JP2007119599A - Urethane adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive having a refractive index of 1.50 or more and an adhesive strength of 500 gf / 25 mm or more suitable for bonding an optical film such as a pressure-sensitive adhesive sheet, a laminate or a polarizing plate. And a method for producing the pressure-sensitive adhesive.
A bonding site represented by the following formula (1) and a urethane group are synthesized from a raw material containing a polyamino compound (E) having a hydroxyl group, a diisocyanate (B ′), a diol (C), and a polyol (D). A urethane resin adhesive having a refractive index of 1.50 or more. Formula (1) —R ¹ —N (R ³ ) —CO—NH—R ² — (wherein R ¹ is a divalent organic residue having an amino group derived from a polyamino compound (E) having a hydroxyl group. , R ² is a polyvalent organic residue derived from polyisocyanate (B) generated after polymerization of diisocyanate (B ′), R ³ contains at least one hydroxyl group derived from a polyamino compound (E) having a hydroxyl group. Represents a valent organic residue.)
[Selection figure] None

Description

  The present invention relates to a polarizing film, a liquid crystal panel using the polarizing film, a diffusion adhesive sheet capable of improving image contrast and visibility, and an adhesive having a refractive index of 1.50 or more used for a liquid crystal display device, and the production thereof. The present invention relates to a method, an adhesive sheet, and a laminate.

In optical applications, the difference in refractive index generated between the substrate and the pressure-sensitive adhesive is one of the causes of light reflection loss. This is because interface reflection occurs between the base material and the adhesive. In particular, it is known that the incident light has an incident angle of 50 ° or more, and the reflected light increases abruptly, resulting in a disadvantage that the reflection loss becomes very large.
In order to overcome this drawback, studies have been made to increase the refractive index by introducing an aromatic ring into the acrylic adhesive (Patent Documents 1 to 3), and studies such as blending a high refractive index material into the acrylic adhesive (Patent Documents 4 and 5). Has been made.
However, in the system in which an aromatic ring is introduced into an acrylic adhesive, the refractive index of the original acrylic adhesive is low, so a large amount of aromatic ring must be introduced to make the refractive index close to 1.50. However, there was a drawback that the adhesive strength was weakened. In addition, in a system in which a high refractive index material is blended, there is a drawback that the blended material bleeds over time.
Therefore, when a urethane pressure-sensitive adhesive having a higher refractive index than that of the acrylic pressure-sensitive adhesive (Patent Document 6) is used, the refractive index increases from the refractive index of 1.46 to 1.47 of the acrylic pressure-sensitive adhesive, and the refractive index becomes 1.48 to 1. It can be raised to about 49. However, there is a drawback that an adhesive having an adhesive strength of 5N or more and a refractive index of 1.50 or more cannot be obtained at the same time.
JP 2002-173656 A JP 2003-013029 A JP 2003-193012 A JP 2002-014225 A JP 2005-154581 A JP 2003-292928 A

  The present invention provides a pressure-sensitive adhesive having a refractive index of 1.50 or more and an adhesive strength of 500 gf / 25 mm or more suitable for bonding an optical film such as a pressure-sensitive adhesive sheet, a laminate or a polarizing plate. It aims at providing the manufacturing method of an adhesive.

ジイソシアネート（Ｂ’）は、芳香族含有ジイソシアネート（ｂ’）または芳香脂肪族含有ジイソシアネート（ｂ’’’）であることが好ましい。
ポリアミノ化合物（Ｅ）は、ポリアミン（Ｈ）と不飽和基を有する化合物（Ｉ）とをマイケル付加反応させてなる化合物であることが好ましい。 The present invention synthesizes from a raw material containing a hydroxyl group-containing polyamino compound (E), diisocyanate (B ′), diol (C), and polyol (D), and has a bonding site and a urethane group represented by the following formula (1). The present invention relates to a urethane resin adhesive having a refractive index of 1.50 or more.
Formula (1)
—R ¹ —N (R ³ ) —CO—NH—R ² —
(In the formula, R ¹ is a divalent organic residue having an amino group, derived from the polyamino compound (E) having a hydroxyl group,
R ² is a polyvalent organic residue derived from polyisocyanate (B) produced after polymerization of diisocyanate (B ′),
R ³ represents a monovalent organic residue containing at least one hydroxyl group derived from the polyamino compound (E) having a hydroxyl group. )
The diol (C) includes at least one compound selected from the group consisting of an aromatic ring-containing diol (c), a sulfur atom (S) -containing diol (c ′), or a bromine atom (Br) -containing diol (c ″). It is preferable.
In particular, the aromatic ring-containing diol (c) is preferably a compound (c1) having a structure represented by the following formula (2) and two hydroxyl groups.
Formula (2)

The diisocyanate (B ′) is preferably an aromatic-containing diisocyanate (b ′) or an araliphatic diisocyanate (b ′ ″).
The polyamino compound (E) is preferably a compound obtained by Michael addition reaction of the polyamine (H) and the compound (I) having an unsaturated group.

  Moreover, the adhesive which contains the said urethane resin adhesive and a hardening | curing agent (K) is also 1 aspect of this invention.

  Since the urethane resin pressure-sensitive adhesive of the present invention has physical properties of a refractive index of 1.50 or higher and an adhesive strength of 500 gf / 25 mm or higher, both high refractive index and high adhesion can be achieved.

  The urethane resin pressure-sensitive adhesive of the present invention includes a urethane resin (A) synthesized from a raw material containing a polyamino compound (E) having a hydroxyl group, a diisocyanate (B ′), a diol (C), and a polyol (D).

The urethane resin (A) is formed by blending a urethane prepolymer (F) having a terminal isocyanato group, a polyamino compound (E) having a hydroxyl group and, if necessary, a polyamine (H). The compound (M) having active hydrogen capable of reacting with an isocyanato group can be blended to obtain a urethane resin (A ′).
The compound (M) having an active hydrogen capable of reacting with an isocyanato group is a compound having a functional group capable of reacting with an isocyanato group, such as a monoamine compound, and an isocyanate group remaining unreacted at the end of the urethane resin (A). To stabilize the reaction activity of the resin.

The urethane resin contained in the pressure-sensitive adhesive of the present invention has a binding site represented by the formula (1) and a urethane group.
The urethane group is formed mainly by the reaction of the hydroxyl group of the polyol (D) or diol (C), which is the raw material of the urethane resin of the present invention, and the isocyanate group of the polyisocyanate (B).
The bonding site represented by the formula (1) is formed mainly by the reaction between the amino group of the polyamino compound (E) having a hydroxyl group and the isocyanate group of the polyisocyanate (B).

The urethane resin pressure-sensitive adhesive of the present invention includes a urethane resin having a partial structural formula represented by the formula (1).
In the formula (1), R ¹ is a divalent organic residue having an amino group derived from the polyamino compound (E),
R ² is a polyvalent organic residue derived from polyisocyanate (B),
R ³ represents an organic residue containing a monovalent oxygen atom derived from the polyamino compound (E).

(Urethane prepolymer (F))
The urethane prepolymer (F) used in the present invention is a compound having at least one isocyanato group at the terminal, obtained by reacting the polyol (D) and the polyisocyanate (B). Moreover, as a raw material of a urethane prepolymer (F), you may contain the compound (L) etc. which have the group and ionic group which can react with the below-mentioned amine, water, or the isocyanato group mentioned later as needed.

(About polyol (D))
As the polyol (D), one or more of high molecular weight polyols, bisphenols such as bisphenol and bisphenol F, glycols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols, and the like Polyols can also be used. Furthermore, compounds having two or more active hydrogen groups obtained by reaction of one or more of these with other compounds such as olefins and aromatic hydrocarbons can also be used.

  High molecular weight polyols are compounds having a repeating unit with a polymerization degree of 2 or more and having two hydroxyl groups, and examples thereof include polyester polyols, polyether polyols, and polycarbonate polyols.

Known polyester polyols can be used as the polyester polyols used in the present invention.
Examples of the polyester polyol include a polyester polyol in which a diol component and a dibasic acid component undergo a condensation reaction.

  Examples of the diol include ethylene glycol, propylene glycol, 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 or the like can be used.

Examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol and the like, and terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid as dibasic acid components. Examples thereof include aliphatic or aromatic dibasic acids such as acids, and aromatic dibasic acids.
In addition, polyester polyol, polycarbonate polyol, silicon polyol, and the like obtained by ring-opening polymerization of lactone cyclic ester compounds such as ε-caprolactone poly (β-methyl-γ-valerolactone) and polyvalerolactone can be used.
The weight average molecular weight of the polyester polyols is preferably 500 to 5,000, more preferably 1,000 to 3,500.

  Known polyether polyols can be used as the polyether polyols used in the present invention. For example, by condensation of tetrahydrofuran, or a polymer, copolymer or graft copolymer of alkylene oxide such as 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 polyols and propoxylated or ethoxylated polyether polyols, can be used.

  Furthermore, as a polymerization initiator at the time of polymerization of alkylene oxide, for example, polypropylene glycol, ethylene glycol, glycerin, sorbitol, trimethylolpropane, trimethylolbutane, trimethylolethane, 1,2,6-hexanetriol, pentaerythritol A polyether polyol which is a trihydric or higher alcohol such as, for example, 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 weight average molecular weight of the polyether polyols is preferably 100 to 100,000, more preferably 500 to 25,000, and 1,000 to 10,000 in order to facilitate the extraction of the side chain effect.

The polycarbonate polyol used in the present invention is a group represented by the following formula (3):
Formula (3)
− [— O—R ⁴ —O—CO—] _m −
(In the formula, R ⁴ represents a divalent organic residue, and m represents an integer of 1 or more.)
A known polycarbonate polyol can be used.
The polycarbonate polyol can be obtained, for example, by 1) a reaction of glycol or bisphenol with a carbonic acid ester, or 2) a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.
Specific examples of the carbonic acid ester used in the production method 1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.
Specific examples of the glycol component or bisphenol used in the production method 1) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2-methyl. -1,8-octanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, 3,9-bis (1 , 1-dimethyl-2-hydroxyethyl, 2,2,8,10-tetraoxospiro [5.5] undecane, bisphenols such as bisphenol and bisphenol F, bisphenols and alkylene oxides such as ethylene oxide and propylene oxide Bisphenols with added can also be used, etc. These compounds can be used singly or as a mixture of two or more.

The glycol can also be used in the method 2) in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.
Specifically, the Kuraray polyol C series of Kuraray Co., Ltd. can be used in the polycarbonate polyol.
Among them, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, and C-2015N are preferable because they are flexible and excellent as a raw material for pressure-sensitive adhesives. .

  The weight average molecular weight of the polycarbonate polyol is preferably 500 to 5,000, more preferably 1,000 to 3,500. When the weight average molecular weight is less than 500, the resin becomes too hard when the urethane resin is synthesized, and becomes brittle. When the weight average molecular weight exceeds 5,000, the cohesive force of the urethane resin is insufficient.

  The polyol (D) can be obtained by reacting one or more compounds selected from the group consisting of the polyether polyol, the polyester polyol, and the polycarbonate polyol with the following polyisocyanate having a number of moles of the polyol (D) or less. A urethane polyol having a terminal hydroxyl group may be used.

(About Diol (C))
As the diol (C), a known diol (C) can be used as long as it is not a polymer having two hydroxyl groups and having a repeating unit.
For the purpose of increasing the refractive index, the aromatic ring-containing diol (c), the sulfur atom (S) -containing diol (c ′), and the bromine atom (Br) -containing diol (c ″) can be increased.

A conventionally well-known thing can be used as aromatic ring containing diol (c). Examples of the aromatic ring include skeletons such as benzene, naphthalene, anthraquinone, biphenyl, fluorene, and carbazole.
A compound in which the aromatic ring-containing diol (c) is a compound (c1) having a structure represented by the above formula (2) and two hydroxyl groups is particularly preferable in terms of increasing the refractive index and reducing the color of the resin itself.
Examples of the compound (c1) having the structure represented by the above formula (2) and two hydroxyl groups include bisphenoxyethanol fluorene, bisphenol fluorene, and biscresol fluorene.
Examples of the aromatic ring-containing diol (c) other than the compound (c1) include bisphenol.

A conventionally well-known thing can be used as S containing diol (c ').
Specifically, 2,2′-dithiodiethanol, 2,2-bis (2-hydroxy-3-mercaptopropoxyphenylpropane), 1,2-bis (2-hydroxyethylthio) ethane, 1,4-bis (2-hydroxyethylthio) butane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-bis (2-hydroxyethoxy) diphenyl sulfone, 3,3′-dimethyl 4,4′-dihydroxydiphenyl sulfone, 3, 3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfone, 4,4 ′, 5,5′-tetramethyl-2,2′-dihydroxydiphenyl sulfone, 2,2 ′, 5,5 '-Tetramethyl-4,4'-dihydroxydiphenyl sulfone, 3,3'-dichloro-4,4'-dihydroxydiphenyl sulfone, 3,3'- Nitro-4,4'-dihydroxydiphenyl sulfone, for example.
Moreover, S containing dithiol can also be used instead of S containing diol (c '). A conventionally well-known thing can be used as S containing dithiol.
Specifically, 2,2 ′-(ethylenedithio) diethanethiol, ethylene glycol bisthioglycolate, butanediol bisthioglycolate, hexanediol bisthioglycolate, ethylene glycol bisthiopropionate, butanediol bis Examples thereof include thiopropionate, p-xylene dithiol, m-xylene dithiol, tetraethylene glycol bis-3-mercaptopropionate.

  As the Br-containing diol (c "), conventionally known diols can be used.

  Diols (C) other than the above include ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, 3,9-bis (1,1- And compounds having two hydroxyl groups such as dimethyl-2-hydroxyethyl 2,2,8,10-tetraoxospiro [5.5] undecane.

(About polyisocyanate (B))
As the polyisocyanate (B) used in the present invention, conventionally known ones can be used, and bifunctional diisocyanate (B ′) is particularly preferred in the synthesis of the urethane prepolymer (F). For example, aromatic diisocyanate (b ′), aliphatic diisocyanate (b ″), araliphatic diisocyanate (b ′ ″), alicyclic diisocyanate (b ″ ″) and the like can be mentioned.

Aromatic-containing diisocyanates (b ′) include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-triisocyanate. Examples include diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene, and the like.
Aromatic-containing isocyanates other than diisocyanates include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-tri Phenylmethane triisocyanate, naphthalene diisocyanate

  Aliphatic diisocyanates (b ″) include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene. Examples thereof include diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic diisocyanate (b ′ ″) include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1. 1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like can be used.

Examples of the alicyclic-containing diisocyanate (b ″ ″) include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1, Examples include 4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.
As the alicyclic-containing isocyanate other than diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane and the like can be used.

  In addition, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, etc. can be used in combination. Polyphenylmethane polyisocyanate (PPI) and these polyisocyanate modified products can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as the polyisocyanate (B).

  As the polyisocyanate (B) used in the present invention, aromatic-containing diisocyanate (b ′) and araliphatic-containing diisocyanate (b ″ ″) are preferable because they have an effect of increasing the refractive index. Xylylene diisocyanate is particularly preferable because it is hardly yellowing.

(Catalyst (G))
A known catalyst (G) can be used during the synthesis of the urethane prepolymer (F). Examples thereof include tertiary amine compounds and organometallic compounds.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU) and the like, and these can be used alone or in combination.

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

Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate, 2- Examples include iron series such as iron ethylhexanoate and iron acetylacetonate, cobalt series such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc series such as zinc naphthenate and zinc 2-ethylhexanoate, and zirconium naphthenate. It is done.
Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene.
Catalysts such as the tertiary amine compounds and organometallic compounds can be used alone in some cases, but can also be used in combination. Especially when polyester diols and polyether diols are used in combination as polyol components, It is preferable to use dibutyltin dilaurate and tin 2-ethylhexanoate together because a uniform urethane prepolymer (F) can be obtained.

The organometallic compound catalyst used in the synthesis of the urethane prepolymer (F) significantly accelerates the reaction in the further reaction with the amine described later. The reaction between an isocyanato group and an amino group is very fast from the beginning, but in the presence of an organometallic compound catalyst, the reaction may be further promoted and may be difficult to control. At this time, if a chelate compound is present, a chelate is formed with the organometallic compound catalyst, and the catalytic activity is adjusted to facilitate control of the reaction with the amine.
Examples of the chelate compound include acetylacetone, dimethylglyoxime, oxine, dithizone, polyaminooxyacids such as ethylenediaminetetraacetic acid (EDT), oxycarboxylic acids such as citric acid, and condensed phosphoric acid. Among the chelate compounds, acetylacetone is soluble in an organic solvent, has volatility, and is preferably easy to remove if necessary.

  Further, the chelate compound remains in the polyurethane resin even after the reaction. In the present invention, when the polyurethane resin is used as the pressure-sensitive adhesive, it is preferable to add a curing agent. At this time, the chelate compound also adjusts the reaction rate between the polyurethane resin and the curing agent. An adhesive having excellent storage stability can be provided.

In the present invention, a known solvent is preferably used when the urethane prepolymer (F) is synthesized. The use of a solvent serves to facilitate reaction control. Examples of the solvent used for this purpose include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide and the like.
In particular, ethyl acetate, toluene, methyl ethyl ketone, or a mixed solvent thereof is preferable from the viewpoint of amine solubility such as the solubility of the urethane resin and the boiling point of the solvent.
Further, the concentration in the urethane prepolymer reaction system when a solvent is used is preferably 50 to 95% by weight of resin solid content, more preferably 60 to 90% by weight. If the concentration is too low, the reactivity is too low. That is not preferable.

(Regarding the polyamino compound (E) having a hydroxyl group)
As the polyamino compound (E) having a hydroxyl group described here, a compound obtained by Michael addition reaction of a polyamine (H) and a compound (I) having an unsaturated group, or two amino groups and one There exists a compound (J) which has the above hydroxyl group.
The polyamino compound (E) having a hydroxyl group is used as a raw material for the urea reaction for the purpose of modifying the urethane resin.

(Compound (J) having two amino groups and one or more hydroxyl groups)
In the present invention, the compound (J) having two amino groups and one or more hydroxyl groups means a known compound having two amino groups and one or more hydroxyl groups.
As the compound (J), MXD-PO1 (manufactured by Mitsubishi Gas Chemical Company), MXD-PO2 (manufactured by Mitsubishi Gas Chemical Company), MXD-EO1 (manufactured by Mitsubishi Gas Chemical Company), MXD-EO2 (manufactured by Mitsubishi Gas Chemical Company), Examples include 2-hydroxyethylaminopropylamine (manufactured by Guangei Chemical Industry Co., Ltd.), aminoethylethanolamine, N- (2-hydroxyethyl) xylylenediamine (manufactured by Meisei Chemical Industry Co., Ltd.), and the like.

(About polyamine (H))
In the present invention, polyamine (H) is a compound having at least two primary or secondary amino groups, and for synthesizing a compound obtained by Michael addition reaction with compound (I) having at least one unsaturated group. Used for. The polyamine (H) is used for synthesizing a urethane urea having at least one primary or secondary amino group at the terminal together with the polyol (D) and the polyisocyanate (B).
As the polyamine (H) used in the present invention, known ones can be used. Specifically, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, Aliphatic polyamines such as diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine,
Cycloaliphatic polyamines such as isophorone diamine and dicyclohexylmethane-4,4′-diamine,
And aromatic polyamines such as phenylenediamine and xylylenediamine.
Furthermore, 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, Diamines having a hydroxyl group in the molecule such as (2-hydroxypropylethylene) diamine and (di-2-hydroxypropylethylene) diamine, dimer amine obtained by converting the carboxyl group of dimer acid to an amino group, and propoxyamine at both ends Polyoxyalkylene glycol diamine having the following formula (4) and the like can also be used.
Formula (4)
H ₂ N—CH ₂ —CH ₂ —CH ₂ —O (C ₁ H _2l —O) _k —CH ₂ —CH ₂ —CH ₂ —NH ₂
(In the formula, l represents an arbitrary integer of 2 to 4, and k represents an arbitrary integer of 2 to 50.)
Among the above polyamines (H), isophorone diamine, 2,2,4-trimethylhexamethylene diamine, and hexamethylene diamine are preferable because of easy control of the reaction and excellent hygiene.

(Compound (I) having an unsaturated group)
The compound (I) having an unsaturated group is used for the purpose of modifying a urethane resin. Accordingly, the type of the compound (I) having an unsaturated group to be used can be arbitrarily selected according to the purpose of modification. The residue of the compound (I) having an unsaturated group constitutes R3 in the above formula (1).

In the above formula (1), examples of the structural formula of R ³ include the following formulas (5) to (15).

In formulas (5) to (15), Y ^{1 to} Y ¹¹ are each independently a hydrogen atom or a monovalent organic residue having a weight average molecular weight of 15 to 20,000, preferably 20 to 10,000. Y ¹¹ is a direct bond or a divalent organic residue.
In the present invention, the organic residue includes an alkyl group, a polyalkylene glycol group, an alkoxy group, a phenoxy group, a hydroxyl group, a carboxyl group, a perfluoroalkyl group, an alkoxysilyl group, an epoxy group, and further an amide group or a dialkylamino group, And nitrogen-containing groups such as quaternary ammonium bases.

  As the unsaturated compound having the above structural formula, for example, the formula (5) is a (meth) acrylic unsaturated compound, the formula (6) is an amide unsaturated compound, the formula (7) is a fatty acid vinyl unsaturated compound, a formula (8) is a vinyl ether unsaturated compound, Formula (9) is an α-olefin unsaturated compound, Formula (10) is an allyl unsaturated compound, Formula (11) is an allyl acetate unsaturated compound, and Formula (12) is A vinyl cyanide unsaturated compound, formula (13) is styrene or vinylbenzene unsaturated compound, formula (14) is an alicyclic olefin unsaturated compound, formula (15) is two amino groups and one or more A part of the compound (J) having a hydroxyl group is shown.

  The type of the compound (I) having an unsaturated group to be used can be arbitrarily selected according to the purpose of modification, but it can be selected by paying attention to the functional group of the compound (I) having an unsaturated group. preferable. Examples of the functional group of the compound (I) having such an unsaturated group include an alkyl group, a polyalkylene glycol group, an alkoxy group, a phenoxy group, a hydroxyl group, a carboxyl group, a perfluoroalkyl group, an alkoxysilyl group, an epoxy group, Further examples include nitrogen-containing groups such as amide groups, dialkylamino groups, and quaternary ammonium bases.

  Examples of the amide unsaturated compound of formula (6) include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, and N-propoxymethyl. -Monoalkylol (meth) acrylamide such as (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-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl-N- Propoxymethyl methacrylate N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Examples include dialalkylol (meth) acrylamides such as acrylamide, N, N-di (pentoxymethyl) acrylamide, and N-methoxymethyl-N- (pentoxymethyl) methacrylamide.

  Examples of the fatty acid vinyl alkyl group-containing unsaturated compound of formula (7) include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, and vinyl stearate. it can.

Examples of the vinyl ether alkyl group-containing unsaturated compound of formula (8) include butyl vinyl ether and ethyl vinyl ether.
Further, the α-olefin type alkyl group-containing unsaturated compound of the formula (9) includes 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadece and other unsaturated compounds. As the vinyl compound, allyl compounds such as allyl acetate, allylbenzene, allyl cyanide,
Examples thereof include vinyl compounds such as vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, and chlorostyrene.
Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene and the like.

Hereinafter, the (meth) acrylic unsaturated compound of the formula (5) will be exemplified.
Examples of (meth) acrylic alkyl group-containing unsaturated compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-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 (meta There are alkyl (meth) acrylates having 1 to 22 carbon atoms such as acrylate, icosyl (meth) acrylate, henecosyl (meth) acrylate, docosyl (meth) acrylate, etc. -10, more preferably, an alkyl group-containing acrylate having an alkyl group having 2 to 8 carbon atoms or a corresponding methacrylate. For the purpose of adjusting leveling properties, it is preferable that the number of carbon atoms is 6 or more. When the number of carbon atoms is 23 or more, the Michael addition reaction is difficult to proceed although it depends on the purpose.

  Examples of the polyalkylene glycol group-containing unsaturated compound include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) ) Acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) and the like.

  The unsaturated compound having a polyalkylene glycol group and having an alkoxy group at the terminal includes methoxyethylene glycol (meth) acrylate, methoxydiethylene 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-pentoxytetraethylene glycol (meth) acrylate, Tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (medium ) Acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meta ) Acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, and the like.

  Furthermore, the unsaturated compound having a polyalkylene glycol group and having a phenoxy group at the terminal includes phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxy Examples include tetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene glycol (meth) acrylate.

Examples of hydroxyl-containing unsaturated compounds other than those described above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. 1-ethynyl-1-cyclohexanol, allyl alcohol and the like.
Carboxylic group-containing unsaturated compounds include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) Examples include acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like. I can do it.
Examples of the dialkylamino group-containing unsaturated compound include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene and the like.
Further, it is obtained by quaternary ammonium conversion of the above dialkylamino group-containing unsaturated compound, and the counter ion is a halogen ion such as Cl-, Br-, I- or the like or QSO3- (Q: an alkyl group having 1 to 12 carbon atoms). Examples of the unsaturated compound containing a quaternary ammonium base having dimethylaminoethyl methyl chloride (meth) acrylate, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3 Examples include-(1- (meth) acrylamidopropyl) ammonium chloride and trimethyl-3- (1- (meth) acrylamide-1,1-dimethylethyl) ammonium chloride.

  Perfluoroalkyl group-containing 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 C1-C20, such as (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Perfluoroalkyl (meth) acrylates having a fluoroalkyl group; perfluoroalkyl group-containing perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and alkylene Saturated compounds can be exemplified.

Examples of the unsaturated compound having an alkoxysilyl group include vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, and derivatives thereof.
Furthermore, epoxy group-containing unsaturated compounds such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate can be exemplified.

Furthermore, when imparting curability by active energy to the Michael addition type urethane resin, the compound (I) having an unsaturated group having two or more unsaturated groups can be used. As the unsaturated group, a compound (I) having two or more (meth) acryloyl groups or an unsaturated group having one acryloyl group and one or more methacryloyl groups is preferably used.
More specifically, examples of the compound (I) having an unsaturated group having one acryloyl group and one or more methacryloyl groups include 2-hydroxy-3-acryloxypropyl methacrylate, two or more As the compound (I) having an unsaturated group having a (meth) acryloyl group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, 1,3 butanediol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate , Nonangio Di (meth) acrylate, glycol di (meth) acrylate, diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, trisacryloyloxyethyl isocyanurate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, adipic acid epoxy (meth) acrylate, hydrogenated bisphenol ethylene oxide di (meth) acrylate, ethylene glycol glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, triethylolpropane tri (meth) acrylate, ethylene oxide Addition trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, ethylene glycolated pentaerythritol tri (meth) acrylate, propylene glycolated pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolethane (meth) acrylate, tetramethylolmethanetri ( Examples thereof include those having 2 or more functional groups such as (meth) acrylate, dipentaerythritol alkylate (meth) acrylate, Actilne 421 (KCROS CHEMICL), Actilne 423 (KCROS CHEMICL). These can be used alone or in combination of two or more.

  The compound (I) having an unsaturated group may be used alone or in combination of two or more.

  The Michael addition reaction between the polyamine (H) and the compound (I) having an unsaturated group is carried out by 1 mole equivalent of active hydrogen of the amino group of the polyamine (H) and the unsaturated group of the compound (I) having an unsaturated group. 1 molar equivalent reacts. Since polyamine (H) easily adds Michael to the vinyl group or ethynyl group of compound (I) having an unsaturated group having an electron-withdrawing group, (meth) acrylic compounds, particularly acrylate compounds are unsaturated. Preferred as compound (I) having a group. In addition, when the acrylate compound and the corresponding methacrylate compound are compared, the acrylate compound is more preferable for the efficiency of the Michael addition reaction.

Moreover, as a synthesis method of the polyamino compound (E) having a hydroxyl group, a known method relating to the Michael addition reaction can be used. When the unsaturated compound is a (meth) acrylic compound, particularly an acrylate compound, the reaction proceeds at 10 to 100 ° C. under a catalyst such as alcohol as necessary. Depending on the type of unsaturated compound used, a reaction temperature of 40 to 80 ° C. is preferred. If the reaction temperature is too high, an ester amide exchange reaction occurs, which is not preferable. In addition, when the unsaturated compound does not have an electron-withdrawing group, the reaction is possible in the presence of the metal catalyst. In this case, when the reaction is performed at 60 to 100 ° C. while heating in the presence of the catalyst, an appropriate reaction rate is obtained. It is preferable.
The synthetic solvent may or may not be used, and the kind thereof is not particularly limited, but known solvents such as methyl ethyl ketone, toluene, acetone, and benzene can be used.
In addition, when a hydroxyl group is not contained in the compound (I) or polyamine (H) having an unsaturated group to be used, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol, n-butyl alcohol, or the like It is preferable to use those mixed solvents. The solution concentration when using the reaction solvent is preferably 20% by weight or more, more preferably 50% by weight or more. If it is more dilute than this, it is not preferable because the reaction hardly proceeds.
The reaction time varies depending on the type of unsaturated compound to be used, but is completed in 30 minutes to 5 hours.

  The ratio of the polyamine (H) to the unsaturated compound-containing compound (I) is as follows: when at least two secondary or primary amino groups remain in the polyamino compound (E) obtained by the reaction The polyamine (H) is preferably reacted at a ratio of 0.1 to 1.0 mol, more preferably 0.2 to 0.98 mol, with respect to 1 mol of the primary amino group of the polyamine (H). When the amount is less than 0.1 mol, the influence of the side chain is hardly expressed.

(About manufacturing process)
In the present invention, the urethanization reaction for producing the urethane prepolymer (F) can be carried out in various ways, but is roughly classified into the following two methods (α) to (β).
(Α) Polyisocyanate (B), polyol (D), diol (C), and optionally compound (L) having an ionic group and a group capable of reacting with an isocyanato group, and / or a solvent, and / or Or the method which prepares the whole quantity of the solution which consists of a catalyst (G).
(Β) A polyol (D), a diol (C), and, if necessary, a compound (L) having a group capable of reacting with an isocyanato group and an ionic group, and / or a solvent are charged into a flask, and a polyisocyanate (B) A method of adding the catalyst (G) as needed after dripping.
When controlling the reaction precisely, (β) is preferable. The reaction temperature for obtaining the urethane prepolymer (F) is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 110 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined weight average 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.

Examples of the compound (L) include an anionic functional group-containing polyol.
As the anionic functional group-containing polyol, for example, a polyol having a carboxyl group, a sulfone group or the like can be used, and it is particularly desirable to use a carboxyl group-containing polyol. Examples of the carboxyl group-containing polyol include dimethylolpropionic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dimethylolalkanoic acid such as dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxy Benzoic acid is mentioned. In particular, dimethylolpropionic acid and 2,2-dimethylolbutyric acid are preferable from the viewpoint of reactivity and solubility. These can be used alone or in combination.

  The blending ratio of the polyol (D) and the polyisocyanate (B) greatly depends on the reactivity of the compound, the abundance ratio of the trivalent or higher compound, the use of the obtained resin, and the like. In order for the urethane prepolymer to have at least one isocyanato group, and to 1 mol of the functional group capable of reacting with the isocyanato group of the compound (L), the isocyanate group of the polyisocyanate (B) is more than 1 mol. It is necessary to be within a range of preferably 1.01 to 4.00 mol, more preferably 1.40 to 3.00 mol.

The urethane prepolymer (F) further becomes a urethane resin having a urethane urea bond by chain extension with the polyamino compound (E).
In the present invention, the isocyanato group-containing compound urethane prepolymer (F) or polyisocyanate has an isocyanato group, and the polyamino compound (E) or compound (M) having an active hydrogen capable of reacting with the isocyanato group has a primary or secondary compound. The urea reaction with a primary amino group is roughly divided into the following two methods (a) to (b).
(A) A method in which a solution composed of an isocyanato group-containing compound is charged into a flask and a solution composed of an amino group-containing compound is dropped.
(A) A method in which a solution comprising an amino group-containing compound is charged into a flask and a solution of a compound having an isocyanato group is dropped.

  Among the methods (a) to (b), a method in which the reaction is stable can be selected. However, if there is no problem in the reaction, the method (a) that is easy to operate is preferable. In the present invention, the temperature of the urea reaction is preferably 100 ° C. or less. More preferably, it is 70 degrees C or less. Even at 70 ° C., the reaction rate is high, and when it cannot be controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a urethane resin having a predetermined molecular weight and structure. The temperature in the reaction system is preferably 50 ° C. or lower, more preferably 40 ° C. or lower.

  Moreover, the compounding ratio of a urethane prepolymer (F) and an amino group containing compound is not specifically limited, It selects arbitrarily by a use and required performance. When an isocyanato group-excess system is used, the number of moles of the amino group in the amino group-containing compound with respect to 1 mole of the isocyanato group in the isocyanato group-containing compound is preferably 0.70 to 0.97, more preferably 0.8 to 0.96. In the group excess system, it is preferably 1.001 to 1.40, more preferably 1.01 to 1.2. Outside this range, a predetermined molecular weight is not obtained, which is not preferable.

  The urethane resin having an isocyanato group at the terminal can be further reacted with a compound (M) having an active hydrogen capable of reacting with the isocyanato group, if necessary.

  The compound (M) having an active hydrogen capable of reacting with an isocyanato group controls the molecular weight or reacts with an unreacted isocyanato group at the end of the urethane resin to stabilize the reaction activity of the resin.

Examples of the compound (M) having an active hydrogen capable of reacting with an isocyanato group used in the present invention include dialkylamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine and diisononylamine. Monoamine having a hydroxyl group such as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl-1,3-propanediol,
Alkylhydrazines such as monomethylhydrazine, 1,1-dimethylhydrazine, and benzylhydrazine;
Hydrazides such as form hydrazide, acetohydrazide, lauric hydrazide,
A monoamine compound having a tertiary amino group and a primary amino group on one side, such as N, N-dimethyl-1,3-propanediamine and N, N diethyl 1,3-propanediamine;
Furthermore, monoamine compounds having an alkoxysilyl group such as γ-aminopropyltriethoxysilane can also be used.

Among the compounds (M) having an active hydrogen that can react with the isocyanato group, a monoamine having a hydroxyl group such as 2-amino-2-methyl-propanol is a urethane resin excellent in storage stability having a terminal hydroxyl group. Can be obtained.
Furthermore, a urethane resin having a hydroxyl group at the end is preferable because the hydroxyl group at the end also serves as a crosslinking site when a polyisocyanate-based curing agent is added and crosslinked. 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 urethane resin, but the reactivity of the amino group is higher and the amino group preferentially reacts with the isocyanate group.
In addition, monoamine compounds such as N, N-dimethyl-1,3-propanediamine and N, Ndiethyl 1,3-propanediamine having a tertiary amino group and a primary amino group on one side are cationic at the end of the urethane resin. It is preferably used to introduce a group.

The amount of the compound (M) having an active hydrogen capable of reacting with an isocyanato group is different depending on whether it is mixed with the polyamino compound (E) or when it is added alone at the end. It is preferably 0.5 mol or less, more preferably 0.3 mol or less, based on 1 mol of the isocyanate group in the compound having, and when added alone at the end, On the other hand, the amount is 0.5 to 3.0 mol, and 1 to 3.0 mol is preferable particularly for the purpose of stabilizing the resin.
When the compound (M) having an active hydrogen capable of reacting with an isocyanato group is added alone at the end, the amount of the compound (M) used is 0.5 mol with respect to 1 mol of the isocyanato group in the compound having an isocyanato group. If it is less, the isocyanato group remains and the stability over time is not good. When the amount of the compound (M) having an active hydrogen capable of reacting with an isocyanato group is more than 3.0 moles per mole of the isocyanate group in the compound having an isocyanato group, the curing agent (K) and the urethane resin The reaction (A) will be inhibited, and the film formability of the coating film will be reduced.
In addition, the end point of reaction is judged by the loss | disappearance of the isocyanate peak by the measurement of isocyanate% resulting from titration, and IR measurement.

The molecular weight of the urethane resin of the present invention is not particularly limited and is not particularly limited, but is preferably 1,000 to 200,000 as a weight average molecular weight in terms of standard polystyrene by GPC. More preferably, it is 5,000-150,000. Moreover, as a number average molecular weight, Preferably it is 1,000-150,000, More preferably, it is 4,000-100,000.
When the number average molecular weight exceeds 150,000, the viscosity becomes extremely high, which makes it difficult to handle. Conversely, when the number average molecular weight is less than 1,000, the performance as a polymer cannot be expressed.

The solution viscosity of the obtained urethane resin is not particularly limited and is selected depending on the use of the resin. Preferably, it is 10 to 50,000 mP · s (25 ° C.), and when used as an adhesive, More preferably, it is 500 to 10,000 mP · s (25 ° C.).
When the viscosity exceeds 50,000 mP · s (25 ° C.), the coating process becomes difficult. When the viscosity is lower than 10 mP · s (25 ° C.), the urethane resin flows at the time of coating, which makes the coating difficult.

(About curing agent (K))
The urethane resin pressure-sensitive adhesive of the present invention becomes a pressure-sensitive adhesive having high cohesive strength when the urethane resin (A ′) of the present invention and the curing agent (K) are used in combination.
As the curing agent (K) used in the present invention, the aforementioned polyisocyanate (B) can be used.
The compounding ratio of the urethane resin (A ′) and the curing agent (K) of the present invention is 0.1 to 10 parts by weight of the curing agent (K) with respect to 100 parts by weight of the urethane resin. When the curing agent (K) is less than 0.1 parts by weight, the cohesive force is reduced, and when it is more than 10 parts by weight, the adhesive force is reduced. Preferably it is 1-5 weight part.
A known blending method can be used for blending the curing agent (K).

(About polycarbodiimide (N))
The urethane resin pressure-sensitive adhesive of the present invention may contain polycarbodiimide (N) in order to increase the hydrolyzability of the polyester.
The polycarbodiimide (N) used in the present invention means one having a carbodiimide group (—N═C═N—), and known polycarbodiimides can be used.
The polycarbodiimide (N) used in the present invention can also be a high molecular weight polycarbodiimide produced by decarboxylation condensation reaction of diisocyanate in the presence of a carbodiimidization catalyst.
Examples of such compounds include those obtained by decarboxylation condensation reaction of the following diisocyanates. 4,4′-diphenylmethane diisocyanate, 3,3′-dimethoxy-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, 3,3 ′ -Dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, One kind of tetramethylxylylene diisocyanate or a mixture thereof can be used.
As the carbodiimidization catalyst, 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl- Phosphorene oxides such as 2-phospholene-1-oxide or their 3-phospholene isomers can be used.
Examples of such high molecular weight polycarbodiimides include the Carbodilite series of Nisshinbo Industries, Ltd. Of these, Carbodilite V-01, 03, 05, 07, 09 is preferable because of its excellent compatibility with organic solvents.
As a method of blending the polycarbodiimide (N) in the urethane resin pressure-sensitive adhesive of the present invention, there are a method of using it mixed with a urethane resin and a method of using a polycarbodiimide having an isocyanate group at its terminal incorporated in the urethane resin, It can be used properly according to the purpose.

(About additives)
In the present invention, the urethane resin may be blended with an organic / inorganic filler for the purpose of improving printability and coating film properties.
Organic fillers are natural products such as starch, acrylics such as polymethyl methacrylate, polystyrenes, styrene-acrylic, nylons such as nylon 6, nylon 12, nylon 6-12, high density polyethylene, low density polyethylene, Examples of the resin fine particles include olefins such as polypropylene and tetrafluoroethylene, polyesters, phenols, and benzoguanamines.

Inorganic fillers are clay, diatomaceous earth, aluminum silicate, calcium silicate, magnesium silicate, hydrotalcite, talc, kaolin, calcined kaolin, barium sulfate, titanium dioxide, calcium sulfate, light calcium carbonate, heavy calcium carbonate, magnesium hydroxide , Magnesium carbonate, Titanium oxide, Zinc carbonate, Zinc oxide, Zinc hydroxide, Zinc sulfide, Lead oxide, Zirconium oxide, Magnesium oxide, Synthetic amorphous silica, Colloidal silica, Alumina, Alumina sol, Pseudobomatite, Aluminum hydroxide, Litopon Zeolite, montmorillonite and the like.
When alumina sol or colloidal silica is used as the filler component, a mixed liquid can be stably obtained when the urethane resin is made water-based by the above-described method and then the filler is mixed.

Furthermore, when the following compounds (i) to (ii) are used, the obtained urethane resin can be grafted to the filler.
(I) When a compound having a hydroxyl group or a carboxyl group is used as the compound (M) having an active hydrogen capable of reacting with an isocyanato group (ii) An alkoxysilyl group as the compound (M) having an active hydrogen capable of reacting with an isocyanato group When a compound having

When the urethane resin has a hydroxyl group, a carboxyl group, and an epoxy group, grafting is possible by adding a silane coupling agent to the mixed solution of the resin and filler, and heating and stirring at 40 to 100 ° C. for 10 minutes to 3 hours. is there.
When the urethane resin has a methylol group or an N-alkoxymethyl group, grafting is possible by heating and stirring the mixed solution of the resin and filler in the presence of an acid catalyst as necessary.
When the urethane resin has an alkoxysilyl group, grafting is possible by heating and stirring the mixed solution of the resin and filler at 40 to 100 ° C. for 10 minutes to 3 hours.

  When a urethane resin is grafted onto alumina sol or colloidal silica, it is preferable that a filler is added after the water is made by the above-described method, or if it is made water during the grafting reaction, a stable graft is obtained.

The blending ratio of the filler and the urethane resin varies depending on the purpose of blending the filler.
For example, for the purpose of preventing blocking or improving the mechanical properties of the coating film,
It is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total amount of the urethane resin (A ′). If it exceeds 50% by weight, the mechanical properties of the coating film, in particular, the bendability and the extensibility are lowered.
Moreover, when aiming at the improvement of the drying property of ink, Preferably it is 50 to 95 weight%, More preferably, it is 60 to 90 weight%. If it is less than 50% by weight, a sufficient drying effect cannot be obtained. When the blending ratio of the filler is high, it is preferable to graft the filler and the resin because the mechanical properties of the coating film are dramatically improved.

In the present invention, the urethane resin (A ′) may contain other anti-blocking, curling, surface gloss adjustment, weather resistance, ink droplet wettability, and the like without departing from the object of the present invention. These resins can be blended.
Examples of other resins include acrylic resin, polyamide, epoxy resin, polyurethane resin, polyvinyl acetate, polyvinyl acetal, polystyrene, fluororesin, polycarbonate, polyether, polyisobutylene, petroleum resin, rosin, nitrocellulose, sucrose ester, Thermoplastic resins such as vinyl chloride / vinyl acetate copolymers, ethylene / vinyl acetate copolymers, α-olefin / maleic anhydride copolymers, styrene / maleic anhydride copolymers, phenol resins, urea Resin, melamine resin, amino resin, polyester resin, alkyd resin, silicon resin, epoxy resin, etc., as well as epoxy acrylate, polyester acrylate, urethane acrylate, polyether acrylate, phosphazene resin, etc. To have a resin, it may be blended one or more of them.
If necessary, fillers such as talc, calcium carbonate, titanium oxide, tackifiers, ultraviolet absorbers, fluorescent dyes such as fluorescent brighteners, colored dyes, colorants, thickeners, antifoaming agents, One or more additives such as a leveling agent, an anti-crater agent, an anti-settling agent, an antioxidant, a light stabilizer, a flame retardant, a wax, and a heat stabilizer can be added as appropriate.

  As the deterioration preventing agent used in the present invention, at least one selected from the group consisting of an antioxidant, an ultraviolet absorber and a light stabilizer is used.

  Examples of the antioxidant used in the present invention include a radical chain inhibitor (primary antioxidant) and a peroxide decomposer (secondary antioxidant).

  Examples of radical chain inhibitors (primary antioxidants) include phenolic antioxidants and amine antioxidants.

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

  Examples of phenolic antioxidants include monophenolic, bisphenolic, and polymeric phenolic antioxidants.

  Monophenol antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and the like.

  Examples of bisphenol antioxidants include 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis. (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane, and the like.

  Examples of the polymer type phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl-4 '-Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, and the like. IRGNOX L 135 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferred because of its compatibility with the resin.

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

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

  Examples of the ultraviolet absorber used in the present invention include benzophenone, benzotriazole, salicylic acid, oxalic anilide, cyanoacrylate, and triazine ultraviolet absorbers.

  Examples of benzophenone ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2′-dihydroxy. -4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane , Etc.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- ( 2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ', 5' ', 6' ',-tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- ( 2H-benzotriazol-2-yl) phenol], [2 (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole, and the like. TUNUVIN 571 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferred because of its compatibility with the resin.

  Examples of the salicylic acid ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, and the like.

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

  Examples of the light stabilizer used in the present invention include hindered amine light stabilizers and ultraviolet light stabilizers.

  As the hindered amine light stabilizer, [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate], bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl Mention may be made of 1,2,2,6,6-pentamethyl-4-piperidyl sebacate. Product names include TINUVIN 765 (Ciba Specialty Chemicals Co., Ltd.), Adeka Stub L-77 (Asahi Denka), Chimssorb 944LD (Ciba Specialty Chemicals Co., Ltd.), TINUVIN 622LD (Ciba Specialty Chemicals Co., Ltd.), TINUVIN 144 (Ciba Specialty Chemicals Co., Ltd.), ADK STAB L-57 (Asahi Denka), ADK STAB L-62 (Asahi Denka), ADK STAB L-67 (Asahi Denka), ADK STAB L-63 (Asahi Denka), ADK STAB L -68 (Asahi Denka), Adeka Stub L-82 (Asahi Denka), Adeka Stub L-87 (Asahi Denka), Goodrite UV-3034 (Goodrich). TINUVIN 765 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferable because of compatibility with the resin.

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

  It is preferable that an antioxidant and an ultraviolet absorber or a light stabilizer are included as the deterioration preventing agent, and it is preferable that all of the antioxidant, the ultraviolet absorber and the light stabilizer are further included. TINUVIN B 75 (Ciba Specialty Chemicals Co., Ltd.), IGNOX L 135 (Ciba Specialty Chemicals Co., Ltd.), TINUVIN 571 (Ciba Specialty Chemicals Co., Ltd.) and TINUVIN 765 (Ciba Specialty Chemicals Co., Ltd.) It is preferable that it can be used without interfering with each other's effects. The amount used is preferably 0 to 10% by weight of the solid content.

  The present invention will be described with reference to examples, but the present invention is not limited thereto. In addition, the part in an Example shows a weight part and% shows weight%.

Synthesis Example 1 (Method for synthesizing Michael addition type amine)
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel is charged with 80 g of isophoronediamine (IPD) and 80 g of toluene, and 67.8 g of 4-hydroxybutyl acrylate and 60.2 g of butyl acrylate are added. Added dropwise at room temperature. After completion of the dropwise addition, the mixture is reacted at 80 ° C. for 1 hour, and then added with 128 g of toluene is defined as compound (1).

Synthesis example 2
Kuraray polyol C-1090 (bifunctional polycarbonate diol, OH number 112, manufactured by Kuraray Co., Ltd.) 129.6 g, bisphenoxyethanol fluorene in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel (Trade name: BPEF, Osaka Gas Chemical Co., Ltd.) 21.1 g, 1,3-bis (isocyanatomethyl) benzene (trade name: Takenate 500, Mitsui Takeda Chemical Co., Ltd.) 49.3 g, toluene 50 g, catalyst Then, 0.017 g of dibutyltin dilaurate is added, and the temperature is gradually raised to 100 ° C. and the reaction is performed for 2 hours. After confirming the remaining amount of isocyanato group by titration, the mixture was cooled to 40 ° C., 327.5 g of toluene and 1.8 g of acetylacetone were added, and 18.5 g of compound (1) dissolved in 40 g of toluene was added dropwise over 1 hour. After further aging for 1 hour, 5.0 g of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.) was added to confirm that the NCO characteristic absorption (2270 cm-1) of the IR chart disappeared. The reaction was terminated, and 2.0 g of TINUVIN B 75 (Ciba Specialty Chemicals Co., Ltd.) was added. This reaction solution was colorless and transparent, had a solid content of 32%, a viscosity of 3,000 cps, a number average molecular weight MN9,500, and a weight average molecular weight MW39,000.

Synthesis example 3
Kuraray polyol C-1090 (bifunctional polycarbonate diol, OH number 112, manufactured by Kuraray Co., Ltd.) 142.6 g, bisphenoxyethanol fluorene in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel (Product name: BPEF, Osaka Gas Chemical Co., Ltd.) 10.8 g, 1,3-bis (isocyanatomethyl) benzene (Product name: Takenate 500, Mitsui Takeda Chemical Co., Ltd.) 46.5 g, Toluene 50 g, Catalyst As a starting material, 0.017 g of dibutyltin dilaurate is charged, and the temperature is gradually raised to 100 ° C., followed by reaction for 2 hours. After confirming the remaining amount of isocyanato group by titration, the mixture was cooled to 40 ° C., 337.2 g of toluene and 1.8 g of acetylacetone were added, and 18.5 g of compound (1) dissolved in 40 g of toluene was added dropwise over 1 hour. After further aging for 1 hour, 6.0 g of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.) was added to confirm that the NCO characteristic absorption (2270 cm-1) of the IR chart had disappeared. The reaction was terminated, and 2.0 g of TINUVIN B 75 (Ciba Specialty Chemicals Co., Ltd.) was added. This reaction solution was colorless and transparent, had a solid content of 32%, a viscosity of 3,000 cps, a number average molecular weight MN12,800, and a weight average molecular weight MW36,400.

Synthesis example 4
Kuraray polyol C-1090 (bifunctional polycarbonate diol, OH number 112, manufactured by Kuraray Co., Ltd.) 129.6 g, bisphenoxyethanol fluorene in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel (Trade name: BPEF, Osaka Gas Chemical Co., Ltd.) 21.1 g, 1,3-bis (isocyanatomethyl) benzene (trade name: Takenate 500, Mitsui Takeda Chemical Co., Ltd.) 49.3 g, toluene 50 g, catalyst Then, 0.017 g of dibutyltin dilaurate is added, and the temperature is gradually raised to 100 ° C. and the reaction is performed for 2 hours. After confirming the remaining amount of isocyanato group by titration, the mixture was cooled to 40 ° C., 302.0 g of toluene and 1.8 g of acetylacetone were added, and then 2-hydroxyethylaminopropylamine dissolved in 40 g of toluene (Guangei Chemical Industry Co., Ltd.) (Product made) 10.2 g was added dropwise over 1 hour, and after aging for another hour, 5.0 g of 2-amino-2-methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.) was added to absorb NCO characteristics (2270 cm) of the IR chart. -1) was confirmed to have disappeared and the reaction was terminated, and 2.0 g of TINUVIN B 75 (Ciba Specialty Chemicals Co., Ltd.) was added. This reaction solution was colorless and transparent, had a solid content of 32%, a viscosity of 2,800 cps, a number average molecular weight MN13,000, and a weight average molecular weight MW 45,000.

Synthesis example 5
In a 2 liter reactor equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube, 222 parts of butyl acrylate, 62 parts of methyl acrylate, 25 parts of acrylic acid, 34 parts of ethyl acetate, azobisisobutyronitrile 0.084 part was prepared and nitrogen substitution was performed for 30 minutes or more. Separately, 222 parts of butyl acrylate, 62 parts of methyl acrylate, 25 parts of acrylic acid, 584 parts of ethyl acetate, and 0.084 parts of azobisisobutyronitrile were prepared in a dropping funnel. Thereafter, the temperature of the reactor was increased, and when the temperature reached 60 ° C., the contents of the dropping funnel began to be dropped and the reaction was started. The dropwise addition was completed in 1 hour, 0.168 parts of azobisisobutyronitrile was added after 2 hours and 3 hours from the start of the reaction, respectively, and stirring was further continued for 5 hours to obtain a resin composition. The polymerization was carried out while maintaining the outer wall of the reactor at 60 ° C. The obtained high molecular weight product had a number average molecular weight MN320,000 and a weight average molecular weight MW13.8 million.

Example 1
About the urethane resin solution synthesize | combined in the synthesis example 2, the adhesive force and the refractive index were measured with the following test method.

The test method is as follows.
<Coating method>
The urethane resin solution was applied to release paper with 20 g / m ² using an applicator and dried at 100 ° C. for 2 minutes to prepare a coated product. What passed 1 week at room temperature was used for the following measurements.
<Adhesive strength>
The pressure-sensitive adhesive sheet coated with a urethane resin solution on the release paper is transferred to a polyethylene terephthalate film (film thickness 25 μm) and attached to a stainless steel plate (SUS304) with a thickness of 0.4 mm at 23 ° C. and 65% RH. Twenty hours after press-bonding in accordance with JIS, the peel strength (180 degree peel, tensile speed 300 mm / min; unit g / 25 mm width) was measured with a shopper type peel tester.

<Refractive index>
The refractive index of the coated product was measured using an Abbe refractometer (Atago Co., Ltd.). The refractive index was as shown in Table 1.
Those having a refractive index of 1.50 or more
Less than 1.50 x
As evaluated.

(Examples 2 to 4, Comparative Example 1)
As shown in Table 1, 4.0 g of the curing agent (K) was added to 100 g of the solid content of the resin solution synthesized in Synthesis Examples 2 to 4, and then the same operation as in Example 1 was performed. It was set as Examples 2-4 and Comparative Example 1. Table 1 also shows the adhesive strength and refractive index of the resin.
As the curing agent (K), a 75% by weight ethyl acetate solution of hexamethylene diisocyanate trimethylolpropane adduct was used.

Claims (6)

A refractive index having a bonding site and a urethane group synthesized from a raw material containing a polyamino compound (E) having a hydroxyl group, a diisocyanate (B ′), a diol (C), and a polyol (D) and represented by the following formula (1): 1. 50 or more urethane resin adhesive.
Formula (1)
—R ¹ —N (R ³ ) —CO—NH—R ² —
(In the formula, R ¹ is a divalent organic residue having an amino group, derived from the polyamino compound (E) having a hydroxyl group,
R ² is a polyvalent organic residue derived from polyisocyanate (B) produced after polymerization of diisocyanate (B ′),
R ³ represents a monovalent organic residue containing at least one hydroxyl group derived from the polyamino compound (E) having a hydroxyl group. )   The diol (C) includes at least one compound selected from the group consisting of an aromatic ring-containing diol (c), a sulfur atom (S) -containing diol (c ′), or a bromine atom (Br) -containing diol (c ″). The urethane resin pressure-sensitive adhesive according to claim 1. The urethane resin pressure-sensitive adhesive according to claim 2, wherein the aromatic ring-containing diol (c) is a compound (c1) having a structure represented by the following formula (2) and two hydroxyl groups.
Formula (2)

  The urethane resin pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the diisocyanate (B ') is an aromatic-containing diisocyanate (b') or an araliphatic-containing diisocyanate (b "').   The urethane resin pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the polyamino compound (E) is a compound obtained by subjecting the polyamine (H) and the compound (I) having an unsaturated group to a Michael addition reaction. An adhesive comprising the urethane resin adhesive according to any one of claims 1 to 5 and a curing agent (K).