JP2002121256A - Michael addition type urethane urea resin and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a Michael addition type urethane urea resin which sufficiently utilizes the characteristics of a urethane urea resin and can simply and effectively control its physical properties, and to provide a method for producing the resin. SOLUTION: This Michael addition type urethane urea resin is produced from raw materials comprising (a) a polyol, (b) a polyisocyanate, (c) a polyamine, and (d) and unsaturated compound and has bond sites represented by formula (1-1) or (1-2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a novel urethane urea resin having various properties by adding a variety of unsaturated compounds while utilizing the characteristics of urethane urea. Further, the urethane urea resin obtained by the present invention is used in addition to coating materials such as paints, ink binders, overcoat varnishes, various functional surface treatment agents, adhesives, fine particle dispersants such as organic and inorganic pigments, and compatibilizers. The present invention provides a Michael addition type urethane urea resin used for the above-mentioned purposes.

[0002]

2. Description of the Related Art Since a urethane resin and an acrylic resin have different characteristics from each other, there is a possibility that a composite compound can exhibit characteristics that cannot be achieved by itself. But,
It is also well known that urethane resin and acrylic resin have poor compatibility except for some acrylic resins. Therefore, various attempts for copolymerization have been studied. However, because of their different polymerization forms, copolymerization is basically difficult, and a two-part or microgel resin obtained by mixing a hydroxyl group-containing acrylic monomer with an isocyanate-terminal urethane resin as a crosslinking agent, or a urethane resin Considering the use of a monofunctional acrylic monomer with a bond to introduce a urethane bond into the side chain, or a urethane acrylic emulsion using a bifunctional acrylic monomer to study the formation of a mutually intrusive resin composite. Have been. However, in the conventional method, the chain of the acrylic monomer is the main skeleton, and the toughness peculiar to the urethane main chain has not been sufficiently exhibited.

[0003] On the other hand, urethane resins basically consist of a polyol component and a polyisocyanate component, and the variation of each component only causes a change in the main chain. It was difficult to change the value as compared with a side chain resin such as a vinyl resin. For example, adhesion to the substrate, cohesive strength,
In order to change the polarity with the intention of improving mechanical strength,
In the case of urethane resin, modification is considered by adding an amine component to make urethane urea resin, but the effect of copolymerization with carboxylic acid group-containing monomer in the case of vinyl resin is not enough. It is.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a Michael-added urethane urea resin capable of easily and effectively controlling its properties while fully utilizing the characteristics of the urethane urea resin, and a method for producing the same. Is provided.

[0005]

The urethane urea resin has a structure in which an unsaturated compound is added to a polyamino compound by Michael as a component thereof, whereby various properties can be easily controlled while maintaining the characteristics of the urethane urea resin. The inventors have found that this is possible and have led to the present invention.

The present invention comprises a raw material containing a polyol (a), a polyisocyanate (b), a polyamine (c) and an unsaturated compound (d), and has the following formulas (1-1) and (1-2)
And a Michael addition type urethane urea resin having a binding site represented by

[0007]

Embedded image

Wherein R ³ is a monovalent organic residue derived from the unsaturated compound (d), X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁴ is a hydrogen atom, and the polyamine (c) A monovalent organic residue or a monovalent organic residue derived from an unsaturated compound (d) is shown.) In addition, the present invention provides a method for reacting a polyol (a) with a polyisocyanate (b) to obtain a terminal. The present invention relates to a Michael addition type urethane urea resin obtained by reacting a polyamine (c) and an unsaturated compound (d) with an amino compound (B) to a urethane prepolymer (A) having an isocyanate group.

Further, the present invention relates to a method for reacting a polyol (a), a polyisocyanate (b) and a polyamine (c) with a polyurethane urea (C) having a primary or secondary amino group at the terminal, to obtain an unsaturated urea (C). The present invention relates to a Michael addition type urethane urea resin obtained by subjecting compound (d) to a Michael addition reaction.

Further, the present invention provides a step (a) of reacting a polyol (a) with a polyisocyanate (b) to form a urethane prepolymer (A), and a Michael addition reaction of the polyamine (c) with the unsaturated compound (d). A method for producing a Michael-added urethane urea resin, comprising: a step b of preparing an amino compound (B) by reacting the urethane prepolymer (A) with the amino compound (B) to produce a Michael-added urethane urea resin. About.

Further, the present invention provides a step d) of reacting a polyol (a), a polyisocyanate (b) and a polyamine (c) to form a polyurethane urea (C) having a primary or secondary amino group at a terminal, and The present invention relates to a method for producing a Michael addition type urethane urea resin, comprising a step e of subjecting the polyurethaneurea (C) to a Michael addition reaction with an unsaturated compound (d).

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Michael addition type urethane urea resin referred to in the present invention is a urethane urea resin having a structure in which an unsaturated compound is added to a polyamino compound by Michael. That is, equation (1-1) or (1
-2) is a urethane urea resin having a binding site represented by -2).

In the formula (1-1) or (1-2), a carbon atom which is not a carbonyl group and is bonded to a nitrogen atom linked to a group containing R ³ is a group in which the Michael addition type urethane urea resin is a polyamine (c). When used as a raw material, polyamine (c)
Carbon atom of origin.

The carbon atom linked to the carbonyl group and the hydrogen atom is a carbon atom derived from polyisocyanate (b) when polyisocyanate (b) is used as a raw material.

R ³ is a monovalent organic residue, and when the Michael addition type urethane urea resin uses the unsaturated compound (d) as a raw material, R ³ is an organic residue derived from the unsaturated compound (d). Specifically, it is a linear or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic group, or a combination of these functional groups. R ³ may include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom such as fluorine, chlorine, and bromine and the like, and may include a substituent such as a hydroxyl group, an amino group, and an epoxy group. When R ³ is an aromatic group, it may have an aliphatic group as a substituent. R ³
Has a weight average molecular weight of preferably from 20 to 20,000, more preferably from 40 to 10,000, and still more preferably from 45 to 5,000.

R ⁴ is a hydrogen atom, an organic residue derived from a polyamine (c), or a monovalent organic residue derived from an unsaturated compound (d), and a terminal is a urethane urea having a secondary amino group ( When C) is used, it is an organic residue derived from the polyamine (c) or the amine compound (B) having formed a terminal site. Specifically, the weight average molecular weight is 15 to 100.
0, preferably 15 to 500, is a monovalent organic residue, and more specifically, the same functional groups as those described for R ³ . When a urethane urea (C) having a primary amino group at the terminal is used, R ⁴ is a hydrogen atom or an organic residue represented by —CH ₂ —CH (X) —R ³ .

X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Formula (1-1) represents the polyamine (c) used
Shows a state in which the unsaturated group contained in the unsaturated compound and the isocyanato group contained in the urethane prepolymer are bonded to at least one primary or secondary amino group contained in the urethane prepolymer. Formula (1-2) shows a state in which an unsaturated group contained in the unsaturated compound (d) is bonded to a primary or secondary amino group contained in the polyamine (c) having a main chain or a branched terminal. .

In the present invention, the polyamine (c) is a compound having at least two primary or secondary amino groups, and the amino compound (B) is synthesized by Michael addition of at least one unsaturated compound. Used for In the present invention, the polyamine (c) is
To react with polyol (a), polyisocyanate (b), and optionally polyamino compound (B) to synthesize urethane urea (C) having at least one primary or secondary amino group at its terminal Used.

The obtained amino compound (B) is used as a starting material for a urea reaction for modifying a urethane resin.

That is, when the amine compound (B) has at least two primary or secondary amino groups,
It is used to react with the urethane prepolymer (A) to obtain a Michael addition type urethane urea resin.

When the amine compound (B) has one primary or secondary amino group, it is used as a reaction terminator (f). In this case, the obtained Michael addition type urethane urea resin has the above formula. It has the terminal structure shown in (1-2).

As the polyamine (c), known ones can be used, and specifically, ethylenediamine,
Fats such as propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, hydrazine and piperazine Alicyclic polyamines such as aromatic polyamines, isophorone diamine, and dicyclohexylmethane-4,4'-diamine; and aromatic polyamines such as phenylenediamine and xylylenediamine. Further, 2-hydroxyethylethylenediamine, N-
(2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, ( Diamines having a hydroxyl group in the molecule, such as di-2-hydroxypropylethylene) diamine and dimer diamine obtained by converting a carboxyl group of dimer acid into an amino group, having propoxyamine at both terminals, and represented by the following formula (2) And the like can also be used.

H ₂ —NCH ₂ —CH ₂ —CH ₂ —O (C _n H _2n —
O) _m -CH ₂ -CH ₂ -CH ₂ -NH ₂ (2) (in the formula (2),
n represents an arbitrary integer of 2 to 4, and m represents an arbitrary integer of 2 to 50. Furthermore, a dendrimer having a primary or secondary amino group at a terminal can be used as the polyamine (c). Such a dendrimer is obtained by Michael addition of methyl acrylate to ammonia or ethylenediamine, and furthermore, a step of introducing a primary amino group at a terminal by a transesterification reaction as one step, and repeating this step as necessary. JP-B-6-70132 and JP-B-7-284 represented by the following structural formula (iv).
No. 0 and Japanese Patent Publication No. Hei 7-108860 are examples of the star bust conjugate. In addition, the reaction of reacting butylenediamine with acrylonitrile and reducing the terminal nitrile group to an amine is one step,
Propyleneimine represented by the following structural formulas (i), (ii) and (v) obtained by repeating this step and described in JP-A-8-512345 and JP-A-9-508170 Series dendrimers. further,
Aromatic amidoamine type dendrimers represented by the following structural formula (iii) and star-shaped or comb-shaped branched aliphatic polyamino compounds described in JP-A-7-00084 can be exemplified. Further, there may be mentioned polyamino compounds obtained by the production method described in JP-A-8-48770 or JP-A-8-92369.

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

Of the above-mentioned polyamines (c), isophoronediamine, 2,2,4-trimethylhexamethylenediamine, and hexamethylenediamine are preferred because of easy control of the reaction and excellent hygiene.

The urethane prepolymer (A) used in the present invention comprises a polyol (a) and a polyisocyanate (b)
Is a compound having at least one isocyanato group. In addition, as a raw material of the urethane prepolymer (A), a polyamine (c),
It may contain water or a compound (e ′) having an ionic functional group and a group capable of reacting with an isocyanato group described below.

Examples of the polyol (a) include one or more of high molecular weight polyols, bisphenols such as bisphenol A and bisphenol F, and glycols obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to bisphenols. Kind,
Other polyols and the like can also be used. In addition, one or more of these and an olefin,
Compounds having two or more active hydrogen groups obtained by reaction with other compounds such as aromatic hydrocarbons can also be used.

In the present invention, the high molecular weight polyol is a compound having a repeating unit having a degree of polymerization of 2 or more and having two hydroxyl groups, and includes polyester polyols and polyether polyols.

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

As the polyester polyol, for example,
There is a polyester polyol obtained by a condensation reaction between a polyol component and a dibasic acid component. Among the polyols, diols 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 A, and three or more Examples of the polyol having a hydroxyl group include glycerin, trimethylolpropane, and pentaerythritol. Examples of the dibasic acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and other aliphatic or aromatic dibasic acids or aromatic dibasic acids. In addition, ε-caprolactone poly (β-methyl-γ-
Polyester polyols, polycarbonate polyols, silicone polyols and the like obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as valerolactone) and polyvalerolactone can be used.

The weight average molecular weight of the polyester polyols is preferably from 1,000 to 5,000, more preferably from 1,500 to 3,500. The amount used is from 0 to 0 in the polyol constituting the urethane prepolymer (A).
50 mol% is preferred.

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

Examples of the polymerization initiator for polymerizing the alkylene oxide include glycerin, sorbitol,
Trimethylolpropane, trimethylolbutane, trimethylolethane, 1,2,6-hexanetriol,
A polyether polyol which is a trihydric or higher alcohol such as pentaerythritol 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, in order to make it easier to draw out the side chain effect.
２５25,000, 1,000-10,000. The use amount of the polyether polyol is preferably 50 to 100 mol% in the polyol constituting the polyurethane.

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

Other polyols include ethylene glycol, diethylene glycol, triethylene glycol, butanediol, propanediol, 1,6
2-hexanediol, neopentyl glycol, cyclohexanedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl 2,2,8,10-tetraoxospiro [5.5] undecane, etc. Compounds having three or more hydroxyl groups, such as compounds having a hydroxyl group, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, methylglucoside, and the like are included.

As the polyol (a), a polyol (e) containing at least one ionic functional group can be used. The ionic functional group is an ionic group such as a quaternary ammonium base, a tertiary amino group, a carboxylate group, a carboxyl group, a sulfonate group, a sulfonic acid group, a phosphonium group, a phosphinic acid group, a sulfate group, or the like. It is a precursor group. The carboxyl group, tertiary amino group and the like are not ionic groups, but are ionic precursors which can be easily converted to ionic groups by neutralization or quaternization reaction with ammonia, tertiary amine, acetic acid or the like.

The polyol (e) containing at least one ionic functional group is used in order to make the Michael addition type urethane urea resin aqueous or to increase the reaction rate at the time of synthesizing the urethane prepolymer (A). It is also preferably used in terms of improving film properties.

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

Glycerin monophosphate disodium salt, sodium dimethylol phosphinate, 5-
Polyester polyol having sodium sulfoisophthalate unit, carboxyl group-containing polyester polyol obtained by addition / condensation reaction of diol with aliphatic or aromatic polybasic anhydride, addition of lactone using dimethylolalkanoic acid as initiator Carboxyl group-containing polyols other than those described above that have been polymerized are exemplified. Of these, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butyric acid, 2,2-bis
(Hydroxymethyl) valeric acid, 2,2-bis (hydroxymethyl) butanoic acid, and a polyol containing a tertiary amino group are preferably used.

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

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

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

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

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

The araliphatic polyisocyanates include:
ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate And 1,3-tetramethylxylylene diisocyanate.

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.

In addition, a trimethylolpropane adduct of the above-mentioned polyisocyanate, a trimer having an isocyanurate ring, and the like can also be used in combination. Polyphenylmethane polyisocyanate (PAPI), naphthylene diisocyanate, and their modified polyisocyanates can be used. As the modified polyisocyanate, a carbodiimide group, a uretdione group, a uretoimine group, a buret group reacted with water, an isocyanurate group, or a modified compound having two or more of these groups can be used. 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-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate),
It is preferable from the viewpoint of weather resistance to use a non-yellowing type or non-yellowing type polyisocyanate compound such as xylylene diisocyanate or 4,4′-methylenebis (cyclohexyl isocyanate) (hydrogenated MDI).

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

In the above formula (1-1) or (1-2), X and R ³
Is an organic residue derived from the unsaturated compound (d) used, and the following formulas (3) to (12) can be exemplified as the structural formula of R ³ when focusing on the type of the unsaturated group.

[0056]

Embedded image

In the formulas (3) to (12), Y ^{1 to} Y ¹⁰ each independently represent a hydrogen atom or a weight average molecular weight of 15 to 20,000,
It is preferably a monovalent organic residue of 20 to 10000, and the same organic residues as described in the description of R ¹ can be mentioned. When the Michael addition type urethane urea resin uses the unsaturated compound (d) as a raw material, it is an organic residue derived from the unsaturated compound (d).

As the unsaturated compound having the above structural formula, for example, the formula (3) is a (meth) acrylic unsaturated compound,
Formula (4) is an amide unsaturated compound, Formula (5) is a fatty acid vinyl unsaturated compound, Formula (6) is a vinyl ether unsaturated compound, Formula (7) is an α-olefin unsaturated compound, Formula (8) Is an allyl unsaturated compound, formula (9) is an allyl acetate unsaturated compound, formula (10) is a vinyl cyanide unsaturated compound, formula (11) is a styrene or vinylbenzene unsaturated compound, and formula (12) Represents an alicyclic olefinic unsaturated compound, respectively.

The type of the unsaturated compound (d) to be used can be arbitrarily selected according to the purpose of the modification, but is preferably selected by focusing on the functional group of the unsaturated compound (d). Examples of the functional group of the unsaturated compound (d) 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,
Epoxy groups, further amide groups and dialkylamino groups,
Examples include nitrogen-containing groups such as quaternary ammonium bases.

More specifically, examples of the (meth) acrylic alkyl group-containing unsaturated compound 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 (meth) acrylate, icosyl (meth) acrylate, henycosyl (meth) acrylate, docosyl (meth) acrylate, etc. There are alkyl (meth) acrylate prime 1-22, preferably 2 to 10 carbon atoms in the case for the purpose of adjusting the polarity, even more preferably 2 carbon atoms
Alkyl group-containing acrylates having ~ 8 alkyl groups or the corresponding methacrylates. When the purpose is to adjust the leveling property, the number of carbon atoms is preferably 6 or more. When the number of carbon atoms is 23 or more, the Michael addition reaction hardly proceeds, although it depends on the purpose.

As the fatty acid vinyl-based unsaturated compound containing an alkyl group, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate,
Examples thereof include vinyl laurate, vinyl palmitate, and vinyl stearate.

Examples of the vinyl ether-based unsaturated compound containing an alkyl group include butyl vinyl ether and ethyl vinyl ether.

Further, as the α-olefin-based unsaturated compound containing an alkyl group, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
-Hexadecene and the like.

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, and 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 can be mentioned.

The unsaturated compounds having a polyalkylene glycol group and having an alkoxy group at the terminal include 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-pentaxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate,
Ethoxy polyethylene glycol (meth) acrylate and the like.

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

For the purpose of improving the affinity with other components, it is preferable to use an unsaturated compound (d) having a polyalkylene glycol group, which is a repeating unit of preferably 2 to 25, more preferably 4 to 22. preferable.

The combined use of an alkyl group-containing unsaturated compound and a polyalkylene glycol group-containing unsaturated compound is preferable when a Michael addition type urethane urea resin is used for the purpose of improving the affinity with other components. The weight ratio is preferably from 1:99 to 50:50, and more preferably from 5:95 to 20:80.

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

Other hydroxyl group-containing unsaturated compounds include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Examples include hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 1-ethynyl-1-cyclohexanol, and allyl alcohol.

Examples of the nitrogen-containing unsaturated compound include an amide group-containing unsaturated compound, a dialkylamino group-containing unsaturated compound, and a quaternary ammonium base-containing unsaturated compound.

Examples of the amide group-containing unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide,
Monoalkylol (meth) acrylamide such as -propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N -Methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxymethyl -N-propoxymethyl methacrylamide, 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-
Examples include dialkylol (meth) acrylamide such as methoxymethyl-N- (pentoxymethyl) methacrylamide.

Examples of the dialkylamino group-containing unsaturated compound include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene and the like.

[0074] Further, obtained by allowed to quaternary ammonium of the dialkylamino group-containing unsaturated compound, Cl as counterion ^-, Br -, I ^- halogen ion or QSO 3 such _- ^(Q:. 1 to carbon atoms As a quaternary ammonium base-containing unsaturated compound having a (12 alkyl group),
(Meth) acrylic acid dimethylaminoethylmethyl chloride salt, trimethyl-3- (1- (meth) acrylamido-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride and Trimethyl-3-
(1- (meth) acrylamide-1,1-dimethylethyl) ammonium chloride and the like.

Examples of the perfluoroalkyl group-containing unsaturated compound 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, per Carbon such as fluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, and perfluorooctylundecyl (meth) acrylate Perfluoroalkyl (meth) acrylates having 1 to 20 perfluoroalkyl groups; perfluoroalkyl such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and perfluoroalkylenes Examples thereof include an alkyl group-containing unsaturated compound.

Examples of the unsaturated compound having an alkoxysilyl group include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof. it can.

Further, glycidyl acrylate, 3,4-
Examples thereof include unsaturated compounds containing an epoxy group such as epoxycyclohexyl acrylate.

As other unsaturated compounds, vinyl compounds include allyl compounds such as allyl acetate, allylbenzene, allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-
Methylstyrene, 2-methylstyrene, chlorostyrene and the like can be mentioned.

Examples of the ethynyl compound include acetylene, ethynylbenzene, ethynyltoluene and the like.

The unsaturated compound (d) may be used alone or
Two or more types can be used in combination.

Polyamine (c) and unsaturated compound (d)
In the Michael addition reaction, 1 mol of active hydrogen of the amino group of the polyamine (c) reacts with 1 mol of the unsaturated group of the unsaturated compound (d). Since the polyamine (c) easily adds Michael to a vinyl group or an ethynyl group of a compound having an electron-withdrawing group, a (meth) acrylic compound, particularly an acrylate compound, is preferred as the compound (d).
In addition, comparing the acrylate compound with the corresponding methacrylate compound, the acrylate compound is preferred because it has a higher efficiency of the Michael addition reaction.

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

In the production method of obtaining the Michael addition type urethane urea resin after previously synthesizing the amino compound (B), the unsaturated compound (d) to be added to the polyamine (c)
Depends on the purpose of using the amine compound (B).

For use in the ureation reaction, one mole of the primary amino group of the polyamine (c) is added so that at least two primary or secondary amino groups remain in the amine compound (B). Preferably 0.1 to 1.0 mol,
More preferably, the reaction is carried out at a rate of 0.2 to 0.98 mol. If the amount is less than this, it is not preferable because the influence of the side chain is hardly exhibited and the storage stability is low.

On the other hand, an unsaturated compound (d) is added to the polyurethane urea (C) having a primary or secondary amino group at a terminal.
In which Michael is added to produce a Michael addition type urethane urea, the primary or secondary amino group of the polyurethane urea (C) and the unsaturated compound (d)
The ratio of the active hydrogen to the primary or secondary amino group of the polyurethane urea (C) is not particularly limited.
Preferably, the ratio is 0.1 to 1.0 mol, more preferably 0.5 to 0.98 mol, per mol. If it is less than this, the effect of denaturation is unlikely to appear.

Further, an amine compound (B) may be used as a terminal stopper.
The ratio of the unsaturated compound (d) to the polyamine (c) in the synthesis of the compound (B) is such that the amine compound (B) is (the number of moles of active hydrogen of the primary or secondary amino group of the polyamine (c)) − (Mole number of unsaturated compound (d)) =
The reaction is preferably performed at a ratio satisfying 0.9 to 1.2, preferably 0.95 to 1.1. If less than this, there is a high possibility that two or more primary or secondary amino groups remain,
Conversely, even if the amount is small, it is highly possible that the amino group does not remain, and does not serve as a reaction terminator.

The Michael addition type urethane urea resin is a urethane prepolymer (A) having a terminal isocyanate group.
And an amine compound (B) and, if necessary, a polyamine (c) react with each other. Further, the polyurethane urea (C) has a urethane prepolymer (A) having a terminal isocyanate group, a polyamine (c) and The amine compound (B) is reacted as needed, and a monoamine compound can be further reacted as a reaction terminator (f) as needed.

The reaction terminator plays a role in controlling the molecular weight or stabilizing the reaction activity of the resin by reacting with the unreacted remaining isocyanate group at the terminal of the Michael addition type urethane urea resin.

As the reaction terminator (f) used in the present invention, for example, diethylamine, di-n-butylamine,
In addition to dialkylamines such as di-n-octylamine, dicyclohexylamine and diisononylamine, monoethanolamine, diethanolamine and 2-amino-2-
Methyl-1-propanol, tri (hydroxymethyl)
Monoamines having a hydroxyl group such as aminomethane and 2-amino-2-ethyl-1,3-propanediol, alkylhydrazines such as monomethylhydrazine, 1,1-dimethylhydrazine and benzylhydrazine, formhydrazide, acetohydrazide, lauric acid Hydrazides such as hydrazide, monoamino compounds having one side with a tertiary amino group and a primary amino group, such as N, N-dimethyl-1,3-propanediamine, N, N diethyl-1,3-propanediamine;
Monoamine compounds having an alkoxysilyl group such as γ-aminopropyltriethoxysilane can be used. Further, an amine compound (B) having only one primary or secondary amino group can also be used as the reaction terminator (f).

Among the above reaction terminators (f), monoamines having a hydroxyl group, such as 2-amino-2-methyl-propanol, can be used to prepare a Michael addition type urethane urea resin having a hydroxyl group at the end and having excellent storage stability. You can get it. Further, a Michael addition type urethane urea resin having a hydroxyl group at the end is preferable because the hydroxyl group at the end also functions as a cross-linking site when a polyisocyanate-based curing agent is added and cross-linked. In the case of a monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanate group of the Michael addition type urethane urea resin, but the reactivity of the amino group is higher and the reaction with the isocyanate group is preferential. I do.

At the time of synthesizing the urethane prepolymer (A), a known catalyst 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.

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

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

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

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

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

The organometallic compound catalyst used when synthesizing the urethane prepolymer (A) is an amino compound (B)
When it further reacts with, it greatly accelerates the reaction. The reaction between an isocyanato group and an amino group is originally very fast, but in the presence of an organometallic compound catalyst, the reaction may be further accelerated and control may be difficult. At this time, if a chelate compound is present, a chelate is formed with the organometallic compound catalyst, and the reaction with the amine compound (B) is easily controlled by adjusting the catalytic ability.

As the chelating compound, acetylacetone, dimethylglyoxime, oxine, dithizone,
Examples thereof include polyaminooxy acids such as ethylenediaminetetraacetic acid (EDTA), oxycarboxylic acids such as citric acid, and condensed phosphoric acid. Among the chelate compounds, acetylacetone is preferable because it is soluble in an organic solvent, has volatility, and can be easily removed if necessary.

The chelate compound remains in the polyurethane urea resin even after the reaction. When the polyurethane resin of the present invention is used as an adhesive, it is preferable to further add a curing agent.At this time, the chelate compound also adjusts the reaction rate between the polyurethane urea resin and the curing agent, and as a result, Can be provided with an adhesive having excellent storage stability.

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

In the present invention, the urethane-forming reaction for producing the urethane prepolymer (A) can be carried out by various methods, but is roughly classified into the following two methods. 1) a compound (e ′) having a polyol (a), a polyisocyanate (b), and, if necessary, at least one ionic functional group and a group capable of reacting with an isocyanate group, and / or a solvent, and / or Or a method in which a solution comprising a catalyst is entirely charged. 2) A polyol (a) and, if necessary, a compound (e ') having at least one ionic functional group and a group capable of reacting with an isocyanate group, and / or a solvent are charged into a flask, and the polyisocyanate (b ), And optionally adding a catalyst after the dropwise addition. 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. If 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.

The mixing ratio of the polyol (a) to the polyisocyanate (b) was determined by the following formula: the mixing ratio of the polyol (a) and the polyisocyanate (b) was determined as follows: It depends greatly on the application of the resin. In order for the urethane prepolymer to have at least one isocyanate group, one of the functional groups capable of reacting with the isocyanate group of the polyol (a) and the compound (e ′) is required.
It is necessary that the isocyanate group of the polyisocyanate (b) is more than 1 mol, preferably 1.01 to 4.00 mol, more preferably 1.40, per mol.
A range of from ~ 3.00 mol is suitable.

In the present invention, the isocyanate group contained in the urethane prepolymer (A) and the polyisocyanate which are the isocyanate group-containing compounds, the amine compound (B) and the polyamine (c) which are the amino group-containing compounds, and the reaction terminator ( The ureation reaction with a primary or secondary amino group of f) is roughly classified into the following two methods. 1) A method comprising charging a solution comprising an isocyanato group-containing compound into a flask and dropping a solution comprising an amino group-containing compound. 2) A method in which a solution comprising an amino group-containing compound is charged into a flask, and a solution of the compound having an isocyanato group is dropped.

The synthesis is carried out in such a way that the reaction becomes stable. If there is no problem in the reaction, the method 1) which is easy to operate is preferred. The temperature of the urea reaction of the present invention is preferably 100 ° C. or lower. More preferably, it is 70 ° C. or lower. The reaction rate is high even at 70 ° C., and if it cannot be controlled, the temperature is more preferably 50 ° C. or lower. If the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a Michael addition type urethane urea resin having a predetermined molecular weight and structure. When an alcohol solvent is used as a solvent for synthesizing the amino compound (B), the temperature in the reaction system is preferably 50 ° C. or lower, more preferably 40 ° C., when the amino compound (B) is dropped.
It is preferable that the temperature be kept at not more than ° C.

The mixing ratio of the urethane prepolymer (A) and the amino compound (B) is not particularly limited and may be arbitrarily selected depending on the application and the required performance. Usually, the isocyanate group 1 in the isocyanate group-containing compound is used. When the number of moles of the functional group of the amino group in the amino group-containing compound relative to the mole is an isocyanato group excess system, preferably 0.70 to 0.97,
It is more preferably 0.8 to 0.96, and preferably 1.001 to 1.40, more preferably 1.01 to 1.2 for an amino group excess system. Outside this range, the molecular weight does not reach a predetermined value, which is not preferable.

The amount of the reaction terminator depends on whether it is mixed with the amine compound (B) or the polyamine (c) or when it is added last alone. The amount is preferably 0.5 mol or less, more preferably 0.3 mol or less with respect to 1 mol of isocyanato group, and when it is added alone at the end, it is preferably with respect to 1 mol of finally present isocyanato group. 0.5 to 3.0 moles, and particularly preferably 1 to 3.0 moles for the purpose of stabilizing the resin.

Outside of this range, adverse effects such as deterioration of film formability and discoloration are observed.

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

The Michael addition type urethane urea resin having a carboxyl group or a tertiary amino group can be ionized for the purpose of dispersing or dissolving in water or for enhancing the ink fixing property.

The anionization of the Michael addition type urethane urea resin having a carboxyl is carried out mainly for dispersing or dissolving in water. The carboxyl group neutralization reaction as a means of anionization may be performed before, simultaneously with, or after the addition of the Michael addition type urethane urea resin to water. As the basic compound used for neutralizing the carboxyl group, ammonia,
Monoethylamine, diethylamine, trimethylamine, triisopropylamine, tributylamine, triethanolamine, methyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1- Examples thereof include organic amines such as propanol, and inorganic alkalis such as sodium hydroxide and potassium hydroxide. These are used alone or in combination of two or more. Among them, those which are water-soluble and have high volatility which are easily dissociated by heat are preferable, and ammonia, trimethylamine and triethylamine are particularly preferable.

Further, 1) a polyol (e) containing at least one ionic functional group, 2) an unsaturated compound (d), 3) a Michael addition type urethane having a tertiary amino group introduced by a reaction terminator. The cationization of urea is
It is carried out for the purpose of dispersing or dissolving in water by acid neutralization and for enhancing the fixability of the aqueous ink.

Examples of the acidic compound used for neutralizing or quaternizing a tertiary amino group as a means for cationization include inorganic acid compounds such as phosphoric acid and hydrochloric acid, and acetic acid, succinic acid, dimethyl sulfate and diethyl sulfate. Organic acid compounds such as alkylsulfuric acid, benzyl chloride, methyl chloride, ethyl chloride, butyl chloride, propyl chloride, ethyl bromide, butyl bromide, butyl iodide and α-chloroparaxylene.

The known quaternizing agents used for quaternization include the above-mentioned organic acid compounds. These quaternizing agents are usually used alone or as a mixture of two or more.
The quaternization reaction can be performed by a conventionally known method, and is completed in a nitrogen atmosphere at 60 to 100 ° C. for 1 to 6 hours after the addition of the quaternizing agent.

The molecular weight of the Michael addition type urethane urea resin is not particularly limited and is preferably limited to 1,000 to 20,000 as a weight average molecular weight in terms of standard polystyrene by GPC. More preferably, it is 5,000 to 150,000. Further, the number average molecular weight is preferably 1,000 to 150,0.
More preferably, it is 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.

The solution viscosity of the obtained Michael-added urethane urea is not particularly limited and is selected depending on the application of the resin. Preferably, the solid content is 50 to 100% and the solid content is 100 to 10,000.
mPa · s (25 ° C.), and more preferably 1000 to 5000 mPa · s at 50% by weight solids when used as an adhesive.
(25 ° C.), and if the viscosity is too high, coating processing may be difficult. If the viscosity is too low, a resin having a sufficient molecular weight may not be formed.

In the Michael addition type urethane urea resin according to the present invention, if necessary, the above-mentioned polyisocyanate can be used as a curing agent. Further, if necessary, another resin such as an acrylic resin, a polyester resin, an amino resin, an epoxy resin, or a polyurethane resin can be used in combination. Further, additives such as organic / inorganic pigments, fillers, colorants, ultraviolet absorbers, antioxidants, defoamers, and light stabilizers may be added according to the application.

The Michael addition type urethane urea resin according to the present invention includes paints, ink binders, overcoat varnishes, surface treatment agents for recording materials, antistatic agents, antifogging agents,
Suitable for coating materials such as various functional surface treatment agents such as water-repellent and oil-repellent treatment agents, interface treatment materials such as adhesives and adhesives, fine particle dispersants such as organic and inorganic pigments, and compatibilizers. You.

[0119]

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

The following shows a synthesis example.

Synthesis Example 1 Isophorone diamine (IPD) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
A) 300 g of toluene and 300 g of toluene were charged, and 176 g of ethyl acrylate (EA) and 184 g of 2-hydroxyethyl acrylate were added dropwise at room temperature. After dropping, at 80 ° C
After reacting for 1 hour, a compound obtained by adding 360 g of toluene is referred to as compound (1). FIG. 1 shows a 13 C-NMR chart of the obtained compound (1), and a chemical formula showing its assignment is shown below.

[0122]

Embedded image

Synthesis Example 2 Isophorone diamine (IPD) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
A) 300 g of toluene and 300 g of toluene were charged, and 226 g of n-butyl acrylate and 229 g of 4-hydroxybutyl acrylate were added dropwise at room temperature. After completion of dropping, at 80 ° C 1
After reacting for an hour, a mixture obtained by adding 455 g of toluene is referred to as compound (2). The NMR chart of the obtained compound (2) is shown in FIG.
The chemical formula showing the assignment is shown below.

[0124]

Embedded image

Synthesis Example 3 Isophorone diamine (IPD) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
A) 300 g and 300 g of toluene were charged, and 176 g of ethyl acrylate and 229 g of 4-hydroxybutyl acrylate were added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and the resultant was added with 405 g of toluene to obtain a compound (3). FIG. 3 shows an NMR chart of the obtained compound (3).
The chemical formula showing the assignment is shown below.

[0126]

Embedded image

Synthesis Examples 4 to 8 Compounds (4) to (8) were synthesized with the compositions shown in Table 1 in the same manner as in Synthesis Example 1.

[0128]

[Table 1]

[0129]

In Table 1, 2-HEA is 2-hydroxyethyl acrylate, EA is ethyl acrylate,
HBA is 4-hydroxybutyl acrylate, n-BA
Is n-butyl acrylate, 2-EHA is 2-ethylhexyl acrylate, IPDI is isophorone diisocyanate, TMHMDA is ED is ethylenediamine, H
MDA indicates hexamethylenediamine.

Synthesis Example 9 Ethylenediamine (ED) 60 was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
g of methanol and 60 g of methanol (MeOH), and 232 g of 2-hydroxyethyl acrylate was added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 50 ° C. for 1 hour, and 232 g of MeOH was added to obtain compound (9). NM of compound (9) obtained
The R chart is shown in FIG. 4, and the chemical formula showing the assignment is shown below.

[0132]

Embedded image

Synthesis Example 10 Hexamethylenediamine (HM) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
DA) 116 g and MeOH 116 g were charged, and EA 190 g was added dropwise at room temperature. After the completion of the dropwise addition, the reaction was carried out at 50 ° C. for 1 hour, and 190 g of MeOH was added to obtain compound (10). FIG. 5 shows an NMR chart of the obtained compound (10), and a chemical formula showing the assignment is shown below.

[0134]

Embedded image

Synthesis Example 11 170 g of IPDA and 170 g of MeOH were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
And 190 g of EA was added dropwise at room temperature. After dropping, 5
After reacting at 0 ° C. for 1 hour, 190 g of MeOH was added to obtain compound (11). FIG. 6 shows an NMR chart of the obtained compound (11), and a chemical formula showing the assignment is shown below.

[0136]

Embedded image

Synthesis Example 12 170 g of IPDA and 85 g of MeOH were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
Was added, and 179 g of dimethylaminoethyl methyl chloride acrylate was added dropwise at room temperature. After dropping, 3 at 50 ° C
After reacting for an hour, 179 g of MeOH was added to obtain compound (12). FIG. 7 shows an NMR chart of the obtained compound (12).
The chemical formula showing the assignment is shown below.

[0138]

Embedded image

Synthesis Example 13 170 g of IPDA and 170 g of isopropyl alcohol (IPA) were charged into a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, and 252 g of dimethylaminoethyl methyl chloride acrylate. And 4-
72 g of hydroxybutyl acrylate was added dropwise at room temperature.
After the completion of the dropwise addition, the mixture was reacted at 50 ° C. for 2 hours, and to which 324 g of IPA was added was designated Compound (13). The resulting compound (1
FIG. 8 shows the NMR chart of 3), and the chemical formula showing the assignment is shown below.

[0140]

Embedded image

Synthesis Example 14 170 g of IPDA and 170 g of IPA were charged into a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, and 232 g of dimethylaminoethyl methyl chloride acrylate and polyethylene glycol (average). (Degree of polymerization = 4.5) 170 g of acrylate was added dropwise at room temperature. After the completion of the dropwise addition, the reaction was carried out at 50 ° C. for 3 hours, and the compound to which 402 g of IPA was added was designated as compound (14). Of the obtained compound (14)
The NMR chart is shown in FIG. 9, and the chemical formula showing the assignment is shown below.

[0142]

Embedded image

Synthesis Examples 15 to 21 Compounds (1) having the compositions shown in Table 1 were prepared in the same manner as in Synthesis Example 1.
5) to (21) were synthesized. Example 1 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., 43 g of isophorone diisocyanate (IPDI: manufactured by Huls Japan KK), 75 g of toluene, and 0.05 g of dibutyltin dilaurate as a catalyst were gradually heated to 100 ° C. and reacted for 2 hours. Was done. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate was added.
After adding 0.9 g of acetylacetone, compound (4) 61
It was added dropwise g in 1 hour, after aging for 1 hour, 2-amino-2-methyl - added propanol (Nagase & Co., Ltd.) 2.1 g, NCO characteristic absorption of IR chart (2270 cm ^-1) is After confirming the disappearance, the reaction was terminated. The reaction solution was colorless and transparent, the solid content was 50% by weight, the viscosity was 2800 mPa · s, the number average molecular weight was MN25,000,
The weight average molecular weight was MW 90,000.

Example 2 A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer and a dropping funnel was charged with polyether polyol PP-.
2000 (bifunctional polyether polyol, OH value 5
6, Sanyo Chemical Industry Co., Ltd.) 257 g, isophorone diisocyanate (IPDI) 43 g, toluene 75 g,
0.025 g of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate and 0.9 g of acetylacetone were added, and 53 g of compound (2) was added dropwise for 1 hour. 2.0 g of amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.)
After confirming that the NCO characteristic absorption (2270 cm ^-1 ) in the chart had disappeared, the reaction was terminated. The reaction solution was colorless and transparent, the solid content was 50% by weight, the viscosity was 3800 mPa · s, the number average molecular weight was MN27,000, and the weight average molecular weight was MW110.
000. FIG. 10 shows an IR chart of the obtained Michael addition type urethane urea.

Example 3 A polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, Sanyo Chemical Industry Co., Ltd.) 257 g, isophorone diisocyanate (IPDI) 43 g, toluene 75 g,
0.025 g of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate and 0.9 g of acetylacetone were added, and 52 g of compound (3) was added dropwise for 1 hour. 2.0 g of amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.)
After confirming that the NCO characteristic absorption (2270 cm ^-1 ) in the chart had disappeared, the reaction was terminated. The reaction solution was colorless and transparent, the solid content was 50% by weight, the viscosity was 3800 mPa · s, the number average molecular weight was MN27,000, and the weight average molecular weight was MW110.
000. FIG. 11 shows an IR chart of the obtained Michael addition type urethane urea.

Example 4 A polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.025 g as a catalyst.
A time reaction was performed. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate and 0.9 g of acetylacetone were added, 50 g of the compound (1) was added dropwise for 1 hour, and the mixture was aged for 1 hour. -Amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.)
After adding 2.2 g, the NCO characteristic absorption of the IR chart (22
After confirming that 70 cm ^-1 ) had disappeared, the reaction was terminated. This reaction solution was colorless and transparent, had a solid content of 50% by weight, a viscosity of 4000 mPa · s, a number average molecular weight MN of 30,000 and a weight average molecular weight of MW 100,000. FIG. 12 shows an IR chart of the obtained Michael addition type urethane urea.

Example 5 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate and 0.9 g of acetylacetone were added, and 48 g of the compound (8) was added dropwise over 1 hour. -Amino-2
-Methyl-propanol (manufactured by Nagase & Co., Ltd.) 2.0
g was added to terminate the reaction. This reaction solution was colorless and transparent, had a solid content of 50% by weight, a viscosity of 3,500 mPa · s, a number average molecular weight MN of 28,000, and a weight average molecular weight of MW 110,00.
It was 0.

Example 6 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 129 g of polyester polyol P-2010 (bifunctional polyester polyol, OH value 56, manufactured by Kuraray Co., Ltd.) 128 g, isophorone diisocyanate (manufactured by Huls Japan Co., Ltd.) 4
3 g, 75 g of toluene, 0.03 g of dibutyltin dilaurate as a catalyst, and 0.02 g of tin 2-ethylhexanoate were charged, and the temperature was gradually raised to 100 ° C., and the reaction was carried out for 2 hours.
After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate and 0.9 g of acetylacetone were obtained.
Was added, 50 g of the compound (1) was added dropwise over 1 hour, and the mixture was aged for 1 hour. Then, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to terminate the reaction. . The reaction solution was colorless and transparent, the solid content was 50% by weight, the viscosity was 5000 mPa · s, and the number average molecular weight was MN 25.0.
The weight average molecular weight was MW 90,000.

Example 7 A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was charged with polyether polyol PP-.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of hexamethylene diisocyanate, 64 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and 100 g of
The temperature was gradually raised to ℃, and the reaction was carried out for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate and 0.9 g of acetylacetone were added.
50 g of the compound (1) was added dropwise over 1 hour, and after aging for 1 hour, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to terminate the reaction.
The reaction solution was colorless and transparent, the solid content was 50% by weight, and the viscosity was 40%.
The number average molecular weight was MN 30,000 and the weight average molecular weight MW was 1100,000.

Example 8 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, Sanyo Chemical Industries, Ltd.) 257 g, 4,4′-diphenylmethane diisocyanate 44 g, toluene 76
g, 0.05 g of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours.
After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate and 0.9 g of acetylacetone were obtained.
Was added, 50 g of the compound (1) was added dropwise over 1 hour, and the mixture was aged for 1 hour. Then, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to terminate the reaction. . The reaction solution was colorless and transparent, the solid content was 50% by weight, the viscosity was 4000 mPa · s, and the number average molecular weight was MN26.0.
The weight average molecular weight was MW 85,000.

Example 9 A polyethylene glycol (Mw) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
= 2000)) 223.5 g, polytetraethylene glycol (Mw = 3000) 5.5 g, dimethylolbutanoic acid 30 g isophorone diisocyanate 126.2 g, methyl ethyl ketone 3
25 g, dibutyltin dilaurate 0.093 g as catalyst
, And the temperature was gradually raised to 85 ° C. to carry out a reaction for 3.5 hours. After confirming the remaining amount of isocyanate group by titration, 30 ° C
After adding 360 g of IPA, compound (12) 258
g was added dropwise in 30 minutes, and after further reacting at 50 ° C. for 1 hour, 4.0 g of DBA was added, and NCO of the IR chart was added.
After confirming that the characteristic absorption (2270 cm ^-1 ) had disappeared, the reaction was terminated. This reaction solution is slightly cloudy, but water 18
Addition of 0 g results in a clear solution. The obtained Michael addition type urethane urea resin solution has a solid content of 33% by weight and a viscosity of 20%.
The number average molecular weight MN was 10,000 and the weight average molecular weight MW was 18,000. The IR chart of the obtained Michael addition type urethane urea is shown in FIG. 13, the 1 H-NMR chart is shown in FIG. 16, and the chemical formula showing the assignment is shown below.

[0152]

Embedded image

Example 10 Stirrer, reflux condenser, nitrogen inlet, thermometer, dropping funnel
Polyethylene glycol (Mw) in a four-necked flask equipped with
= 2000)) 47.5 g, polytetraethylene glycol (M
w = 3000) 1.1 g, dimethylolbutanoic acid 6.3 g isophoro
Diisocyanate 26.7 g, methyl ethyl ketone 55 g,
0.02 g of dibutyltin dilaurate was charged as a catalyst
Then, the temperature was gradually raised to 85 ° C., and the reaction was carried out for 3.5 hours.
After confirming the remaining amount of isocyanate group by titration, cool to 30 ° C.
After adding 110 g of IPA, 24.5 g of compound (13) was added.
4.4 g of IPDA was dropped in 30 minutes, and the temperature was further increased to 50 ° C. for 1 hour.
After the reaction, 1.0 g of DBA was added and the IR chart
NCO characteristic absorption (2270cm^{- 1}) Has disappeared
After confirmation, the reaction was completed. The obtained Michael addition type urethane
The solution of the urea resin is colorless and transparent, and has a solid content of 35% by weight.
%, Viscosity 2000 mPa · s, number average molecular weight MN 12,000
0, weight average molecular weight MW 20,000. Obtained
Fig. 1 shows the IR chart of the Michael addition type urethane urea.
FIG. 4 shows the 1H-NMR chart in FIG. Symbol of the attribution
Is the same as in the ninth embodiment.

Example 11 A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel was charged with polyethylene glycol (Mw).
= 2000)) 46.5 g, polytetraethylene glycol (M
w = 3000) 1.1 g, dimethylolbutanoic acid 6.2 g isophorone diisocyanate 26.3 g, methyl ethyl ketone 70 g,
0.02 g of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 85 ° C. to carry out a reaction for 3.5 hours.
After confirming the remaining amount of isocyanate group by titration, the mixture was cooled to 30 ° C., 105 g of IPA was added, and 29 g of compound (14) and I
4.4 g of PDA was added dropwise in 30 minutes, and after further reacting at 50 ° C. for 1 hour, 1.0 g of DBA was added to confirm that the NCO characteristic absorption (2270 cm ⁻¹ ) of the IR chart had disappeared. finished. The solution of the obtained Michael addition type urethane urea resin is colorless and transparent, and has a solid content of 37% by weight.
The viscosity was 2,200 mPa · s, the number average molecular weight was MN 12,800, and the weight average molecular weight was MW 22,500. FIG. 15 shows an IR chart of the obtained Michael addition type urethane urea.
FIG. 18 shows the 1H-NMR chart. The symbols of the attributions are the same as in Example 9.

Example 12 A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel was charged with polyether polyol PP-.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate and 0.9 g of acetylacetone were added, 37 g of compound (18) was added dropwise over 1 hour, and the mixture was aged for 1 hour. -Amino-2
-Methyl-propanol (manufactured by Nagase & Co., Ltd.) 2.1
g was added to terminate the reaction. This reaction solution was colorless and transparent, had a solid content of 50% by weight, a viscosity of 3,500 mPa · s, a number average molecular weight MN of 27,000, and a weight average molecular weight of MW 95,000.
Met.

Example 13 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate and 0.9 g of acetylacetone were added, and 50 g of compound (19) was added.
After dropping for 2 hours and aging for 1 hour, 2-amino-
1. 2-methyl-propanol (manufactured by Nagase & Co., Ltd.)
The reaction was terminated by adding 2 g. This reaction solution was colorless and transparent, had a solid content of 50% by weight, a viscosity of 3000 mPa · s, a number average molecular weight MN of 27,000 and a weight average molecular weight of MW 94,00.
It was 0.

Example 14 A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was charged with polyether polyol PP-.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate and 0.9 g of acetylacetone were added, and 56 g of the compound (20) was added.
After dropping for 2 hours and aging for 1 hour, 2-amino-
1. 2-methyl-propanol (manufactured by Nagase & Co., Ltd.)
The reaction was terminated by adding 0 g. This reaction solution was colorless and transparent, had a solid content of 50% by weight, a viscosity of 2500 mPa · s, a number average molecular weight MN of 27,000, and a weight average molecular weight of MW 96,000.
It was 0.

Example 15 A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel was charged with polyether polyol PP-.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, 75 g of toluene and 0.05 g of dibutyltin dilaurate as a catalyst were gradually heated to 100 ° C. and reacted for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate and 0.9 g of acetylacetone were added, and 35 g of compound (21) was added.
After dropping for 2 hours and aging for 1 hour, 2-amino-
1. 2-methyl-propanol (manufactured by Nagase & Co., Ltd.)
The reaction was terminated by adding 0 g. This reaction solution was colorless and transparent, had a solid content of 50% by weight, a viscosity of 2500 mPa · s, a number average molecular weight MN of 29,000 and a weight average molecular weight of MW 100,0.
00.

Example 16 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 129 g of polyester polyol P-2010 (bifunctional polyester polyol, OH value 56, manufactured by Kuraray Co., Ltd.) 128 g, isophorone diisocyanate (manufactured by Huls Japan KK)
43 g, toluene 75 g, dibutyltin dilaurate 0.03 g as a catalyst, tin 2-ethylhexanoate 0.02 g
, And the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours. After confirming the remaining amount of the isocyanato group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate and 0.1 ml of acetylacetone were added.
After adding 9 g, 37 g of the compound (18) was added dropwise over 1 hour, and after aging for 1 hour, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to terminate the reaction. did. The reaction solution is colorless and transparent and has a solid content of 5
0% by weight, viscosity 3500 mPa · s, number average molecular weight MN2
4,000, weight average molecular weight MW 90,000.

Example 17 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of hexamethylene diisocyanate, 64 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and 100 g of
The temperature was gradually raised to ℃, and the reaction was carried out for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate and 0.9 g of acetylacetone were added.
35 g of the compound (18) was added dropwise over 1 hour, and after aging for 1 hour, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to terminate the reaction.
This reaction solution was colorless and transparent, had a solid content of 50% by weight, and had a viscosity of 30%.
The number average molecular weight was MN 25,000, and the weight average molecular weight MW was 98,000.

Example 18 Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, Sanyo Chemical Industries, Ltd.) 257 g, 4,4′-diphenylmethane diisocyanate 44 g, toluene 76
g, 0.05 g of dibutyltin dilaurate was charged as a catalyst, and the temperature was gradually raised to 100 ° C. to carry out a reaction for 2 hours.
After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 227 g of ethyl acetate and 0.9 g of acetylacetone were obtained.
Was added, 37 g of the compound (18) was added dropwise over 1 hour, and after aging for 1 hour, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) was added to terminate the reaction. . The reaction solution was colorless and transparent, the solid content was 50% by weight, the viscosity was 3000 mPa · s, and the number average molecular weight was MN23.0.
The weight average molecular weight was MW 83,000.

Example 19 A 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel was charged with polyethylene glycol (Mw).
= 2000) 50.9 g, polytetraethylene glycol (Mw
= 3000) 1.25 g, dimethylolbutanoic acid 6.8 g, isophorone diisocyanate 28.8 g, methyl ethyl ketone 70
g, 0.02 g of dibutyltin dilaurate as a catalyst, and gradually heated to 85 ° C., and reacted for 3.5 hours. After confirming the remaining amount of isocyanate group by titration, the mixture was cooled to 30 ° C., 80 g of IPA was added, and 12.3 g of IPDA was added.
After dropping in 0 minutes and further reacting at 50 ° C. for 1 hour, IR
After confirming that the NCO characteristic absorption (2270 cm -1) of the chart has disappeared, 4.1 g of acrylate (polyethylene glycol (average degree of polymerization = 4.5)) was further added at 50 ° C.
For 2 hours. The solution of the obtained Michael addition type urethane urea resin is colorless and transparent, and has a solid content of 35% by weight.
The viscosity was 2000 mPa · s, the number average molecular weight was MN 12,000, and the weight average molecular weight was MW 25,000.

Reference Example 2 g of the curing agent (C) was added to 100 g of the Michael addition type urethane urea resin (B) solution synthesized in Examples 1 to 4, and the adhesive strength, holding power, tack,
A removability test was performed. As the curing agent (C), a hexamethylene diisocyanate trimethylolpropane adduct 75% by weight ethyl acetate solution was used.

The test method is as follows.

<Coating Method> The above-mentioned Michael addition type urethane urea resin solution was dried on a release paper with an applicator using a dry coating film 25.
It was coated to a thickness of μm and dried at 100 ° 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 Michael addition type urethane urea resin solution to release paper was transferred to a polyethylene terephthalate film (25 μm thick).
23 on 0.4mm thick stainless steel plate (SUS304)
At 65 ° C. and 65% RH, roll-bonded according to JIS, and after 20 minutes, peel strength (1) with a shopper type peel tester.
80 degree peel, pulling speed 300mm / min; unit g /
(25 mm width).

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

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

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

Table 2 shows the test results.

[0171]

[Table 2]

[0172]

According to the invention of the Michael addition type urethane urea resin and the method for producing the same according to the present invention, it has become possible to easily and effectively control the physical properties of the urethane urea resin while fully utilizing the characteristics of the urethane urea resin. . As a result, for example, by using the resin of the present invention as a pressure-sensitive adhesive, it has become possible to develop pressure-sensitive adhesive properties in a medium pressure-sensitive region, which has been difficult with conventional urethane resins and acrylic resins.

[Brief description of the drawings]

FIG. 1 13C-NMR of the amino compound obtained in Synthesis Example (1)
chart

FIG. 2 1H-NMR of the amino compound obtained in Synthesis Example (2)
chart

FIG. 3 1H-NMR of the amino compound obtained in Synthesis Example (3)
chart

FIG. 4 1H-NMR of the amino compound obtained in Synthesis Example (9)
chart

FIG. 5 1H-NMR of the amino compound obtained in Synthesis Example (10)
chart

FIG. 6 shows 1H-NMR of the amino compound obtained in Synthesis Example (11).
chart

FIG. 7 shows 1H-NMR of the amino compound obtained in Synthesis Example (12).
chart

FIG. 8 shows 1H-NMR of the amino compound obtained in Synthesis Example (13).
chart

FIG. 9 shows 1H-NMR of the amino compound obtained in Synthesis Example (14).
chart

FIG. 10 is an IR chart of the Michael addition type urethane urea resin obtained in Example (2).

FIG. 11 is an IR chart of the Michael addition type urethane urea resin obtained in Example (3).

FIG. 12 is an IR chart of the Michael addition type urethane urea resin obtained in Example (4).

FIG. 13 is an IR chart of the Michael addition type urethane urea resin obtained in Example (9).

FIG. 14 is an IR chart of the Michael addition type urethane urea resin obtained in Example (10).

FIG. 15 is an IR chart of the Michael addition type urethane urea resin obtained in Example (11).

FIG. 16 is a 1H-NMR chart of the Michael addition type urethane urea resin obtained in Example (9).

FIG. 17 is a 1H-NMR chart of a Michael addition type urethane urea resin obtained in Example (10).

FIG. 18 is a 1H-NMR chart of a Michael addition type urethane urea resin obtained in Example (11).

Continued on the front page (72) Inventor Yukifumi Mashimo 2-3-13-1 Kyobashi, Chuo-ku, Tokyo Inside Toyo Ink Manufacturing Co., Ltd. (72) Inventor Miki Kawashima 2-3-1-13 Kyobashi, Chuo-ku, Tokyo Toyo Inki F-term (Reference) in Manufacturing Co., Ltd. (Reference) HC71 LA13 RA07 RA08 RA17

Claims (5)

[Claims] Claims 1. A raw material containing a polyol (a), a polyisocyanate (b), a polyamine (c), and an unsaturated compound (d), and having the following formula (1-1) or (1-
A Michael addition type urethane urea resin having a binding site represented by 2). Embedded image (Wherein R ³ is a monovalent organic residue derived from the unsaturated compound (d),
X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ⁴ represents a hydrogen atom, a monovalent organic residue derived from the polyamine (c), or a monovalent organic residue derived from the unsaturated compound (d); . ) 2. A polyamine (c) and an unsaturated compound (d) are mixed with a urethane prepolymer (A) having a terminal isocyanate group obtained by reacting a polyol (a) with a polyisocyanate (b). A Michael addition type urethane urea resin obtained by reacting an amino compound (B) obtained by an addition reaction. 3. A reaction product obtained by reacting a polyol (a), a polyisocyanate (b) and a polyamine (c),
A Michael addition type urethane urea resin obtained by subjecting a polyurethane urea (C) having a primary or secondary amino group at a terminal to a Michael addition reaction of an unsaturated compound (d). 4. A step (a) of reacting a polyol (a) with a polyisocyanate (b) to form a urethane prepolymer (A), wherein a polyamine (c) and an unsaturated compound (d) are subjected to a Michael addition reaction to produce an amino compound. A method for producing a Michael-added urethane urea resin, comprising a step b for producing (B) and a step c for reacting the urethane prepolymer (A) with the amino compound (B) to produce a Michael-added urethane urea resin. 5. A step d of reacting a polyol (a), a polyisocyanate (b) and a polyamine (c) to form a polyurethane urea (C) having a primary or secondary amino group at a terminal, and the polyurethane urea A process for producing a Michael addition type urethane urea resin, comprising a step e of subjecting the unsaturated compound (d) to a Michael addition reaction with (C).