A) obtained by reacting a polyol (a) and a polyisocyanate (b) with a Michael addition reaction of a polyamine (c) and an unsaturated compound (d). A first step of reacting the resulting amine compound (B) to synthesize a Michael addition type urethane urea resin having an isocyanato group at a terminal,
A second step of reacting the Michael addition type urethane urea resin with a reaction terminator (f), and a third step of blending a curing agent (D) with the reaction product of the second step. And a method for producing an adhesive.

[0014] The present invention also relates to a laminate comprising a substrate and the above-mentioned pressure-sensitive adhesive.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Michael addition type urethane urea resin referred to in the present invention is a urethane urea resin having a structure in which an unsaturated compound is added to a polyamino compound by Michael.

In the present invention, the polyamine (c) is a compound having at least two primary or secondary amino groups, and the amino compound (B) is synthesized by Michael addition of at least one unsaturated compound. The obtained amino compound (B) is used as a raw material for a urea reaction for the purpose of modifying a urethane resin.

In the present invention, the polyamine (c) is
A polyisocyanate compound, a polyol compound, and, if necessary, react with an isocyanato group of a polyurethane urea obtained by reacting a polyamino compound,
It can also be used to introduce at least one primary or secondary amino group at the end of the polyurethane urea.

As the polyamine (c) used in the present invention, known ones can be used. Specifically, ethylenediamine, propylenediamine, trimethylenediamine,
Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-
Aliphatic polyamines such as trimethylhexamethylenediamine, tolylenediamine, hydrazine, and piperazine, isophoronediamine, dicyclohexylmethane-4,4 '
-Aliphatic polyamines including alicyclic polyamines such as diamines, and aromatic polyamines such as phenylenediamine and xylylenediamine. Further, 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine , (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine and other diamines having a hydroxyl group in the molecule, dimer diamines obtained by converting carboxyl groups of dimer acid into amino groups, and propoxyamine at both terminals And a polyoxyalkylene glycol diamine represented by the following formula (2) can also be used. H ₂ -NCH ₂ -CH ₂ -C
H ₂ —O (C _n H _2n —O) _m —CH ₂ —CH ₂ —CH ₂ —NH ₂
(2) (in the formula (2), n is an arbitrary integer of 2 to 4, and m is 2 to 50)
Indicates an arbitrary integer of. ) Among the above-mentioned polyamines (c), isophoronediamine, 2,2,4-trimethylhexamethylenediamine, and hexamethylenediamine are preferred because of easy control of the reaction and excellent hygiene.

The urethane prepolymer (A) used in the present invention is a compound obtained by reacting a polyol compound (a) and a polyisocyanate compound (b) and having at least one isocyanate group. In addition, as a raw material of the urethane prepolymer (A), a polyamine (c), water, or a compound (e ′) having an ionic functional group and a group capable of reacting with an isocyanate group described below is included as necessary. May be.

Examples of the polyol (a) include high molecular weight polyols, bisphenols such as bisphenol A and bisphenol F, glycols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols, and other polyols. Can be used. These may be mixtures.
Further, compounds having two or more active hydrogen groups obtained by reacting one or more of these compounds with other compounds such as olefins and aromatic hydrocarbons can also be used.

The high molecular weight polyols are compounds having a repeating unit having a degree of polymerization of 2 or more and having two hydroxyl groups, and include polyester polyols and polyether polyols.

As the polyester polyols used in the present invention, known polyester polyols can be used.

As the polyester polyol, for example,
There is a polyester polyol obtained by a condensation reaction between a glycol component and a dibasic acid component. Ethylene glycol, propylene glycol which is a diol as a glycol component,
Dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol,
1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, bisphenol A, and a polyol. Glycerin, trimethylolpropane, pentaerythritol and the like, and dibasic acid components such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid; Or an aromatic dibasic acid is mentioned. A polyester polyol obtained by ring-opening polymerization of a cyclic ester compound such as lactones such as ε-caprolactone poly (β-methyl-γ-valerolactone) and polyvalerolactone;
Polycarbonate polyol, silicone polyol and the like can be used.

The molecular weight of the polyester polyols can be used from a low molecular weight to a high molecular weight, preferably a polyester polyol having a molecular weight of 1,000 to 5,000 and bifunctional or more, more preferably a molecular weight of 1,500 to 5,000.
3,500 or more bifunctional polyester polyols are used. The use amount thereof is preferably 0 to 50 mol% in the polyol (a) constituting the urethane prepolymer (A).

As the polyether polyols used in the present invention, known polyether polyols can be used. For example, by condensation of alkylene oxide polymers, copolymers or graft copolymers such as tetrahydrofuran, or ethylene oxide, propylene oxide, butylene oxide, or hexanediol, methylhexanediol, heptanediol, octanediol or a mixture thereof. Those having two or more hydroxyl groups, such as polyether glycols and propoxylated or ethoxylated polyether glycols, can be used.

Furthermore, low molecular weight polyols such as glycerin, sorbitol, trimethylolpropane, trimethylolbutane, trimethylolethane, 1,2,2 are used as polymerization initiators in the polymerization of alkylene oxides.
3 such as 6-hexanetriol and pentaerythritol
A polyether polyol using an alcohol having a valency or higher is also preferably used. Adducts of partially esterified polyhydric alcohols and polyether polyols can also be used. In this case, the polyether moiety may be a block polymer or a random polymer. The terminal to which the polyether polyol is added is a hydroxyl group, but may be partially an alkyloxy group or an aromatic hydrocarbonoxy group.

The molecular weight of the polyether polyols can be used from a low molecular weight to a high molecular weight, but is preferably a polyether polyol having a molecular weight of 1,000 to 5,000 and having two or more functions, more preferably a molecular weight of 1,000 to 400.
A polyfunctional polyol having a functionality of 0 or more than 2 is used. The use amount thereof is preferably 50 to 100 mol% in the polyol (a) constituting the polyurethane prepolymer (A).

The polyol (a) may be a urethane polyol having a terminal hydroxyl group by reacting the above polyether polyol and / or polyester polyol with the following polyisocyanate compound in an equimolar equivalent or less.

Other polyols include ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6-
Two hydroxyl groups such as hexanediol, neopentyl glycol, cyclohexanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl 2,2,8,10-tetraoxospiro [5.5] undecane) And compounds having three or more hydroxyl groups, such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, and methyl glucoside.

As the polyol (a), a polyol (e) containing at least one ionic functional group can also be used. An ionic functional group is an ionic group such as a quaternary ammonium group, a tertiary amino group, a carboxylate group, a carboxyl group, a sulfonate group, a sulfonic acid group, a phosphonium group, a phosphinic acid group, a sulfate group, or the like. It is a precursor group. Carboxyl groups, tertiary amino groups, etc. do not contain ionic groups, but can be easily converted to ionic groups by neutralization or quaternization reaction with ammonia, tertiary amine, acetic acid, etc. Shall be included.

The polyol (e) containing at least one ionic functional group is suitably used in terms of making the Michael addition type urethane urea resin aqueous or increasing the reaction rate during the synthesis of the urethane prepolymer (A). You.

Specific examples of the polyol (e) containing at least one ionic functional group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, 2,2 Carboxyl group-containing polyol compounds such as -bis (hydroxymethyl) valeric acid and 2,2-bis (hydroxymethyl) butanoic acid, and tertiary such as N, N-bis (2-hydroxypropyl) aniline and N-methyldiethanolamine Examples include amino group-containing polyols.

Glycerin monophosphate disodium salt, dimethylol sodium phosphinate,
Polyester polyol having sodium sulfoisophthalate unit, carboxyl group-containing polyester polyol obtained by addition / condensation reaction of low molecular weight glycol with aliphatic or aromatic polybasic anhydride, lactone with dimethylolalkanoic acid as initiator Other examples include a carboxyl group-containing polyol other than the above, which is subjected to ring-opening polymerization. Of these, 2,2-bis (hydroxymethyl)
Propionic acid, 2,2-bis (hydroxymethyl) butyric acid, 2,2-
Bis (hydroxymethyl) valeric acid, 2,2-bis (hydroxymethyl) butanoic acid and polyols containing a tertiary amino group are preferably used.

In order to introduce an ionic functional group, it is not polyol (a) in combination with polyol (a).
A compound (e ′) having a group capable of reacting with an isocyanate group and an ionic functional group may be used.

Examples of such a compound (e ') include diaminocarboxylic acid, sodium diaminobenzenesulfonate, sodium hydroxyethylphosphonate, and N-methylethanolamine.

As the polyisocyanate compound (b) used in the present invention, conventionally known compounds can be used. For example, aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate And isocyanate.

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,
Examples thereof include 3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, and 4,4 ', 4 "-triphenylmethane triisocyanate.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI),
Pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like can be given.

As the araliphatic polyisocyanate,
ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate And 1,3-tetramethylxylylene diisocyanate.

Examples of the alicyclic polyisocyanate include 3-
Isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2 , 6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like.

Further, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, and the like can also be used in combination. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and their modified polyisocyanates can be used. As the modified polyisocyanate, a carbodiimide group, a uretdione group, a uretoimine group, a buret group reacted with water, an isocyanurate group, or a modified compound having two or more of these groups can be used. The reaction product of the above-mentioned polyhydric alcohol polyether adduct and diisocyanate can also be used as the polyisocyanate compound (b).

The polyisocyanate compound (b) used in the present invention includes 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Use of a non-yellowing polyisocyanate compound such as isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), xylylene diisocyanate, hydrogenated MDI, etc. is preferred from the viewpoint of weather resistance.

The unsaturated compound (d) used in the present invention is used for modifying a urethane urea resin. Therefore, the kind of the unsaturated compound to be used can be arbitrarily selected according to the purpose of the modification.

Examples of the unsaturated compound (d) having the above structure include (meth) acrylate compounds, fatty acid vinyl compounds, alkyl vinyl ether compounds, α-olefin compounds, vinyl compounds, ethynyl compounds and the like. The unsaturated compound (d) may have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, and a silanol group.

As the (meth) acrylate compound,
There are alkyl (meth) acrylate and alkylene glycol (meth) acrylate.

More specifically, examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, -Ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (Meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate , Nonadecyl (meth) acrylate, icosyl (meth) acrylate, henycosyl (meth) acrylate, docosyl (meth) acrylate and other alkyl (meth) acrylates having 1 to 22 carbon atoms. Preferably, an alkyl group-containing acrylate having a C 2-10, more preferably C 2-8 alkyl group or a corresponding methacrylate is used. When the number of carbon atoms is 23 or more, the Michael addition reaction becomes difficult to proceed.

Examples of the alkylene glycol (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and hexaethylene glycol mono (meth) acrylate. Such as polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth), etc. Methoxyethylene glycol (meth) acrylate, such as a monoacrylate having a polyoxyalkylene chain or a corresponding monomethacrylate. Xydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (Meth) acrylate, n-
Pentaxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth)
Acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentaxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) Acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth)
Phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxy, etc. such as acrylate, ethoxy polyethylene glycol (meth) acrylate, monoacrylate having a polyoxyalkylene chain having a terminal alkoxy group and a corresponding monomethacrylate, etc. Triethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate,
There is a polyoxyalkylene-based acrylate having a phenoxy or aryloxy group at a terminal such as phenoxytetrapropylene glycol (meth) acrylate or a corresponding methacrylate.

Among the acrylates having a polyoxyalkylene chain or the corresponding methacrylate, the compound having a hydroxyl group terminal has a catalytic effect at the time of the Michael addition reaction. It is preferably used because it can be used.

Examples of the unsaturated compound having a carboxyl group include maleic acid, fumaric acid, itaconic acid, citraconic acid, or an alkyl or alkenyl monoester thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (Meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. You can do it.

Other hydroxyl group-containing unsaturated compounds include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Examples include hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene.

Examples of the nitrogen-containing unsaturated compound include (meth)
Acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N
Monoalkylol (meth) acrylamide such as -ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N , N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (Ethoxymethyl) acrylamide, N-ethoxymethyl-N-propoxymethylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N
-(Propoxymethyl) methacrylamide, N, N-
Di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) methacrylamide,
N, N-di (pentoxymethyl) acrylamide, N-
Acrylamide unsaturated compounds such as dialkylol (meth) acrylamide such as methoxymethyl-N- (pentoxymethyl) methacrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate methylethylaminoethyl (meth) acrylate, Examples thereof include unsaturated compounds having a dialkylamino group such as dimethylaminostyrene and diethylaminostyrene.

Still other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, and 2-perfluorohexylethyl (meth). Acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-
Perfluorononylethyl (meth) acrylate, 2-
Perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluorooctylundecyl (meth) acrylate, etc. Perfluoroalkylalkyl (meth) acrylates having a perfluoroalkyl group of from 20 to 20; perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene; and perfluoroalkylenes and the like. Alkyl group-containing vinyl monomer, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyl Etc. can be mentioned silanol group-containing vinyl compounds and derivatives thereof such as trimethoxy silane, it can be used more from these groups.

Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate and the like.

As the alkyl vinyl ether compound,
Butyl vinyl ether, ethyl vinyl ether and the like. Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene.

Examples of the vinyl compound include allyl compounds such as allyl acetate, allyl alcohol, allylbenzene and allyl cyanide, vinyl cyanide, vinylcyclohexane,
Vinyl methyl ketone, styrene, α-methylstyrene, 2
-Methylstyrene, chlorostyrene, and the like.

As the ethynyl compound, acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1
-Cyclohexanol and the like. These can be used alone or in combination of two or more.

Polyamine (c) and unsaturated compound (d)
Is reacted with 1 molar equivalent of active hydrogen of the amino group of the polyamine (c) and 1 molar equivalent of the unsaturated group of the unsaturated compound (d). The polyamine (c) easily adds Michael to the vinyl group or ethynyl group of the unsaturated compound (d) having an electron-withdrawing group.
Acrylic compounds, particularly acrylate compounds, are preferred as compound (d). In addition, comparing the acrylate compound with the corresponding methacrylate compound, the acrylate compound is preferred because it has a higher efficiency of the Michael addition reaction.

As a method for synthesizing the amine compound (B), a known method relating to the Michael addition reaction can be used as it is. When the unsaturated compound is a (meth) acrylic compound, particularly an acrylate compound, the reaction proceeds at 10 to 100 ° C., if necessary, in the presence of a catalyst such as an alcohol. Although it depends on the type of unsaturated compound used, it is preferably 40 to
A reaction temperature of 80 ° C. is preferred. If the reaction temperature is too high, an ester amide exchange reaction occurs, which is not preferable. When the unsaturated compound does not have an electron-withdrawing group, the reaction can be performed in the presence of a metal catalyst. In this case, if the reaction is performed at 60 to 100 ° C. while heating in the presence of the catalyst, an appropriate reaction rate can be obtained. It is preferable. A synthetic solvent may or may not be used. The type of the solvent is not particularly limited, and a known solvent such as methyl ethyl ketone, toluene, acetone, and benzene can be used. When the unsaturated compound (d) or polyamine (c) used does not contain a hydroxyl group, an alcoholic solvent such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butyl alcohol, or a mixture thereof. Preferably, a solvent is used. When a reaction solvent is used, the solution concentration is preferably 20% or more, more preferably 50% or more. If the concentration is less than this, the reaction does not easily proceed, which is not preferable. The reaction time varies depending on the type of the unsaturated compound used, but is completed in 30 minutes to 5 hours.

The ratio of the polyamine (c) to the unsaturated compound (d) is determined when at least two secondary or primary amino groups remain in the amine compound (B) obtained by the reaction. Although not particularly limited, it is preferably from 0.1 to 1 mol of the primary amino group of the polyamine (c).
The reaction is preferably carried out at a rate of 1.0 mol, more preferably 0.2 to 0.98 mol. If the amount is less than this, the influence of the side chain is unlikely to appear.

The Michael addition type urethane urea resin is a urethane prepolymer (A) having a terminal isocyanate group.
And an amine compound (B) obtained by Michael addition of a polyamine (c) and an unsaturated compound (d), and if necessary, a polyamine (c), and if necessary, a reaction terminator A monoamine compound can be blended as (f).

The reaction terminator (f) is a compound having a functional group capable of reacting with the isocyanate group, and reacts with the unreacted remaining isocyanate group at the terminal of the Michael addition type urethane urea resin to stabilize the reaction activity of the resin. Let it.

As the reaction terminator (f) used in the present invention, for example, diethylamine, di-n-butylamine,
In addition to dialkylamines such as di-n-octylamine, dicyclohexylamine and diisononylamine, monoethanolamine, diethanolamine and 2-amino-2-
Methyl-1-propanol, tri (hydroxymethyl)
Monoamine having a hydroxyl group such as aminomethane, 2-amino-2-ethyl-1,3-propanediol, 2-aminopropanol and 3-aminopropanol, and alkylhydrazine such as monomethylhydrazine, 1,1-dimethylhydrazine and benzylhydrazine. , Hydrazides such as formhydrazide, acetohydrazide and lauric hydrazide; N, N-dimethyl-1,3-propanediamine;
Monoamine compounds having a tertiary amino group and a primary amino group on one side such as N-diethyl 1,3-propanediamine can be used.

Among the reaction terminators (f), monoamines having a hydroxyl group, such as 2-amino-2-methyl-propanol, can obtain a Michael addition type urethane urea resin having a hydroxyl group at the terminal, and can be stored stably. Excellent in nature,
Further, it is preferable because it also functions as a crosslinking site when a polyisocyanate-based curing agent is added to the Michael addition type urethane urea resin to perform crosslinking. In the case of a monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanate group of the Michael addition type urethane urea resin, but the amino group has higher reactivity and reacts preferentially with the isocyanate group.

In the present invention, a known catalyst can be used as a catalyst used in synthesizing the urethane prepolymer (A). For example, tertiary amine compounds, organometallic compounds and the like can be mentioned.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like.
Alternatively, they can be used together.

The organometallic compounds include tin compounds and non-tin compounds.

The tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide,
Dibutyltin dimaleate, dibutyltin dilaurate (D
BTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, 2-ethylhexanoic acid Tin etc. are mentioned.

Examples of the non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate. Iron, such as iron, 2-ethylhexanoate and iron acetylacetonate; cobalt, such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc, such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium naphthenate And the like.

Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate, and the like are preferable in terms of reactivity and hygiene.

The above catalysts such as tertiary amine compounds and organometallic compounds can be used alone in some cases.
In particular, when polyester diols and polyether diols are used in combination as polyol components, a stable and uniform urethane prepolymer (A) can be obtained by using dibutyltin dilaurate and tin 2-ethylhexanoate together. Is preferred.

When synthesizing the urethane prepolymer (A) of the present invention, a known solvent is suitably used. The use of a solvent plays a role in facilitating reaction control. As the solvent used for such a purpose, for example, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene,
Dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethylsulfoxide, N-methylpyrrolidone and the like. Ethyl acetate, toluene, methyl ethyl ketone, or a mixed solvent thereof is particularly preferable from the viewpoint of the solubility of the amino compound (B) such as the solubility of the polyurethane urea resin and the boiling point of the solvent. When the solvent is used, the concentration in the urethane prepolymer reaction system is preferably 50 to 95%, more preferably 60 to 90%, as the resin solid content. If the concentration is too low, the reactivity is too low. Not preferred.

The urethane reaction for producing the urethane prepolymer (A) by reacting the polyol (a) with the polyisocyanate (b) can be carried out by various methods. 1) a case where the reaction is carried out by charging the entire amount; and 2) a compound (e) having a polyol (a) and, if necessary, at least one ionic functional group and a group capable of reacting with an isocyanate group;
(E ') or a method in which a solvent is charged into a flask, and a polyisocyanate (b) is added dropwise, and then a catalyst is added as necessary. If the reaction is to be precisely controlled, 2) is preferable. The reaction temperature for obtaining the urethane prepolymer (A) is preferably 120 ° C. or lower. More preferably, 5
0-110 ° C. If the temperature is higher than 110 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined molecular weight and structure cannot be obtained. The urethanization reaction is preferably performed at 50 to 110 ° C for 1 to 20 hours in the presence of a catalyst.

The mixing ratio of the polyol (a) and the polyisocyanate (b) is such that the active hydrogen capable of reacting with the isocyanate groups of the polyol (a), the compounds (e) and (e ') is such that the terminal isocyanate groups remain. It is necessary that the molar equivalent of the isocyanato group of the polyisocyanate (b) is larger than 1 with respect to the molar equivalent of 1. An appropriate compounding ratio largely depends on the reactivity of the compound, the abundance ratio of the compound having three or more valences, the use of the obtained resin, and the like. When synthesizing the urethane prepolymer having both ends isocyanate, the equivalent ratio of the isocyanate group to the active hydrogen group of the hydroxyl group or the functional group capable of reacting with the isocyanato group is 1.01 to 4.00, preferably 1.40 to 3 A range of 0.000 is appropriate.

In the present invention, the urea reaction for obtaining the Michael-added urethane urea resin from the urethane prepolymer (A), the amine compound (B), and if necessary, the polyamine (c) and the reaction terminator (f) is carried out. 1) A urethane prepolymer (A) solution is charged into a flask, and an amine compound (B) and, if necessary, a polyamine (c)
2) amine solution (B) and, if necessary, a solution comprising polyamine (c) and reaction terminator (f) are charged into a flask, and urethane prepolymer (A) The method is roughly divided into a method of dropping a solution.
The synthesis is carried out in such a way that the reaction becomes stable, but if there is no problem in the reaction, the method 1) which is easy to operate is preferable. The temperature of the urea reaction of the present invention is preferably 100 ° C. or lower. More preferably, it is 70 ° C. or lower. The reaction rate is high even at 70 ° C., and if it cannot be controlled, the temperature is more preferably 50 ° C. or lower.
If the temperature is higher than 100 ° C., it is difficult to control the reaction rate,
It is difficult to obtain a Michael addition type urethane urea resin having a predetermined molecular weight and structure. When an alcoholic solvent is used as a solvent for synthesizing the amine compound (B), the temperature in the reaction system is preferably adjusted to 50 ° C. or lower, more preferably 40 ° C. or lower when the amine compound (B) is dropped. Preferably.

Further, the urethane prepolymer (A), the amine compound (B) and, if necessary, the polyamine (c)
Is not particularly limited and may be arbitrarily selected depending on the intended use and required performance. Usually, the functional group ratio of the amine group (B) and the amino group of the monoamine compound to the isocyanate group remaining in the urethane prepolymer is used. (Remaining NC
(O / 1 primary or secondary amine) when isocyanate group excess system is preferably 0.70 to 0.97, more preferably
0.8 to 0.96, preferably 1.001 to 1.40 in an amine excess system,
More preferably, it is 1.01 to 1.2.

When the reaction terminator (f) is added, it may be added together with the amine compound (B) or, if necessary, the polyamine (c) to the urethane prepolymer, and / or It may be added after completion of the urea reaction.

The end point of the reaction is determined by measuring isocyanate% by titration and disappearance of isocyanate peak by IR measurement.

The weight average molecular weight of the Michael addition type urethane urea resin is preferably 10,000 or more in terms of standard polystyrene equivalent molecular weight by GPC. More preferably,
More than 30,000. If the weight-average molecular weight is less than 10,000, the adhesive properties, particularly the holding power, decrease remarkably, which is not preferable.

The solution viscosity of the obtained Michael-added urethane urea is not particularly limited and is selected depending on the use of the resin.
ps (25 ° C.), more preferably 100% at 50% solids.
The viscosity is 0 to 5000 cps (25 ° C.). If the viscosity is too high, coating may be difficult. If the viscosity is too low, a resin having a sufficient molecular weight may not be formed.

As the curing agent (D) used in the present invention, the above-mentioned polyisocyanate compound (b) can be used.

The mixing ratio of the Michael addition type urethane urea resin and the curing agent (D) used in the present invention is 0.5 to 10 parts by weight of the curing agent (D) per 100 parts by weight of the Michael addition type urethane urea resin. is there. When the curing agent (D) is 0.
When the amount is less than 5 parts by weight, the cohesive strength decreases, and when the amount is more than 10 parts by weight, the adhesive strength decreases. Preferably it is 1 to 5 parts by weight.

The pressure-sensitive adhesive containing the Michael addition type urethane urea resin according to the present invention may optionally contain other resins,
For example, acrylic resin, polyester resin, amino resin,
Epoxy resins and polyurethane resins can be used in combination. In addition, depending on the application, a filler such as a tackifier, talc, calcium carbonate, titanium oxide, a coloring agent, an ultraviolet absorber, an antioxidant, an antifoaming agent, and an additive such as a light stabilizer may be blended. good.

The polyurethane urea resin pressure-sensitive adhesive according to the present invention may be a tape, a label, a seal, a decorative sheet, a non-slip sheet, a double-sided sheet based on a release sheet such as a plastic film, metal foil, paper, foam, or release paper. It is suitably used for a laminate such as an adhesive tape. Further, it can also be used for a pressure-sensitive adhesive layer of a laminate obtained by laminating substrates of the same or different types. The laminate may be further laminated with a base material or further laminated with a finishing layer.

When a release sheet is used as a substrate, it can be transferred to a sheet such as a plastic film after application, or bonded to a plastic sheet or the like.

[0085] Examples of the plastic film in the present invention include a polyvinyl chloride film, a polyethylene terephthalate (PET) film, a polyurethane film, a nylon film, a treated polyolefin film, an untreated polyolefin film and the like. In particular, a PET film is preferable from the viewpoint of adhesion to a substrate and ease of coating.

As other substrates, metal plates such as iron, aluminum, tinplate, and tin, cloth, wood, plastic plates such as polymethacryl acrylate, polycarbonate, and Teflon (registered trademark), and glass plates can be used.

The thickness of the substrate is preferably from 15 to 100 μm. The amount of the adhesive applied to the substrate is 5
１００100 μm is preferred. In addition, in order to apply the polyurethane resin pressure-sensitive adhesive of the present invention on a substrate, it can be appropriately applied by a known coating method.

As the paper base material in the present invention, plain paper,
Examples include coated paper and art paper. The thickness of these substrates is preferably from 15 to 5,000 μm. Further, the coating amount of the pressure-sensitive adhesive on the substrate is preferably 5 to 100 μm.

[0089]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 300 g of isophoronediamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
300 g of toluene was charged, 184 g of 2-hydroxyethyl acrylate, and 3-ethylhexyl acrylate 3
24 g are added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and the mixture obtained by adding 508 g of toluene was designated as compound (1).

Synthesis Example 2 300 g of isophoronediamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
300 g of toluene is charged, and 184 g of 2-hydroxyethyl acrylate and 176 g of ethyl acrylate are added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and 360 g of toluene was added thereto to obtain a compound (2).

Synthesis Example 3 300 g of 2,2,4-trimethylhexamethylenediamine and 300 g of toluene were charged into a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel. 198 g of acrylate and 190 g of ethyl acrylate are added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and then added with 388 g of toluene to obtain compound (3).

Synthesis Example 4 Isophorone diamine (IPD) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
A) 300 g of toluene and 300 g of toluene were charged, and 226 g of n-butyl acrylate and 229 g of 4-hydroxybutyl acrylate were added dropwise at room temperature. After completion of dropping, at 80 ° C 1
After reacting for an hour, a mixture obtained by adding 455 g of toluene is referred to as compound (4).

Synthesis Example 5 Isophorone diamine (IPD) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
A) 300 g and 300 g of toluene were charged, and 176 g of ethyl acrylate and 229 g of 4-hydroxybutyl acrylate were added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and the mixture obtained by adding 405 g of toluene was designated as compound (5).

Synthesis Example 6 300 g of isophorone diamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
300 g of toluene and 0.2 g of copper acetate were charged, and 187 g of vinyl cyanide was added dropwise. After completion of dropping, 3
After reacting for an hour, one obtained by adding 187 g of toluene was used as compound (6).

Synthesis Example 7 300 g of isophorone diamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
300 g of toluene and 0.2 g of copper acetate were charged, and 360 g of ethynylbenzene was added dropwise. After the completion of the dropwise addition, the mixture was reacted at 100 ° C. for 3 hours, and 360 g of toluene was added to obtain a compound (7).

Synthesis Example 8 300 g of isophorone diamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
300 g of toluene and 0.2 g of copper acetate were charged, and 438 g of 1-ethynyl-1-hexanol was added dropwise. After the completion of the dropwise addition, the reaction was carried out at 80 ° C. for 1 hour, and then 438 g of toluene was added to obtain compound (8).

Synthesis Example 9 300 g of 2,2,4-trimethylhexamethylenediamine, 300 g of toluene and 0.2 g of copper acetate were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel. 201 g of vinyl cyanide was added dropwise. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and 201 g of toluene was added to obtain a compound (9).

Synthesis Example 10 Polyether polyol PP was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, 75 g of toluene, and 0.05 g of dibutyltin dilaurate as a catalyst, gradually raise the temperature to 100 ° C., and carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 61 g of the compound (1) was added dropwise for 1 hour, and the mixture was aged for 1 hour. The reaction is terminated by adding 2.1 g of methyl-propanol (manufactured by Nagase & Co., Ltd.). The reaction solution was colorless and transparent, and had a solid content of 50% and a viscosity of 50%.
The number average molecular weight was MN 25,000, and the weight average molecular weight MW was 90,000. Synthesis Example 11 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, Sanyo Chemical Industry Co., Ltd.) 257 g, isophorone diisocyanate (IPDI) 43 g, toluene 75 g,
0.025 g of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate was added.
g was dropped in 1 hour, and after aging for 1 hour, 2.0 g of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.) was added, and the NCO characteristic absorption (2270 cm -1) of the IR chart was measured. After confirming the disappearance, the reaction was terminated. The reaction solution was colorless and transparent, the solid content was 50%, and the viscosity was 3
The number average molecular weight MN was 27,000 and the weight average molecular weight MW was 110,000. Synthesis Example 12 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, Sanyo Chemical Industry Co., Ltd.) 257 g, isophorone diisocyanate (IPDI) 43 g, toluene 75 g,
0.025 g of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate was added.
g was dripped in 1 hour, and after aging for 1 hour, 2.0 g of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.) was added, and the NCO characteristic absorption (2270 cm -1) of the IR chart was confirmed. After confirming the disappearance, the reaction was terminated. The reaction solution was colorless and transparent, the solid content was 50%, and the viscosity was 3
The number average molecular weight MN was 27,000 and the weight average molecular weight MW was 110,000.

Synthesis Example 13 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, 75 g of toluene, and 0.05 g of dibutyltin dilaurate as a catalyst, gradually raise the temperature to 100 ° C., and carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 50 g of compound (2) was added dropwise for 1 hour, and the mixture was aged for 1 hour. The reaction is terminated by adding 2.2 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution was colorless and transparent, and had a solid content of 50% and a viscosity of 40%.
The number average molecular weight MN was 30,000 and the weight average molecular weight MW was 100,000.

Synthesis Example 14 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, 75 g of toluene, and 0.05 g of dibutyltin dilaurate as a catalyst, gradually raise the temperature to 100 ° C., and carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 48 g of the compound (3) was added dropwise over 1 hour, and the mixture was aged for 1 hour. The reaction is terminated by adding 2.0 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution was colorless and transparent, and had a solid content of 50% and a viscosity of 35%.
The number average molecular weight was MN 28,000, and the weight average molecular weight MW was 110,000.

Synthesis Example 15 Polyether polyol PP was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 129 g of polyester polyol P-2010 (bifunctional polyester polyol, OH value 56, manufactured by Kuraray Co., Ltd.) 128 g, isophorone diisocyanate (manufactured by Huls Japan KK)
43 g, toluene 75 g, dibutyltin dilaurate 0.03 g as a catalyst, tin 2-ethylhexanoate 0.02 g
, And the temperature is gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 50 g of compound (2) was added dropwise for 1 hour, and the mixture was aged for 1 hour. The reaction is terminated by adding 2.2 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution is colorless and transparent, has a solid content of 50%, and has a viscosity of 5000 cp.
s, number average molecular weight MN 25,000, weight average molecular weight M
W90,000.

Synthesis Example 16 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of hexamethylene diisocyanate, 64 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and 100 g of
The temperature was gradually raised to ℃ and the reaction was carried out for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 50 g of compound (2) was added dropwise for 1 hour, and the mixture was aged for 1 hour. The reaction is terminated by adding 2.2 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). The reaction solution was colorless and transparent, the solid content was 50%, the viscosity was 4000 cps, and the number average molecular weight was MN3.
000 and a weight average molecular weight MW of 110,000.

Synthesis Example 17 Polyether polyol PP was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, Sanyo Chemical Industries, Ltd.) 257 g, 4,4′-diphenylmethane diisocyanate 44 g, toluene 76
g) and 0.05 g of dibutyltin dilaurate as a catalyst, gradually raise the temperature to 100 ° C., and carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate was added.
g was dripped in 1 hour, and after aging for 1 hour, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to terminate the reaction. This reaction solution was colorless and transparent, had a solid content of 50%, a viscosity of 4000 cps, a number average molecular weight MN of 26,000 and a weight average molecular weight of MW 85.0.
00.

Synthesis Example 18 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 37 g of compound (6) was added dropwise over 1 hour, and the mixture was aged for 1 hour. The reaction was terminated by adding 2.1 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution was colorless and transparent, and had a solid content of 50% and a viscosity of 35%.
The number average molecular weight was MN 27,000, and the weight average molecular weight MW was 95,000.

Synthesis Example 19 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 50 g of the compound (7) was added dropwise over 1 hour, and the mixture was aged for 1 hour. The reaction was terminated by adding 2.2 g of methyl-propanol (manufactured by Nagase & Co., Ltd.). The reaction solution was colorless and transparent, the solid content was 50%, and the viscosity was 30.
The number average molecular weight MN was 27,000 and the weight average molecular weight MW was 94,000.

Synthesis Example 20 Polyether polyol PP was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 56 g of the compound (8) was added dropwise over 1 hour, and the mixture was aged for 1 hour. The reaction was terminated by adding 2.0 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution was colorless and transparent, had a solid content of 50%, and had a viscosity of 25%.
The number average molecular weight MN was 27,000 and the weight average molecular weight MW was 96,000.

Synthesis Example 21 Polyether polyol PP was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 35 g of compound (9) was added dropwise over 1 hour, and the mixture was aged for 1 hour. The reaction was terminated by adding 2.0 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution was colorless and transparent, had a solid content of 50%, and had a viscosity of 25%.
The number average molecular weight was 29,000 and the weight average molecular weight MW was 100,000.

Synthesis Example 22 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 129 g of polyester polyol P-2010 (bifunctional polyester polyol, OH value 56, manufactured by Kuraray Co., Ltd.) 128 g, isophorone diisocyanate (manufactured by Huls Japan KK)
43 g, toluene 75 g, dibutyltin dilaurate 0.03 g as a catalyst, tin 2-ethylhexanoate 0.02 g
, And the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 37 g of compound (6) was added dropwise over 1 hour, and the mixture was aged for 1 hour. The reaction was terminated by adding 2.2 g of methyl-propanol (manufactured by Nagase & Co., Ltd.). The reaction solution is colorless and transparent, has a solid content of 50%, and has a viscosity of 3500 cp.
s, number average molecular weight MN 24,000, weight average molecular weight M
W90,000.

Synthesis Example 23 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of hexamethylene diisocyanate, 64 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and 100 g of
The temperature was gradually raised to ℃, and the reaction was carried out for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 35 g of compound (6) was added dropwise over 1 hour, and the mixture was aged for 1 hour.
2.2 g of methyl-propanol (manufactured by Nagase & Co., Ltd.)
Was added to terminate the reaction. The reaction solution was colorless and transparent, the solid content was 50%, the viscosity was 3000 cps, and the number average molecular weight was MN2.
It was 5,000 and the weight average molecular weight MW was 98,000.

Synthesis Example 24 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, Sanyo Chemical Industries, Ltd.) 257 g, 4,4′-diphenylmethane diisocyanate 44 g, toluene 76
g, 0.05 g of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours.
After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate was added.
7 g was dripped in 1 hour, and after aging for 1 hour, 2-
The reaction was terminated by adding 2.2 g of amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution was colorless and transparent, had a solid content of 50%, a viscosity of 3000 cps, a number average molecular weight MN of 23,000, and a weight average molecular weight of MW 83,0.
00.

Synthesis Example 25 Polyether polyol PP was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6. 182 g of isophorone diisocyanate (manufactured by Huls Japan KK);
5 g, 200 g of toluene and 0.05 g of dibutyltin dilaurate as a catalyst were charged, and the temperature was gradually raised to 100 ° C., and the reaction was carried out for 3 hours. When the remaining isocyanato group was confirmed by IR and disappeared, the reaction was terminated and cooled. This reaction solution was colorless and transparent, had a solid content of 50%, a viscosity of 3500 cps, a number average molecular weight MN of 25,000, and a weight average molecular weight of MW 95,
000.

Synthesis Example 26 Polyester polyol P-2 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH value 56,
185.5 g of Kuraray Co., Ltd., 14.5 g of hexamethylene diisocyanate, 200 g of toluene, and 0.05 g of dibutyltin dilaurate as a catalyst were charged.
The temperature was gradually raised to ° C., and the reaction was carried out for 3 hours. When the remaining isocyanato group was confirmed by IR and disappeared, the reaction was terminated and cooled. The reaction solution was colorless and transparent, had a solid content of 50%, and had a viscosity of 4%.
The number average molecular weight MN was 30,000 and the weight average molecular weight MW was 90,000.

Synthesis Example 27 1,6-hexanediol 3 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
5.4 g, 88.8 g of isophorone diisocyanate (manufactured by Huls Japan KK), 124 g of toluene, and 0.02 g of dibutyltin dilaurate as a catalyst were charged.
The temperature was gradually raised to 00 ° C., and the reaction was performed for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 154 g of a 44% (weight / weight) toluene solution of isophoronediamine was added dropwise over 1 hour, and after aging for 1 hour,
The reaction was terminated by adding 17.8 g of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution is colorless and transparent, has a solid content of 50%, a viscosity of 1500 cps,
Number average molecular weight MN 2,000, weight average molecular weight MW 7,
000.

Synthesis Example 28 75 g of butyl acrylate, 20 g of 2-ethylhexyl acrylate, 5 g of 2-hydroxyethyl acrylate, 135 g of ethyl acetate, 15 g of toluene, and 15 g of toluene were placed in a four-necked flask equipped with a stirrer, nitrogen inlet tube, thermometer, and dropping funnel. A solution containing 0.2 g of benzoyl oxide was placed in a reactor equipped with a reflux condenser, and heated at 80 to 85 ° C. under a nitrogen gas stream.
A time reaction was performed. This solution is colorless and transparent and has a solid content of 40
% And a viscosity of 5,200 cps.

[0116]

Example 1 100 g of the Michael addition type urethane urea resin solution synthesized in Synthesis Example 10 was mixed with 2 g of a curing agent (D).
Adhesion, holding power, ball tack, and removability were tested by a predetermined method. The curing agent (D) is a hexamethylene diisocyanate trimethylolpropane adduct 75%
An ethyl acetate solution was used.

The test method is as follows.

<Coating Method> The above-mentioned Michael addition type urethane urea resin solution was dried on a release paper with an applicator and dried.
The coating is performed to a thickness of μm and dried at 100 ° C. for 2 minutes to prepare a coating. After one week at room temperature, it was used for the following measurements.

<Adhesive Strength> An adhesive sheet obtained by applying a Michael addition type urethane urea resin solution to release paper was transferred to a polyethylene terephthalate film (25 μm in thickness).
23 on 0.4mm thick stainless steel plate (SUS304)
At 65 ° C. and 65% RH, roll-bonded according to JIS, and after 20 minutes, peel strength (1) with a shopper type peel tester.
80 degree peel, pulling speed 300mm / min; unit g /
(25 mm width).

<Holding Force> An adhesive sheet obtained by coating a release paper with a Michael addition type urethane urea resin solution was transferred to a polyethylene terephthalate film (25 μm thick).
Laminated on a stainless steel plate (SUS304) with a heat of 0.4 mm with a lamination area of 25 mm x 25 mm, JIS
Roll-pressed according to, and leave it at 40 ° C for 20 minutes, then 1k
A load of g was applied, and the number of seconds to fall or the shift after 60 minutes was measured.

<Ball tack> An adhesive sheet obtained by applying a Michael addition type urethane urea resin solution to a release paper was transferred to a polyethylene terephthalate film (25 μm in thickness). 23 ° C, 6 by Dow-type rolling ball method
It was measured under the condition of 5% RH.

<Removability> A pressure-sensitive adhesive sheet obtained by applying a Michael addition type urethane urea resin solution to release paper was transferred to a polyethylene terephthalate film (25 μm in thickness) or paper (30 μm in thickness). SU
S304), after adhering to a glass plate, at 40 ° C., 80% R
It was left under the condition of H, cooled to 23 ° C. and 65% RH, then peeled off, and the adhesive residue was visually evaluated. After peeling, there was no adhesive transfer to the adherend at all. ご Very slight thing ○ Partially present △ Completely transferred ×

Examples 2 to 15 In the same manner as in Example 1, the Michael addition type urethane urea resin pressure-sensitive adhesives synthesized in Synthesis Examples 10 to 24 were blended in order to obtain Examples 2 to 15.

Comparative Examples 1 to 4 Resins synthesized in Synthesis Examples 25 to 28 were mixed and measured in the same manner as in Example 1, and Comparative Examples 1 to 4 were obtained.

Table 1 shows the results of the adhesive composition, adhesive strength, holding power, ball tack and removability test results of Examples 1 to 15 and Comparative Examples 1 to 4.

[0126]

[Table 1]

[0127]

The adhesive containing the Michael addition type urethane urea resin of the present invention has an adhesive strength of 900 g / 25 m in all cases.
m or more, and both holding power and ball tack are good. The removability is good regardless of whether a stainless steel plate or a glass plate is used. On the other hand, in the urethane resin pressure-sensitive adhesives shown in Comparative Examples 1 and 2, those having large adhesive strength have poor holding power, and those having good holding power have low adhesive strength. In all cases, the removability is poor. Also,
The acrylic pressure-sensitive adhesive shown in Comparative Example 4 has poor removability. As described above, with the pressure-sensitive adhesive using the Michael addition type urethane urea resin of the present invention, the pressure-sensitive adhesive strength is in the middle pressure-sensitive area, the holding power, the ball tack are good, and the pressure-sensitive adhesive excellent in removability can be obtained. It became so.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB33 AH03A AH03H AK15 AK42 AK51A AL06A AT00B BA02 CA02A CA30A DG10 DJ01 GB90 JL13A JL14 4J004 AA14 AB01 CA02 CA04 CA05 CA06 CA07 CA08 CB02 CB04 CA03 CC03 FA03 CA15 CA22 CB03 CC03 CD07 CD08 DA01 DF02 DF11 DF12 DF16 DF20 DF22 DG03 DG04 DG05 DG06 DG14 DM01 HA07 HA08 HB06 HC03 HC12 HC13 HC17 HC22 HC34 HC35 HC45 HC46 HC52 HC64 HC67 HC70 HC71 HC73 LA13 RA08 EF1 EF EF EF EF EF EF EF EF EF EF EF EF EF EF EF GA20 HC16 JA09 JB09 KA16 LA06 PA23 QA01

Claims (7)

[Claims] An amine obtained by subjecting a urethane prepolymer (A) obtained by reacting a polyol (a) and a polyisocyanate (b) to a Michael addition reaction of a polyamine (c) and an unsaturated compound (d). An adhesive comprising a Michael addition type urethane urea resin obtained by reacting the compound (B) and having an isocyanate group at a terminal. 2. An amine obtained by subjecting a urethane prepolymer (A) obtained by reacting a polyol (a) and a polyisocyanate (b) to a Michael addition reaction of a polyamine (c) and an unsaturated compound (d). An adhesive comprising a Michael addition type urethane urea resin obtained by reacting a compound (B) with a reaction terminator (f). 3. The pressure-sensitive adhesive according to claim 2, wherein the reaction terminator (f) is a monoamine compound having a hydroxyl group. 4. The pressure-sensitive adhesive according to claim 1, further comprising a curing agent (D). 5. The pressure-sensitive adhesive according to claim 1, wherein the polyamine (c) is isophoronediamine or 2,2,4-trimethylhexamethylenediamine. 6. An amine obtained by subjecting a urethane prepolymer (A) obtained by reacting a polyol (a) and a polyisocyanate (b) to a Michael addition reaction of a polyamine (c) and an unsaturated compound (d). A first step of reacting the compound (B) to synthesize a Michael addition type urethane urea resin having a terminal isocyanate group, and a second step of reacting the Michael addition type urethane urea resin with a reaction terminator (f) And a third step of blending a curing agent (D) with the reaction product of the second step. 7. A laminate comprising a base material and the pressure-sensitive adhesive according to any one of claims 1 to 5.