JP2003137963A - Polyurethane resin composition, and adhesive using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a urethane resin composition having both high heat resistance and moist heat resistance through ameliorating the drawbacks of both poor heat resistance and moist heat resistance inherent in urethane resins produced using polyether polyols or polyester polyols, and to provide a urethane resin adhesive having high heat resistance, moist heat resistance and re- releasability. SOLUTION: This urethane resin composition, which is synthesized from raw materials comprising (e') a polyamino compound, (b) a polyisocyanate and (a) a polycarbonate polyol, has both linkage parts of formula (1): -R<1> -N(R<3> )- CO-NH-R<2> - (wherein, R<1> is a bivalent organic residue having an amino group derived from the polyamino compound (e'); R<2> is a polyvalent organic residue derived from the polyisocyanate (b); and R<3> is an organic residue containing monovalent oxygen atom) and formula (2): -[-O-R<8> -O-CO-]m - (wherein, R<8> is a bivalent organic residue; and m is an integer of >=1).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a urethane resin composition containing a polycarbonate polyol and a method for producing the same. More specifically, the present invention relates to coating materials such as paints, binders for inks, overcoat varnishes and various functional surface treatment agents, as well as adhesives, pressure sensitive adhesives, fine particle dispersants such as organic and inorganic pigments, and compatibilizers. The present invention relates to a urethane urea resin used for the above. In particular, the pressure-sensitive adhesive is useful as a heat-resistant, heat-moisture-resistant pressure-sensitive adhesive and a pressure-sensitive adhesive for optical applications such as adhesion of polarizing plates.

[0002]

Urethane resins basically consist of a polyol component and a polyisocyanate component, and resins having various physical properties can be designed by selecting each component. In particular, the polyol component has a wide selection range and various polyols can be used. Among them, polyester-based polyols have good performance and are widely used. However, the urethane resin using the polyester-based polyol does not have sufficient hydrolysis resistance, and there is a phenomenon that the urethane resin deteriorates when wet and hot. Regarding adhesives, in recent years, there has been a great demand for those having excellent heat resistance and moisture heat resistance for industrial use. An example is a pressure-sensitive adhesive for temporary fixing in the processing step. These pressure-sensitive adhesives are required to have not only excellent heat resistance and resistance to moist heat, but also physical properties excellent in removability such that no glue remains after use. Further, there is a pressure-sensitive adhesive for adhering a polarizing plate as a pressure-sensitive adhesive for an optical film, but this pressure-sensitive adhesive is also often used under high temperature and high humidity, and heat resistance and wet heat resistance are important. In these urethane adhesives, those having a low glass transition point are required for the polyol serving as the soft segment. Among them, when a polyether-based polyol or a polyester-based polyol is used, it is excellent as an adhesive. Shows physical properties. However, there are advantages and disadvantages when using these polyols. Urethane resin adhesives using polyether-based polyols do not have sufficient heat resistance, and urethane resin adhesives using polyester-based polyols are generally superior in heat resistance to those of polyether-based ones. The hydrolyzability was not sufficient, and there was a phenomenon that the urethane resin pressure-sensitive adhesive deteriorates when wet and hot.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the drawbacks of poor heat resistance and wet heat resistance of urethane resins using polyether polyols and polyester polyols, and has excellent heat resistance and wet heat resistance. An object and a manufacturing method thereof are provided.

Regarding the pressure-sensitive adhesive, the present invention provides a urethane resin pressure-sensitive adhesive excellent in heat resistance, wet heat resistance and removability, and a method for producing the same.

[0005]

[Means for Solving the Problems] By using a polycarbonate polyol having excellent heat resistance and moist heat resistance as a polyol component of a urethane resin, the heat resistance and moist heat resistance of the urethane resin composition itself are improved. The inventors have found that the improvement of heat resistance and resistance to moist heat also improves the removability at the time of heat resistance and moist heat resistance, leading to the present invention.

That is, the present invention provides a polyamino compound (e
'), Polyisocyanate (b), and polycarbonate polyol (a) were synthesized from the following formula (1)
And a urethane resin composition having both the binding sites represented by (2). Equation ^{(1) -R 1 -N (R} 3) -CO-NH-R 2 - ( in the formula (1), R ¹ is a divalent organic residue having an amino group derived from a polyamino compound (e ') , R ² represents a polyvalent organic residue derived from polyisocyanate (b), and R ³ represents an organic residue containing a monovalent oxygen atom.) Formula (2) — [— O—R ⁸ —O —CO—] _m − (In the formula (2), R ⁸ represents a divalent organic residue, and m represents an integer of 1 or more.)

The present invention also relates to the urethane resin composition, wherein R ³ is a monovalent organic residue containing at least one hydroxyl group.

The present invention also relates to the urethane resin composition, wherein the polyamino compound (e ') is a compound obtained by subjecting the polyamine (e) and the compound (f) having an unsaturated group to a Michael reaction.

The present invention also relates to the above urethane resin composition, wherein the polyamino compound (e ') is a compound represented by the following formula (3). Formula (3)

[Chemical 2] (In the formula (3), Y represents a monovalent hydrocarbon group containing one or more functional groups having active hydrogen, but may also contain NH in the main chain. N represents 0 or 1. , R ⁴ and R
⁵ independently represents a hydrogen atom or a monovalent hydrocarbon group containing no hydroxyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent hydrocarbon group. )

Further, according to the present invention, a polyurethane prepolymer (A) obtained by reacting a polyol containing a polycarbonate polyol (a) with a polyisocyanate (b) in the presence of a catalyst (c) is treated with a polyamino compound (e). The method relates to a method for producing a urethane resin composition, which is characterized in that the chain is extended by

Further, according to the present invention, a polyurethane prepolymer (A) obtained by reacting a polyol containing a polycarbonate polyol (a) with a polyisocyanate (b) in the presence of a catalyst (c) is treated with a polyamino compound (e). And a compound (h) capable of reacting with an isocyanato group, and a urethane resin composition having an isocyanato group at the terminal which is chain-extended by the method described above.

The present invention also relates to the above-mentioned method for producing a urethane resin, wherein the polyamino compound (e ') contains a hydroxyl group.

The present invention also relates to a pressure-sensitive adhesive containing the urethane resin composition.

The present invention also relates to an adhesive containing the urethane resin composition and a curing agent (D).

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

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION (Urethane Prepolymer (A)) The urethane prepolymer (A) used in the present invention
Is a compound having at least one isocyanato group at the terminal, which is obtained by reacting a polyol containing a polycarbonate polyol (a) and a polyisocyanate (b). Further, as a raw material for the urethane prepolymer (A),
If necessary, the compound (j) having a group capable of reacting with an amine, water, or an isocyanato group described below and an ionic group may be included.

[0017] The (polycarbonate for the polyol containing polyol (a)) polycarbonate polyol used in the present invention (a), a group represented by the following formula (2), Equation (2) - [- O- R 8 -O -CO-] _m - (. wherein, R ⁸ is a divalent organic residue, m is the integer of 1 or more) are those having, be a known polycarbonate polyol (a) it can. Polycarbonate polyol (a) is, for example, 1) a reaction of glycol or bisphenol with a carbonic acid ester. 2) Obtained by the reaction of phosgene with glycol or bisphenol in the presence of 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, 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 A and bisphenol F, and bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols can also be used. These compounds can be used alone or as a mixture of two or more. The glycol can be used also in the method of 2) in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali. Specific examples of the polycarbonate polyol include Kuraray Polyol C series manufactured by Kuraray Co., Ltd. Among them, PMHC-
1050, PMHC-2050, C-1090, C-2
090, C-1065N, C-2065N, C-101
5N and C-2015N are preferable because they are flexible and excellent as a raw material for an adhesive. The weight average molecular weight of the polycarbonate polyol (a) is preferably 1,000 to
It is 5,000, more preferably 1,500 to 3,500. If the weight average molecular weight is less than 1,000, the resin becomes too hard and becomes brittle when the urethane resin is synthesized. When the weight average molecular weight exceeds 5,000, the cohesive force of the urethane resin is insufficient. Examples of the polyol other than the polycarbonate polyol (a) used for the urethane prepolymer (A) include the following. One or more 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 are also used. You can Furthermore, compounds having two or more active hydrogen groups obtained by reacting one or more of these with other compounds such as olefins and aromatic hydrocarbons can also be used.

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

As the polyester polyols used in the present invention, known polyester polyols can be used. Examples of polyester polyols include polyester polyols in which a polyol component and a dibasic acid component have undergone a condensation reaction. Among the polyols, diols include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-.
1,5-pentanediol, 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, 2,2,2.
8,10-tetraoxospiro [5.5] undecane,
Bisphenol A may be mentioned, and examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol and the like, and dibasic acid components such as terephthalic acid, adipic acid and azelaic acid,
Examples thereof include aliphatic or aromatic dibasic acids or aromatic dibasic acids such as sebacic acid, phthalic anhydride, isophthalic acid and trimellitic acid. Further, polyester polyols, polycarbonate polyols, silicon polyols and the like obtained by ring-opening polymerization of cyclic ester compounds such as lactones 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 1,000 to 5,000, more preferably 1,50.
It is 0 to 3,500. As the polyether polyols used in the present invention, known polyether polyols can be used. For example, tetrahydrofuran, or a polymer of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide,
Copolymer or graft copolymer, or hexanediol, methylhexanediol, heptanediol,
It is possible to use polyether polyols obtained by condensation of octane diol or a mixture thereof, propoxylated or ethoxylated polyether polyols having two or more hydroxyl groups. Further, as a polymerization initiator when polymerizing alkylene oxide, for example, polypropylene glycol, ethylene glycol, glycerin, sorbitol, trimethylolpropane, trimethylolbutane, trimethylolethane,
Polyether polyols which are trivalent or higher alcohols such as 1,2,6-hexanetriol and pentaerythritol are 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. Although the terminal to which the polyether polyol is added is a hydroxyl group, it 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, so that the side chain effect can be easily obtained.
˜25,000, 1,000 to 10,000. Polyols other than the polycarbonate polyol (a) are
It may be a urethane polyol having a hydroxyl group at the terminal by reacting the above polyether polyol and / or polyester polyol with less than the equimolar equivalent of the following polyisocyanate. Other polyols include ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6
-Hexanediol, neopentyl glycol, cyclohexanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl 2,2,8,10-tetraoxospiro [5.5] undecane, etc. Examples thereof include compounds having a hydroxyl group, compounds having three or more hydroxyl groups such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol and methyl glucoside.

(Regarding Polyisocyanate (b)) As the polyisocyanate (b) used in the present invention,
Conventionally known compounds can be used, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

As the aromatic polyisocyanate, 1,
3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
2,4-Tolylene diisocyanate, 2,6-Tolylene diisocyanate, 4,4'-Toluidine diisocyanate, 2,4,6-Triisocyanate toluene, 1,
3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate and the like can be mentioned.

As the aliphatic polyisocyanate, 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 mentioned.

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 , 1,3-tetramethylxylylene diisocyanate and the like.

As the alicyclic polyisocyanate, 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 can be mentioned.

Further, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, or the like can be used in combination. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and modified products of these polyisocyanates may 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 product having two or more kinds of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as the polyisocyanate (b).

The polyisocyanate (b) used in the present invention includes 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate),
From the viewpoint of weather resistance, it is preferable to use a non-yellowing type or hardly yellowing type polyisocyanate compound such as xylylene diisocyanate or 4,4′-methylenebis (cyclohexyl isocyanate) (hydrogenated MDI).

(Catalyst (c)) When synthesizing the urethane prepolymer (A), a known catalyst (c) can be used. 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.

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

Examples of the non-tin compound 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 so on. Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable in terms of reactivity and hygiene. The above-mentioned catalysts such as tertiary amine compounds and organometallic compounds may be used alone in some cases, but may be used in combination.
Particularly, when polyester diols and polyether diols are used in combination as the polyol component, a stable and uniform urethane prepolymer (A) can be obtained by using dibutyltin dilaurate and tin 2-ethylhexanoate in combination.
Is obtained, which is preferable.

The organometallic compound catalyst used when synthesizing the urethane prepolymer (A) significantly accelerates the reaction when it further reacts with the amine described below. The reaction between the isocyanato group and the amino group is originally very fast, but in the presence of the organometallic compound catalyst, the reaction may be further promoted and may be difficult to control. At this time, if a chelate compound is present, it forms a chelate with the organometallic compound catalyst and adjusts the catalytic ability to facilitate control of the reaction with the amine. Examples of the chelate compound include acetylacetone, dimethylglyoxime, oxine, dithizone, polyaminooxy acids such as ethylenediaminetetraacetic acid (EDTA), oxycarboxylic acids such as citric acid, condensed phosphoric acid, and the like. Among the chelate compounds, acetylacetone is preferable because it is soluble in an organic solvent, has volatile properties, and can be easily removed if necessary.

The chelate compound remains in the polyurethane urea resin after the reaction. When the polyurethane resin of the present invention is used as a pressure-sensitive adhesive, it is preferable to add a curing agent, but at this time, the chelate compound also adjusts the reaction rate of the polyurethane urea resin and the curing agent, resulting in It is possible to give a pressure-sensitive adhesive having excellent storage stability.

Known solvents are preferably used during the synthesis of the urethane prepolymer (A) of the present invention. The use of a solvent serves to facilitate reaction control. As the solvent used for such purpose, for example, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene,
Examples thereof include dioxane, acetonitrile, tetrahydrofuran, diglyme, dimethol sulfoxide, N-methylpyrrolidone and dimethylformamide. Ethyl acetate, toluene, methyl ethyl ketone, or a mixed solvent thereof is particularly preferable from the viewpoint of solubility of the amine such as solubility of urethane urea resin and boiling point of solvent. The concentration in the urethane prepolymer reaction system when a solvent is used is preferably 50 to 95% by weight of resin solids, more preferably 60 to 90% by weight.
%, And if the concentration is too low, the reactivity becomes too low, which is not preferable.

(About polyamino compound (e ')) As the polyamino compound (e') described here, a compound (a) having an amine (d) represented by the formula (3), a polyamine (e) and an unsaturated group ( Examples thereof include a compound obtained by subjecting f) to a Michael addition reaction. The polyamino compound (e ′) is
It is preferable to have a hydroxyl group so as to be a reaction point later. The polyamino compound (e ′) is used as a raw material for a urea-forming reaction for the purpose of modifying a urethane resin. That is, the polyamino compound (e ') is a polyamine (e) having at least two primary or secondary amino groups.
When it is, it is used to obtain a urethane urea resin by reacting with the urethane prepolymer (A). Furthermore, the polyamino compound (e ′) is a polyamine (e)
When a compound (f) having a quaternary ammonium salt group and an unsaturated group is added to Michael by
It functions as a cationicity imparting agent for imparting cationicity. The polyamino compound (e ′) may or may not have a primary or secondary amino group.

(Regarding the amine (d) represented by the formula (3)) In the present invention, the amine (d) represented by the formula (3) is a known compound as long as it is a compound defined by the formula (3). Can be used. In the formula (3), Y represents a monovalent hydrocarbon group containing at least one functional group having active hydrogen,
The main chain may contain NH. n represents 0 or 1, R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent hydrocarbon group containing no hydroxyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom. Alternatively, it represents a monovalent hydrocarbon group. Here, the monovalent hydrocarbon group not containing a hydroxyl group includes a linear or branched alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and the like. Is mentioned. Further, as the functional group having active hydrogen, a hydroxyl group,
Examples of the monovalent hydrocarbon group include an amino group and a carboxyl group, and specifically include one or more functional groups having active hydrogen, 3-aminopropyl group, (2-hydroxypropyl) aminomethylphenylmethyl group And a hydrocarbon group containing an amino group, a hydrocarbon group containing a carboxyl group, and a hydrocarbon group containing a hydroxyl group. As the amine (d), MXDA-PO1 (manufactured by Mitsubishi Gas Chemical Company), MXDA-PO2 (manufactured by Mitsubishi Gas Chemical Company), MXD
A-EO1 (manufactured by Mitsubishi Gas Chemical Company), MXDA-EO2
(Manufactured by Mitsubishi Gas Chemical Co., Inc.), 2-hydroxyethylaminopropylamine (manufactured by Koei Chemical Industry Co., Ltd.), aminoethylethanolamine, N- (2-hydroxyethyl) xylylenediamine (manufactured by Meisei Chemical Industry Co., Ltd.) and the like. Can be mentioned.

(Regarding Polyamine (e)) In the present invention, the polyamine (e) is a compound having at least two primary or secondary amino groups, and a compound (f) having at least one unsaturated group. It is used for synthesizing a Michael addition-reacted compound. Further, the polyamine (e) is used for synthesizing a urethane urea having at least one primary or secondary amino group at a terminal together with a polyol containing the polycarbonate polyol (a) and the polyisocyanate (b). As the polyamine (e) used in the present invention, known ones can be used, and specifically, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, Diethylenetriamine,
Aliphatic polyamines such as triaminopropane, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, hydrazine and piperazine, alicyclic polyamines such as isophoronediamine, dicyclohexylmethane-4,4'-diamine, and phenylenediamine And aromatic polyamines such as xylylenediamine. Furthermore, 2-
Hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxy Diamines having a hydroxyl group in the molecule, such as propylethylene) diamine and (di-2-hydroxypropylethylene) diamine,
Also, a dimer diamine obtained by converting the carboxyl group of dimer acid into an amino group, a polyoxyalkylene glycol diamine having propoxyamine at both ends and represented by the following formula (4), and the like can be used. Equation _{(4) H 2 N-CH} 2 -CH 2 -CH 2 -O (C l H 2l -O) k -CH 2 -C
H ₂ —CH ₂ —NH ₂ (In the formula (4), l represents an arbitrary integer of 2 to 4 and k represents an arbitrary integer of 2 to 50.) Further, as a polyamine (e), a primary or secondary polyamine is formed. Dendrimers having a primary amino group can also be used. Such a dendrimer can be obtained by Michael-adding methyl acrylate to ammonia or ethylenediamine and further introducing a primary amino group at the terminal by ester amide exchange reaction as one step, and repeating the step if necessary. Japanese Patent Publication No. 6-70132 and Japanese Patent Publication No. 7-284 shown by the following structural formula (iv)
The star bust conjugates described in Japanese Patent No. 0 and Japanese Patent Publication No. 7-108860 can be mentioned. Further, the reaction of reacting butylenediamine and acrylonitrile to reduce the terminal nitrile group to an amine is one step,
Propylene imines described in JP-A-8-512345 and JP-A-9-508170, which are represented by the following structural formulas (i), (ii), and (v) obtained by repeating the steps. Examples include dendrimers. further,
Examples thereof include aromatic amide amine dendrimers represented by the following structural formula (iii) and star-shaped or comb-shaped branched aliphatic polyamino compounds disclosed in JP-A-7-00084. Furthermore, the polyamine obtained by the manufacturing method shown by Unexamined-Japanese-Patent No. 8-48770 or 8-92369 can be mentioned.

[0038]

[Chemical 3] Structural formula (i) 4-Cascade: 1,4-Diaminobutane [4]: propylamine

[0039]

[Chemical 4] Structural formula (ii) 8-Cascade: 1,4-Diaminobutane [4] (1-azabutylidene) ⁴ propylamine

[0040]

[Chemical 5] Structural formula (iii)

[0041]

[Chemical 6] Structural formula (iv) 12-Cascade: ammonia [3] :( 1,4-diaza-5-oxoheptylidene) ² : 3-aza -4-oxohexylamine

[0042]

[Chemical 7] Structural formula (v) 12-Cascade: ammonia [3] :( 1-azapropylidene) ² : ethylamine Among the polyamines (e) above, isophoronediamine,
2,2,4-Trimethylhexamethylenediamine and hexamethylenediamine are preferable because the reaction can be easily controlled and hygiene is excellent.

(Unsaturated Group-Containing Compound (f)) The unsaturated group-containing compound (f) used in the present invention is
Used for the purpose of modifying urethane urea resin. Therefore, the kind of the compound (f) having an unsaturated group to be used can be arbitrarily selected according to the purpose of modification.

Examples of the structural formula of R ^{3 in} the above formula (1) include the following formulas (5) to (15).

[0045]

[Chemical 8]

In the formulas (5) to (15), Y ^{1 to} Y ¹¹ are each independently a hydrogen atom or a weight average molecular weight of 15 to 2
It is a monovalent organic residue of 0,000, preferably 20 to 10,000.
Y ¹¹ is a direct bond or a divalent organic residue. In the present invention, as the organic residue, 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 an amide group or a dialkylamino group, Examples thereof include nitrogen-containing groups such as quaternary ammonium base.

As the unsaturated compound having the above structural formula, for example, the formula (5) is a (meth) acrylic unsaturated compound,
Formula (6) is an amide unsaturated compound, Formula (7) is a fatty acid vinyl unsaturated compound, 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, Formula (12) is a vinyl cyanide unsaturated compound, Formula (13) is a styrene or vinylbenzene unsaturated compound, Formula (14) Is an alicyclic olefinic unsaturated compound, and formula (15) represents a part of the compound (d) represented by formula (3).

The type of the compound (f) having an unsaturated group to be used can be arbitrarily selected according to the purpose of modification, but the compound (f) having an unsaturated group is selected by focusing on the functional group of the compound (f). Preferably. Examples of the functional group contained in the compound (f) having 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, Furthermore, examples include an amide group, a dialkylamino group, a nitrogen-containing group such as a quaternary ammonium salt group, and the like.

Examples of the amide unsaturated compound of the formula (6) include (meth) acrylamide and N-methylol (meth).
Acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide,
Monoalkylol (meth) acrylamides such as 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-methoxymethyl-N- (pentoxymethyl) meth Examples include dialkyrol (meth) acrylamide such as acrylamide. Examples of the fatty acid vinyl-based alkyl group-containing unsaturated compound of the 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-based unsaturated compound containing an alkyl group of the formula (8) include butyl vinyl ether and ethyl vinyl ether. Furthermore, as the α-olefin-based alkyl group-containing unsaturated compound of the formula (9), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecese, and other unsaturated compounds, as vinyl compounds, allyl compounds such as allyl acetate, allylbenzene and allyl cyanide, vinyl cyanide, vinylcyclohexane, vinylmethylketone, styrene, α-methylstyrene, Examples thereof include vinyl compounds such as 2-methylstyrene and chlorostyrene. Examples of the ethynyl compound include acetylene, ethynylbenzene and ethynyltoluene. Hereinafter, the (meth) acrylic unsaturated compound of the formula (5) will be exemplified. Examples of the (meth) acrylic alkyl group-containing unsaturated compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 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)
Carbon number 1 such as acrylate, nonadecyl (meth) acrylate, icosyl (meth) acrylate, henicosyl (meth) acrylate, docosyl (meth) acrylate
Alkyl group-containing acrylate or corresponding methacrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably having 2 to 8 carbon atoms, for the purpose of adjusting the polarity. Is mentioned. When the purpose is to adjust the leveling property and the like, the number of carbon atoms is preferably 6 or more. If the number of carbon atoms is 23 or more, the Michael addition reaction is difficult to proceed, depending on the purpose.

As the polyalkylene glycol group-containing unsaturated compound, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, polyethylene glycol. Examples include 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.

Further, the unsaturated compound containing a polyalkylene glycol group and having an alkoxy group at the terminal is 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-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-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate,
Examples thereof include ethoxy polyethylene glycol (meth) acrylate.

Further, as the unsaturated compound containing a polyalkylene glycol group and having a phenoxy group at the terminal, phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) Examples thereof include acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene glycol (meth) acrylate.

As the hydroxyl group-containing unsaturated compound other than the above, 2-hydroxyethyl (meth) acrylate, 2-
Examples thereof include hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, and allyl alcohol. As the carboxyl group-containing unsaturated compound, maleic acid, fumaric acid, itaconic acid, citraconic acid, or their alkyl or alkenyl monoesters, phthalic acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) Acryloxyethyl monoester, terephthalic acid β- (meth)
Examples thereof include acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid. Examples of the dialkylamino group-containing unsaturated compound include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene and the like. Also,
It is obtained by converting the above-mentioned unsaturated compound containing a dialkylamino group into a quaternary ammonium compound, and C is used as a counter ion.
Halogen ions such as l-, Br-, I- or QSO3-
Examples of the quaternary ammonium salt group-containing unsaturated compound having (Q: C 1-12 alkyl group) include (meth) acrylic acid dimethylaminoethyl methyl chloride salt, trimethyl-3- (1- (meth) acrylamide-1, 1-dimethylpropyl) ammonium chloride, trimethyl-3-
(1- (meth) acrylamidopropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamido-1,1-dimethylethyl) ammonium chloride and the like can be mentioned.

As the perfluoroalkyl group-containing unsaturated compound, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl ( (Meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, per Carbon such as fluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluorooctylundecyl (meth) acrylate Perfluoroalkyl (meth) acrylates having 1 to 20 perfluoroalkyl groups; perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and perfluoro such as alkylenes An alkyl group-containing unsaturated compound can be exemplified.

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

Further, in the case of imparting curability to the Michael addition type urethane urea resin by active energy, the compound (f) having an unsaturated group having two or more unsaturated groups can be used. As the unsaturated group, a compound (f) 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, or as the compound (f) having an unsaturated group having one acryloyl group and one or more methacryloyl groups, 2-hydroxy-3-acryloxypropyl methacrylate, two or more Examples of the compound (f) having an unsaturated group having a (meth) acryloyl group include 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 , Nonan Oruji (meth) acrylate, glycol di (meth) acrylate, Jiechirenji (meth) acrylate, polyethylene glycol di (meth) acrylate, tris-acryloyloxyethyl 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, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, ethylene glycol-modified pentaerythritol tri (meth) acrylate, propylene glycol-modified pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolethane (meth) acrylate, tetramethylolmethane tri (meth) ) Acrylate, dipentaerythritol alkylate (meth) acrylate,
Actilane 421 (AKCROS CHEMIC
AL), Actilane 423 (AKCROSCHE
MICAL) and the like having two or more functional groups. These may be used alone or in combination of two or more.

The above-mentioned compound (f) having an unsaturated group can be used alone or in combination of two or more kinds.

The Michael addition reaction between the polyamine (e) and the compound (f) having an unsaturated group is carried out by the polyamine (e)
1 molar equivalent of active hydrogen of the amino group of 1 reacts with 1 molar equivalent of the unsaturated group of the compound (f) having an unsaturated group. Since the polyamine (e) easily Michael-adds to the vinyl group or ethynyl group of the compound (f) having an unsaturated group having an electron-withdrawing group, the (meth) acrylic compound, especially the acrylate compound is unsaturated. Group-containing compound (f)
Is preferred as Further, when comparing the acrylate-based compound and the corresponding methacrylate-based compound, the acrylate-based compound is preferable because the efficiency of the Michael addition reaction is good. Further, as the method for synthesizing the polyamino compound (e ′), a known method relating to the Michael addition reaction can be used as it is. When the unsaturated compound is a (meth) acrylic compound, especially an acrylate compound, the reaction proceeds at 10 to 100 ° C. under a catalyst such as alcohol, if necessary. Depending on the type of unsaturated compound used, it is preferably 40 to 8
A reaction temperature of 0 ° C. is preferred. If the reaction temperature is too high, an ester amide exchange reaction occurs, which is not preferable. Also,
When the unsaturated compound does not have an electron-withdrawing group, the reaction becomes possible in the presence of a metal catalyst, and in this case, it is preferable to react at 60 to 100 ° C. while heating in the presence of a catalyst, since an appropriate reaction rate is obtained. . Further, the synthetic solvent may or may not be used, and the kind thereof is not particularly limited, but a known solvent such as methyl ethyl ketone, toluene, acetone and benzene can be used. When the compound (f) or polyamine (e) having an unsaturated group to be used does not contain a hydroxyl group, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, isobutyl alcohol or n-butyl alcohol, or It is preferable to use a mixed solvent thereof. 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 is difficult to proceed, which is not preferable. The reaction time varies depending on the type of unsaturated compound used, but is completed in 30 minutes to 5 hours.

The ratio of the polyamine (e) to the compound (f) having an unsaturated group is such that at least two secondary or primary amino groups remain in the polyamino compound (e ') obtained by the reaction. When it does, it is not particularly limited, but is preferably 0.1 to 1.0 mol, more preferably 0.2 to 1.0 mol with respect to 1 mol of the primary amino group of the polyamine (e).
It is preferable to react at a ratio of 0.98 mol. If it is less than this, the effect of the side chain is less likely to appear.

The Michael addition type urethane urea resin is a urethane prepolymer (A) having an isocyanato group at the terminal.
And a compound (f) having a polyamine (e) and an unsaturated group
Polyamino compound (e ') formed by adding and Michael
And, if necessary, the polyamine (e) is blended, and if necessary, a monoamine compound can be blended as the reaction terminator (f). The reaction terminator (f) is a compound having a functional group capable of reacting with an isocyanato group, and reacts with the unreacted residual isocyanato group at the terminal of the Michael addition type urethane urea resin to stabilize the reaction activity of the resin.

(Regarding Manufacturing Process) The urethanization reaction for forming the urethane prepolymer (A) in the present invention can be carried out by various methods, but is roughly classified into the following two methods. 1) A polyol containing a polycarbonate polyol (a), a polyisocyanate (b), and optionally a compound (j) having a group capable of reacting with an isocyanato group and an ionic group, and / or a solvent, and / or a catalyst ( c)
A method of charging the entire solution consisting of. 2) A polyol containing the polycarbonate polyol (a), and optionally a compound (j) having a group capable of reacting with an isocyanato group and an ionic group, and / or a solvent are charged into a flask, and the polyisocyanate (b) is added dropwise. After that, the catalyst (c) is added if necessary. When the reaction is precisely controlled, 2) is preferable. The reaction temperature for obtaining the urethane prepolymer (A) is preferably 120 ° C. or lower. More preferably, it is 50 to 110 ° C. When the temperature is higher than 110 ° C, it becomes difficult to control the reaction rate, and it becomes impossible to obtain a urethane prepolymer having a predetermined weight average and structure. The urethanization reaction is carried out in the presence of a catalyst at 50 to 110.
It is preferable to carry out at 20C for 1 to 20 hours. Examples of the compound (j) include 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, but it is particularly preferable to use a carboxyl group-containing polyol. As the carboxyl group-containing polyol, dimethylolpropionic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolpentanoic acid, dimethylolalkanoic acid such as dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxy Examples include benzoic acid. Particularly, 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 mixing ratio of the polyol containing the polycarbonate polyol (a) and the polyisocyanate (b) greatly depends on the reactivity of the compound, the abundance ratio of the compound having a valence of 3 or more, the use of the obtained resin and the like. In order for the urethane prepolymer to have at least one isocyanato group, for the polyol containing the polycarbonate polyol (a) and 1 mol of the functional group capable of reacting with the isocyanato group of the compound (j), the polyisocyanate (b) is used. It is necessary that the isocyanato group of is more than 1 mol,
The amount is preferably 1.01 to 4.00 mol, more preferably 1.40 to 3.00 mol.

The urethane prepolymer (A) further comprises
The urethane resin having a urethane urea bond is chain-extended with the polyamino compound (e ′). In the present invention,
Primary or secondary amino which is contained in the urethane prepolymer (A) which is an isocyanato group-containing compound or in the polyisocyanate, and in the polyamino compound (e ') or in the compound (h) having active hydrogen capable of reacting with the isocyanato group. The urea reaction with a group is
There are two methods. 1) A method in which a solution containing an isocyanato group-containing compound is placed in a flask and a solution containing an amino group-containing compound is added dropwise. 2) A method of charging a solution containing an amino group-containing compound into a flask and dropping a solution of a compound having an isocyanato group. The synthesis is carried out by a stable reaction, 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. Even at 70 ° C, the reaction rate is high, and if it cannot be controlled, 50 ° C or lower is more preferable.
When the temperature is higher than 100 ° C, it is difficult to control the reaction rate,
It is difficult to obtain a urethane urea resin having a predetermined molecular weight and structure. The temperature in the reaction system is preferably 50
It is preferable to keep the temperature at or below 0 ° C., more preferably at 40 ° C. or below. Further, the compounding ratio of the urethane prepolymer (A) and the amino group-containing compound is not particularly limited and may be arbitrarily selected depending on the application and the required performance. Usually, the amino group is 1 mol of the isocyanate group in the isocyanato group-containing compound. The number of moles of the amino group functional group in the containing compound is preferably 0.70 to 0.97, more preferably 0.8 to 0.96 in the case of an isocyanato group excess system, preferably 1.001 to 1.40 in the amino group excess system, and more preferably It is 1.01 to 1.2.
If it is out of this range, the molecular weight does not become a predetermined value, which is not preferable. The resin composition having a urethane urea bond has a partial structural formula represented by formula (1). In equation (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 the polyisocyanate (b), and R ³ is a polyamino compound (e ′). ) Represents a monovalent oxygen atom-derived organic residue.

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

The compound (h) having active hydrogen capable of reacting with the isocyanato group plays a role of controlling the molecular weight and reacting with the unreacted isocyanate group remaining at the end of the urethane resin to stabilize the reaction activity of the resin. .

Examples of the compound (h) 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. Other than monoethanolamine,
Diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane,
A monoamine having a hydroxyl group such as 2-amino-2-ethyl-1,3-propanediol, monomethylhydrazine,
Alkyl hydrazines such as 1,1-dimethylhydrazine and benzylhydrazine, hydrazides such as form hydrazide, acetohydrazide and lauric acid hydrazide, N,
Monoamine compounds having a tertiary amino group and a primary amino group on one side, such as N-dimethyl-1,3-propanediamine and N, N diethyl 1,3-propanediamine, and alkoxysilyl such as γ-aminopropyltriethoxysilane. A monoamine compound having a group can also be used.

Among the compounds (h) having active hydrogen capable of reacting with the above-mentioned isocyanato group, monoamines having a hydroxyl group such as 2-amino-2-methyl-propanol are excellent in storage stability because the terminal is a hydroxyl group. Urethane urea resin can be obtained. Further, a urethane urea resin having a hydroxyl group at the terminal is preferable because the hydroxyl group at the terminal also functions as a crosslinking site when a polyisocyanate-based curing agent is added to crosslink. In the case of a monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanato group of the urethane urea resin, but the reactivity of the amino group is higher and it preferentially reacts with the isocyanato group. Further, monoamine compounds 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, are cations at the ends of the urethane urea resin. It is preferably used for introducing a functional group.

The amount of the compound (h) having an active hydrogen capable of reacting with an isocyanato group varies depending on whether the compound is added together with the polyamino compound (e ') or added last alone. Is preferably 0.5 mol or less, more preferably 0.3 m, relative to 1 mol of the isocyanato group in the compound having an isocyanato group.
The amount is preferably not more than ol and is 0.5 to 3.0 mol per 1 mol of the isocyanate group which is finally present when it is added alone at the end, especially when the purpose is to stabilize the resin. Is preferably 1 to 3.0 mol. Outside this range, adverse effects such as deterioration of film forming property and discoloration are observed. The end point of the reaction is the isocyanate% measurement by titration,
It is judged by the disappearance of the isocyanate peak by IR measurement.

The molecular weight of the urethane urea resin is not particularly limited as long as it is used, but it is preferably 1,000 as a weight average molecular weight in terms of standard polystyrene by GPC.
˜200,000 is preferable. More preferably, 5.0
It is 00 to 150,000. The number average molecular weight is preferably 1,000 to 150,000, more preferably 4,000 to 100,000. If it is larger than this, the viscosity becomes too high and it becomes difficult to handle. Conversely, if it is smaller than this, the performance as a polymer cannot be exhibited. When used as a coating agent for forming an ink receiving layer, the weight average molecular weight is 10,000 to 50,000 and the number average molecular weight is 8,000 in view of the balance of surface tack, water resistance and solubility.
More preferably, it is in the range of 0 to 30,000.

The solution viscosity of the obtained urethane urea is not particularly limited and is selected depending on the use of the resin, but preferably, the solid content used is 10 to 10,000 mPa · s (25
℃), and more preferably 500 to 5,000 mPa · s (25 ℃) in terms of solid content when used as an adhesive, and if the viscosity is too high, the coating process may become difficult. If it is too low, a resin having a sufficient molecular weight may not be produced.

(Curing Agent (D)) The urethane resin composition of the present invention, when used in combination with the curing agent (D), becomes an adhesive having a high cohesive force. As the curing agent (D) used in the present invention, the above polyisocyanate (b) can be used. The compounding ratio of the urethane urea resin and the curing agent (D) used in the present invention is 0.1 to 10 parts by weight of the curing agent (D) with respect to 100 parts by weight of the urethane urea resin. When the amount of the curing agent (D) is less than 0.1 part by weight, the cohesive force is reduced, and when it is more than 10 parts by weight, the adhesive force is reduced. It is preferably 1 to 5 parts by weight. A known compounding method can be used for compounding.

(Regarding Additives) The urethane urea resin of the present invention may contain an organic / inorganic filler for the purpose of improving printability and coating properties. In the present invention, the organic filler is a natural product such as starch, acrylic such as polymethylmethacrylate, polystyrene, styrene-acrylic, nylon 6, nylon 12, nylon.
Examples thereof include nylon-based resin such as 6-12, high-density polyethylene, low-density polyethylene, polypropylene, olefin such as tetrafluoroethylene, polyester-based, phenol-based, and benzoguanamine-based resin fine particles. In the present invention, the inorganic filler is 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, pseudo-boehmite, hydroxide Inorganic fillers such as aluminum, lithopone, zeolite and montmorillonite can be mentioned. When using alumina sol or colloidal silica as the filler component,
When the urethane urea resin is made aqueous by the above-mentioned method and then the filler is mixed, a mixed solution can be stably obtained.

Furthermore, 1) When a compound having a hydroxyl group or a carboxyl group is used as the compound (h) having active hydrogen capable of reacting with an isocyanato group, 2) As a compound (h) having active hydrogen capable of reacting with an isocyanato group. When a compound having an alkoxysilyl group is used, the obtained urethane urea resin can be grafted on the filler. When the urethane urea resin has a hydroxyl group, a carboxyl group, or an epoxy group, it can be grafted by adding a silane coupling agent to the liquid mixture of the resin and the filler and heating and stirring at 40 to 100 ° C for 10 minutes to 3 hours. Is. When the urethane urea resin has a methylol group or an N-alkoxymethyl group, it can be grafted by heating and stirring the mixed solution of the resin and the filler in the presence of an acid catalyst, if necessary. When the urethane urea resin has an alkoxysilyl group, the mixed solution of the resin and the filler is 40 to 100 ° C., and 1
Grafting is possible by heating and stirring for 0 minutes to 3 hours.

When the urethane urea resin is grafted to the alumina sol or colloidal silica, it is preferable that the filler is mixed after hydration by the above-mentioned method or hydration during the grafting reaction because a stable graft body can be obtained.

The blending ratio of the filler and the urethane urea resin varies depending on the purpose of blending the filler. For the purpose of, for example, preventing blocking or improving the mechanical properties of the coating film, the total amount of the coating agent is used as a standard. , Preferably 5
-50% by weight, more preferably 10-40% by weight, and if the amount is more than 50% by weight, the mechanical properties of the coating film, especially bendability,
Extensibility is reduced. Further, for the purpose of improving the drying property of the ink, it is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, and if it is less than this, sufficient 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.

The urethane urea resin of the present invention contains other resins for the purpose of preventing blocking, curling, adjusting surface gloss, improving weather resistance, improving wettability of ink droplets, etc.
For example, acrylic resin, polyamide, epoxy resin, polyurethane resin, polyvinyl acetate, polyvinyl acetal, polystyrene, fluorine resin, polycarbonate, polyether, polyisobutylene, petroleum resin, rosin, nitrocellulose, sucrose ester, vinyl chloride / vinyl acetate copolymer Polymer, ethylene / vinyl acetate copolymer, α
-Olefin / maleic anhydride type copolymer, styrene /
Other than thermoplastic resins such as maleic anhydride copolymers, phenol resins, urea resins, melamine resins, amino resins, polyester resins, alkyd resins, silicon resins, epoxy resins, epoxy acrylate, polyester acrylate, urethane acrylate, poly One kind or two or more kinds of resins, such as ether acrylate and phosphazene resin, which are hardened by ultraviolet rays or electron beams can be blended within a range not hindering the object of the present invention. In addition, if necessary, a filler such as talc, calcium carbonate, titanium oxide,
Fluorescent dyes such as tackifiers, UV absorbers, optical brighteners,
Coloring dyes, colorants, thickeners, defoamers, leveling agents, anticraters, antisettling agents, antioxidants, light stabilizers,
Additives such as flame retardants, waxes and heat stabilizers may be appropriately added alone or in combination of two or more.

As the deterioration inhibitor 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 radical chain inhibitors (primary antioxidants) and peroxide decomposers (secondary antioxidants).

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

Examples of the peroxide decomposer (secondary antioxidant) include sulfur type antioxidants and phosphorus type antioxidants.

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

As the monophenol type antioxidant,
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.

As the bisphenol type antioxidant,
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-)
6-t-butylphenol), 4,4′-thiobis (3
-Methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β-
(3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-
And tetraoxaspiro [5.5] undecane.

Examples of the polymeric phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4. , 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis-
[Methylene-3- (3 ', 5'-di-t-butyl-4'
-Hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5) '-Di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,
4,6- (1H, 3H, 5H) trione, tocophenol, and the like. IRGANOX L 135 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferable because of its compatibility with resins.

As the sulfur type antioxidant, dilauryl 3,3'-thiodipropionate, dimyristyl 3,
3'-thiodipropionate, distearyl 3,3'-
Thiodipropionate and the like can be mentioned.

Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, and the like.

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

As the benzophenone type ultraviolet absorber,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-
4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane, Etc. can be mentioned.

As the benzotriazole type ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) is used.
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 can be mentioned. TUNUVIN 571 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferable because of its compatibility with resins.

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

Examples of the cyanoacrylate type ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-.
Diphenyl acrylate, etc. can be mentioned.

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 1,2,
2,6,6-Pentamethyl-4-piperidyl sebacate can be mentioned. The product name is TINUVI
N 765 (Ciba Specialty Chemicals Co., Ltd.), ADEKA STAB LA-77 (Asahi Denka), Chima
sosorb 944LD (Ciba Specialty Chemicals Co., Ltd.), TINUVIN 622LD (Ciba Specialty Chemicals Co., Ltd.), TINUV
IN 144 (Ciba Specialty Chemicals Co., Ltd.), ADEKA STAB LA-57 (Asahi Denka), ADEKA STAB LA-62 (Asahi Denka), ADEKA STAB LA-67
(Asahi Denka), ADEKA STAB LA-63 (Asahi DENKA), ADEKA STAB LA-68 (Asahi DENKA), ADEKA STAB LA-8
2 (Asahi Denka), ADEKA STAB LA-87 (Asahi Denka), G
goodrite UV-3034 (Goodrich)
Can be mentioned. TINUVIN 765 (Ciba Specialty Chemicals Co., Ltd.) is particularly preferable because of its compatibility with resins.

As the UV stabilizer, nickel bis (octylphenyl) sulfide, [2,2'-thiobis (4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-
Di-tert-butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type quencher, nickel-
Dibutyldithiocarbamate and the like can be mentioned.

As the deterioration inhibitor, it is preferable to include an antioxidant and an ultraviolet absorber or a light stabilizer, and it is preferable to further include all of the antioxidant, the ultraviolet absorber and the light stabilizer. TINUVIN B 75 (Ciba Specialty Chemicals Co., Ltd.) is IRGANOX
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 they can be used without their mutual effects interfering with each other.
The amount used is preferably 0 to 10% by weight of the solid content.

[0096]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

A synthesis example is shown below.

Synthesis Example 1 Isophoronediamine (IPD
A) 400 g and toluene 400 g were charged, and 4-hydroxybutyl acrylate 678 g was added dropwise at room temperature. After completion of dropping, the mixture was reacted at 80 ° C. for 1 hour and then toluene 678
The compound to which g is added is referred to as compound (1).

Synthesis Example 2 Kuraray Polyol C-1090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 112, manufactured by Kuraray Co., Ltd.) 675 g, isophorone diisocyanate (manufactured by Huls Japan 225 g), toluene 225 g, dibutyltin dilaurate 0.07 as a catalyst.
Charge 5 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After confirming the remaining amount of isocyanato group by titration, 40 ℃
After cooling to 1663 g of ethyl acetate and 2.7 g of acetylacetone, 286 g of compound (1) dissolved in 180 g of ethyl acetate was added dropwise over 1 hour, and after aging for 1 hour, 2-amino-2-methyl -6.5 g of propanol (manufactured by Nagase & Co., Ltd.) was added, and it was confirmed that the NCO characteristic absorption (2270 cm-1) on the IR chart had disappeared, and the reaction was terminated. The reaction solution was colorless and transparent, had a solid content of 32%, a viscosity of 4,800 cps, a number average molecular weight of MN49,500, and a weight average molecular weight of MW163,000.
Met.

Synthesis Example 3 Kuraray polyol C-2090 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
(Bifunctional polycarbonate diol, OH value 56.5,
Kuraray Co., Ltd.) 514 g, isophorone diisocyanate (Huls Japan Co., Ltd.) 86 g, toluene 150 g, dibutyltin dilaurate 0.05 as a catalyst
0 g is charged, 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, 40 ℃
After cooling to 853 g of ethyl acetate and 1.8 g of acetylacetone, 15.7 g of 2-hydroxyethylaminopropylamine (manufactured by Koei Chemical Industry Co., Ltd.) dissolved in 120 g of ethyl acetate was added dropwise over 1 hour. After aging for 1 hour, 5.5 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added, and it was confirmed that the NCO characteristic absorption (2270 cm -1) on the IR chart had disappeared and the reaction was completed. Finished. The reaction solution was colorless and transparent, had a solid content of 35%, a viscosity of 4,400 cps, a number average molecular weight of MN23,000, and a weight average molecular weight of MW6,200.
It was 0.

Synthesis Example 4 A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was placed in a Kuraray polyol PMHC-1.
050 (bifunctional polycarbonate diol, OH value 11
2.7, manufactured by Kuraray Co., Ltd., 674 g, isophorone diisocyanate (manufactured by Huls Japan Co., Ltd.) 226
g, 225 g of toluene, and 0.075 g of dibutyltin dilaurate as a catalyst are charged, the temperature is gradually raised to 100 ° C., and the reaction is performed for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 1663 g of ethyl acetate and 2.7 g of acetylacetone were added, and then 180 g of ethyl acetate
251 g of the compound (1) dissolved in
After further aging for 1 hour, 6.0 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added,
It was confirmed that the NCO characteristic absorption (2270 cm -1) on the IR chart had disappeared, and the reaction was terminated. The reaction solution was colorless and transparent, had a solid content of 32%, a viscosity of 14,500 cps,
Number average molecular weight MN48,000, weight average molecular weight MW1
It was 65,000.

Synthesis Example 5 Kuraray Polyol C-2015 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
N (bifunctional polycarbonate diol, OH value 57, manufactured by Kuraray Co., Ltd.) 513 g, isophorone diisocyanate (manufactured by Huls Japan KK) 87 g, toluene 1
50 g, dibutyl tin dilaurate as catalyst 0.050
After charging g, the temperature is gradually raised to 100 ° C. and the reaction is performed for 2 hours. After confirming the remaining amount of the isocyanato group by titration, it was cooled to 40 ° C., and 884 g of ethyl acetate and acetylacetone 1.
After adding 8 g, 70 g of compound (1) dissolved in 120 g of ethyl acetate was added dropwise over 1 hour, and after aging for 1 hour, 2-amino-2-methyl-propanol (Nagase & Co., Ltd.) 5. NC of IR chart with 2g added
It was confirmed that the O characteristic absorption (2270 cm -1) had disappeared, and the reaction was terminated. The reaction solution was colorless and transparent, had a solid content of 35%, a viscosity of 1,300 cps, and a number average molecular weight of MN3.
It was 1,000 and the weight average molecular weight was MW61,500.

Synthesis Example 6 A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was placed in a Kuraray polyol C-1015.
N (bifunctional polycarbonate diol, OH value 112,
Kuraray Co., Ltd.) 450 g, isophorone diisocyanate (Huls Japan Co., Ltd.) 150 g, toluene 150 g, dibutyltin dilaurate 0.0 as a catalyst
Charge 50 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After checking the remaining amount of isocyanato group by titration,
After cooling to 0 ° C. and adding 1112 g of ethyl acetate and 1.8 g of acetylacetone, 46 g of MXDA-PO2 (manufactured by Mitsubishi Gas Chemical Co., Inc.) dissolved in 120 g of ethyl acetate.
Was added dropwise over 1 hour, and after aging for 1 hour, 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.)
4.5g was added, and the NCO characteristic absorption (2
It was confirmed that 270 cm-1) had disappeared and the reaction was terminated. This reaction solution was colorless and transparent, had a solid content of 32%, a viscosity of 4,500 cps, a number average molecular weight of MN47,500, and a weight average molecular weight of MW143,000.

Synthesis Example 7 Kuraray polyol C-2065 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
N (bifunctional polycarbonate diol, OH value 53.
5, 518 g of Kuraray Co., Ltd., 82 g of isophorone diisocyanate (manufactured by Huls Japan KK), 150 g of toluene, and dibutyltin dilaurate as a catalyst of 0.1 g.
Charge 050 g, gradually raise the temperature to 100 ° C., and carry out the reaction for 2 hours. After confirming the amount of isocyanato group remaining by titration, 4
After cooling to 0 ° C., 881 g of ethyl acetate and 1.8 g of acetylacetone were added, and then 66 g of compound (1) dissolved in 120 g of ethyl acetate was added dropwise over 1 hour, followed by aging for 1 hour, and then 2-amino-2. -Methyl-propanol (manufactured by Nagase & Co., Ltd.) (5.2 g) was added, and it was confirmed that the NCO characteristic absorption (2270 cm -1) on the IR chart had disappeared, and the reaction was terminated. The reaction solution was colorless and transparent and had a solid content of 35%, a viscosity of 1,500 cps, a number average molecular weight MN32,000 and a weight average molecular weight MW63,500.

Synthesis Example 8 Kuraray Polyol C-1065 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
N (bifunctional polycarbonate diol, OH value 114.
9, 475 g of Kuraray Co., Ltd., 153 g of isophorone diisocyanate (manufactured by Huls Japan KK), 150 g of toluene, and 0.050 g of dibutyltin dilaurate as a catalyst are charged, 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., 1110 g of ethyl acetate and 1.8 g of acetylacetone were added, and 170 g of compound (1) dissolved in 120 g of ethyl acetate was added dropwise over 1 hour, and further. After aging for 1 hour, 4.5 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to give I.
It was confirmed that the NCO characteristic absorption (2270 cm -1) on the R chart had disappeared and the reaction was terminated. The reaction solution was colorless and transparent, had a solid content of 32%, a viscosity of 4,300 cps, a number average molecular weight of MN45,500, and a weight average molecular weight of MW14.
It was 1,000.

Synthesis Example 9 Polyester polyol P-2 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
010 (bifunctional polyester polyol, OH value 57,
Kuraray Co., Ltd.) 257 g, isophorone diisocyanate (Huls Japan Co., Ltd.) 43 g, toluene 75 g, dibutyltin dilaurate 0.025 as catalyst
After charging g, the temperature is gradually raised to 100 ° C. and the reaction is performed for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., ethyl acetate 164 g, acetylacetone 0.
After adding 9 g, 39 g of the compound (1) was added dropwise over 1 hour, and after aging for 1 hour, 3.3 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added and an IR chart. NCO characteristic absorption (2270cm-1)
Was confirmed to have disappeared, and the reaction was terminated. The reaction solution is colorless and transparent, has a solid content of 50% and a viscosity of 6,000 cp.
s, number average molecular weight MN27,500, weight average molecular weight M
It was W57,000.

Synthesis Example 10 Polyether polyol PP-is 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 number 5
6, manufactured by Sanyo Chemical Industry Co., Ltd.) 257 g, isophorone diisocyanate (manufactured by Huls Japan KK) 43
g, 75 g of toluene, and 0.025 g of dibutyltin dilaurate as a catalyst are charged, and the temperature is gradually raised to 100 ° C.
React for time. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 164 g of ethyl acetate and 0.9 g of acetylacetone were added, and 39 g of the compound (1) was added to 1 g.
After dripping for 2 hours and aging for 1 hour, 2-amino-
2-methyl-propanol (made by Nagase & Co., Ltd.) 3.
3g was added, and the NCO characteristic absorption of IR chart (227
It was confirmed that 0 cm-1) had disappeared, and the reaction was terminated. The reaction solution is colorless and transparent, has a solid content of 50%, a viscosity of 2,
It was 800 cps, number average molecular weight MN 29,000, and weight average molecular weight MW 78,000.

Adhesive effect

Example 1 1.28 g of the curing agent (D) was added to 100 g of the urethane resin solution synthesized in Synthesis Example 2, and the adhesive strength, removability after heat resistance test, and moist heat resistance test were performed by a predetermined method. The subsequent removability was measured. As the curing agent (D), a 75% ethyl acetate solution of hexamethylene diisocyanate trimethylolpropane adduct was used.

The test method is as follows. <Coating method> The above-mentioned urethane urea resin solution is coated on a release paper with an applicator so as to give a dry coating film of 25 μm, and 1
It was dried at 00 ° C for 2 minutes to prepare a coated product. After one week at room temperature, it was used for the following measurements. <Adhesive strength> An adhesive sheet obtained by applying a urethane urea resin solution to release paper was transferred to a polyethylene terephthalate film (film thickness 25 μm), and was placed on a stainless steel plate (SUS304) having a thickness of 0.4 mm at 23 ° C. and 65% RH. 20 minutes after roll bonding according to JIS, peel strength (180 degree peel, pulling speed 300 mm / min; unit g / 25 mm width) was measured with a Shopper type peel tester. <Removability after heat resistance test and moisture heat resistance test> An adhesive sheet obtained by coating a urethane urea resin solution on release paper was transferred to a polyethylene terephthalate film (film thickness 25 μm) or paper (film thickness 30 μm), Stainless plate (SU
S304), and then 80 ° C dry, 80 ° C-9
Leave at 0% RH for 1,000 hours,
After cooling to 5% RH, peeling was performed, and the adhesive residue was visually evaluated. After peeling, there was no transfer of glue to the adherend ◎ Very slight ○ Partially present △ Completely transferred ×

Examples 2 to 7 and Comparative Examples 1 and 2 The urethane resin was changed to that shown in Table 1, and the curing agent (D) was used.
The amount added was changed as shown in Table 1, and the same operation as in Example 1 was performed thereafter. Table 1 also shows the solid content of the urethane resin, the adhesive strength, the removability after the heat resistance test, and the removability after the wet heat resistance test.

[0112]

[Table 1]

[0113]

EFFECTS OF THE INVENTION According to the present invention, the drawbacks such as poor heat resistance and wet heat resistance of urethane resins using polyether polyols and polyester polyols are improved, and heat resistance,
It has become possible to provide a urethane resin composition having excellent wet heat resistance and a method for producing the same.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J034 BA08 CA02 CA03 CA04 CA05                       CA14 CA15 CA16 CA17 CA22                       CA24 CA34 CB01 CB02 CB03                       CB05 CB07 CB08 CC02 CC03                       CC12 CC23 CC26 CC29 CC34                       CC45 CC52 CC61 CC62 CC65                       CC67 CC69 CD01 CD04 CD05                       CD06 CD12 CD13 CD15 CD16                       CE03 DA01 DA03 DB04 DB07                       DC02 DC06 DF02 DF11 DF12                       DF16 DF17 DF20 DF21 DF22                       DG02 DG03 DG04 DG05 DG08                       DG10 DG12 DG14 DM01 HA01                       HA02 HA06 HA07 HA08 HB06                       HB08 HB11 HC03 HC12 HC13                       HC17 HC22 HC25 HC26 HC34                       HC35 HC45 HC46 HC52 HC61                       HC63 HC64 HC65 HC67 HC70                       HC71 HC73 KA01 KB02 KC08                       KC16 KC17 KC18 KC35 KD02                       KD04 KD08 KD12 KD21 KD24                       KD25 KE02 RA08                 4J040 EF061 EF071 EF121 EF131                       KA16 LA01 LA07 LA08 LA10

Claims (10)

[Claims] 1. A urethane resin having both binding sites represented by the following formulas (1) and (2) synthesized from a raw material containing a polyamino compound (e '), a polyisocyanate (b) and a polycarbonate polyol (a). Composition. Equation ^{(1) -R 1 -N (R} 3) -CO-NH-R 2 - ( in the formula (1), R ¹ is a divalent organic residue having an amino group derived from a polyamino compound (e ') , R ² represents a polyvalent organic residue derived from polyisocyanate (b), and R ³ represents an organic residue containing a monovalent oxygen atom.) Formula (2) — [— O—R ⁸ —O —CO—] _m − (In the formula (2), R ⁸ represents a divalent organic residue, and m represents an integer of 1 or more.) Is wherein R ^3, containing at least one hydroxyl group 1
The urethane resin composition according to claim 1, which is a valent organic residue. 3. The urethane resin composition according to claim 1, wherein the polyamino compound (e ′) is a compound obtained by subjecting a polyamine (e) and a compound (f) having an unsaturated group to a Michael reaction. 4. The polyamino compound (e ′) is a compound (d) represented by the following formula (3):
The urethane resin composition described. Formula (3) (In the formula (3), Y represents a monovalent hydrocarbon group containing one or more functional groups having active hydrogen, but may also contain NH in the main chain. N represents 0 or 1. , R ⁴ and R
⁵ independently represents a hydrogen atom or a monovalent hydrocarbon group containing no hydroxyl group, and R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent hydrocarbon group. ) 5. A polyurethane prepolymer (A) obtained by reacting a polyol containing a polycarbonate polyol (a) with a polyisocyanate (b) in the presence of a catalyst (c) is chained with a polyamino compound (e ′). A method for producing a urethane resin composition, which comprises extending. 6. A polyurethane prepolymer (A) obtained by reacting a polyol containing a polycarbonate polyol (a) with a polyisocyanate (b) in the presence of a catalyst (c) is chained with a polyamino compound (e '). A method for producing a urethane resin, which comprises reacting an extended urethane resin composition having an isocyanato group at a terminal with a compound (h) capable of reacting with an isocyanato group. 7. The method for producing a urethane resin according to claim 5 or 6, wherein the polyamino compound (e ') contains a hydroxyl group. 8. A pressure-sensitive adhesive comprising the urethane resin composition according to claim 1. 9. A pressure-sensitive adhesive comprising the urethane resin composition according to claim 1 and a curing agent (D). 10. A laminate comprising a base material and the pressure-sensitive adhesive according to claim 8 or 9. [0000]