JP2016138177A - Resin composition for joining laminated sheets - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for joining laminated sheets, more particularly, a solvent-free resin composition for joining laminated sheets, which can develop adhesion performance equal to or higher than that of a conventional composition by aging for a shorter time compared to the prior art without rigorously controlling ambient humidity, and which has a long pot life and high workability.SOLUTION: The resin composition for joining a laminated sheet comprises a polyisocyanate component (A), a polyol component (B), and a compound (F) containing a urea group and has the following characteristics (1) and (2). (1) The composition contains the compound (F) having a urea group in an amount of 1 to 60 pts.wt. with respect to the whole amount of the resin composition for joining laminate sheets. (2) The compound (F) is obtained by allowing an amino compound (C), prepared by Michael addition reaction of a polyamine compound (c) and a compound (d) having an unsaturated double bond, to react with a diisocyanate compound (e).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for joining a two-component laminate sheet of a polyisocyanate component and a polyol component (hereinafter also referred to as a joining resin composition) and a laminate using the same. The present invention relates to a laminated sheet joining resin composition useful as a packaging material for medical products, cosmetics and the like, a laminate using the same, and a packaging material.

  Bonding between various plastic films and bonding between plastic film and metal vapor deposition film or metal foil has good properties such as adhesion after curing reaction and rubber elasticity. A polyurethane-based bonding resin composition using a reaction is often used.

  As the polyurethane-based bonding resin composition, a solvent type and a solventless type have been proposed. Since the solvent-type bonding resin composition generally has a high initial adhesiveness, when the two adhering materials are brought into close contact with each other through the bonding resin composition, the adhesion between the two adhering materials is hardly lowered. . However, when a solvent-type bonding resin composition is used, the solvent is volatilized in the bonding step, which causes a problem from the viewpoint of working environment or safety. In addition, there is a problem that a solvent may remain in a product after bonding, which may give a consumer discomfort due to a bad odor.

  For this reason, the request | requirement of the removal of organic solvent becomes strong, and research of solvent-free is actively performed. Since the solvent-free polyurethane-based bonding resin composition generally has low initial tackiness, the bonding resin composition can be cured even when both adherends are brought into close contact with each other via this bonding resin composition. Before the reaction proceeded, there was a case where floating occurred and the adhesion between the two adherent materials was insufficient. Therefore, during the curing reaction of the bonding resin composition, it must be pressure-bonded (clamped) so that the adhesion between the two adherend materials is not sufficient, and the bonding work cannot be performed reasonably. was there.

For example, Patent Document 1 discloses a solventless laminated sheet bonding resin composition containing a polyol component (1) and a polyisocyanate component (2) composed of two types of polyisocyanate compounds.
Further, Patent Document 2 contains a polyol component (1) and a polyisocyanate component (2) essential for a trifunctional polyisocyanate compound, the branching point concentration is in a specific range, and hydroxyl group: isocyanate group = 1. : A solvent-free laminated sheet bonding resin composition of 1: 1 to 1: 3 is disclosed.
Patent Document 3 discloses a solvent-free laminated sheet bonding resin composition containing a polyol component (A) and an isocyanate component (B) essentially containing isophorone diisocyanate.
Patent Document 4 discloses a solventless laminated sheet bonding resin composition containing a polyol component (A), a polyisocyanate compound (B), and a powder (C) having a specific particle size.
Further, Patent Document 5 discloses a laminated sheet-bonding resin composition containing a polyisocyanate component (a) and a polyol component (b), wherein the polyisocyanate component (a) is a monomer-based 4,4 ′ methylene. A resin composition for bonding laminated sheets comprising diphenyl diisocyanate (i) and an isocyanate functional prepolymer (ii) is disclosed.

As a method of obtaining a laminate using the resin composition for bonding laminated sheets, after applying the bonding resin composition to the substrate (target of adhesion), another substrate is applied to the formed bonding resin composition layer. In general, a method of advancing the curing reaction of the bonding resin composition layer sandwiched between both base materials in a state where the (adhesion target) is superposed is common. The process of “promoting the curing reaction of the bonding resin composition layer” is referred to as an aging process.
In the inventions described in Patent Documents 1 to 4, specifically, an alicyclic polyisocyanate component or an aliphatic polyisocyanate component is essential as a polyisocyanate component. Since the reaction of the alicyclic polyisocyanate component and the aliphatic polyisocyanate component is relatively mild, the aging process requires 2 to 5 days at 40 to 50 ° C.
Accordingly, there has been a demand for providing a resin composition for joining laminated sheets that can exhibit the same or better adhesive performance by aging in a shorter time than before.

Compared with the alicyclic polyisocyanate component and the aliphatic polyisocyanate component, the aromatic polyisocyanate component is rich in reactivity, and therefore, it does not meet the problem of shortening the aging time.
Therefore, there has been a demand for providing a resin composition for joining laminated sheets that can exhibit the same or better adhesive performance by aging in a shorter time than before without strictly controlling the environmental humidity to a low humidity.

The invention described in Patent Document 5 discloses that the polyol component (b) is preferably composed only of triol (paragraph numbers 0052 and 0054). However, since triol is richer in reactivity than the diol component, after mixing the polyol component and the polyisocyanate component, the viscosity becomes extremely large in a short time, that is, the pot for the resin composition for laminating sheet bonding. There was a problem of shortening life. In particular, in the case of a solvent-free laminated sheet bonding resin composition, an increase in viscosity in a short time has a great influence on coating properties and productivity, which is a big problem from an industrial viewpoint.

JP-A-8-60131 JP 2003-96428 A JP 2006-57089 A JP 2011-162579 A JP 2012-131980 A

  The problem to be solved by the present invention against the technical background of the prior art described above is that the environmental humidity is strictly controlled with respect to the resin composition for bonding laminated sheets, in particular, the solvent-free resin composition for bonding laminated sheets. At least, it is a laminated sheet bonding resin composition capable of expressing equal or better adhesive performance by aging in a shorter time than before, and is to provide a bonding resin composition having a long pot life and high workability. .

  The present invention has been made in view of the above problems, and includes a polyisocyanate component (A), a polyol component (B), and a resin composition for bonding laminated sheets containing a compound (F) containing a urea group. The inventors have found that the above-mentioned goal can be achieved, and have completed the present invention.

That is, the present invention includes a laminated sheet bonding resin comprising the polyisocyanate component (A), the polyol component (B), and the compound (F) containing a urea group, and characterized by the following (1) and (2): Relates to the composition.
(1) The compound (F) containing a urea group is contained in an amount of 1 to 60 parts by weight with respect to the total amount of the laminated sheet bonding resin composition.
(2) The compound (F) is obtained by reacting an amino compound (C) obtained by Michael addition reaction of a polyamine compound (c) and a compound (d) having an unsaturated double bond with a diisocyanate compound (e). Is a compound.

  Further, in the present invention, the above-mentioned laminated sheet bonding is characterized in that the equivalent ratio of the isocyanate group to the hydroxyl group (isocyanate group / hydroxyl group) in the resin composition for bonding laminated sheets is 0.5 to 2.5. The present invention relates to a resin composition.

In the present invention, the polyisocyanate component (A)
An isocyanate group in the aromatic polyisocyanate (a1);
It is polyisocyanate (A2) obtained by reacting a hydroxyl group in polyether polyol (a2-1) and / or polyester polyol (a2-2) with an isocyanato group-excess condition. The present invention relates to a resin composition.

  The present invention also relates to the above resin composition for joining laminated sheets, wherein the resin composition for joining laminated sheets contains substantially no organic solvent.

  Moreover, this invention relates to the laminated body formed by laminating | stacking at least 2 sheet-like base material using the said resin composition for laminated sheet joining.

  Moreover, this invention relates to the packaging material which uses the said laminated body.

In addition, the present invention includes a step 1 in which the resin composition for bonding laminated sheets is applied to the first sheet-like substrate to form a resin layer;
Step 2 of superimposing a second sheet-like substrate on the resin layer;
The present invention relates to a method for producing a laminate comprising the step 3 of curing the resin layer.

  By using the resin composition for joining laminated sheets of the present invention, it is possible to provide a laminated sheet that can exhibit adhesive performance equal to or higher than that of conventional products with short-time aging, and can be produced stably with high productivity. . In addition, since it is a resin composition for bonding laminated sheets with excellent adhesion after curing reaction, it is possible to bond various plastic films used as packaging materials, or to paste plastic films and metal vapor deposition films or metal foils. Even when combined, good adhesion performance can be obtained without causing appearance defects.

  Hereinafter, preferred embodiments of the present invention will be described.

  The polyisocyanate component (A) of the present invention will be described.

  A conventionally well-known thing can be used as a polyisocyanate component (A), for example, aromatic polyisocyanate (a1), aliphatic polyisocyanate, aliphatic polyisocyanate which has an aromatic ring, alicyclic polyisocyanate, etc. Is mentioned. Further, the following specific compounds obtained by modifying the polyisocyanate with a polyol or water may be used in combination of two or more.

  As aromatic polyisocyanate (a1), 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-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.

  Aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2, Examples include 4,4-trimethylhexamethylene diisocyanate.

  Examples of the aliphatic polyisocyanate having an aromatic ring include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4- Examples thereof include diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

  As alicyclic polyisocyanate, isophorone diisocyanate, 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 (isocyanatemethyl) cyclohexane and the like.

  Further, a trimethylolpropane adduct of the above polyisocyanate, a trimer having an isocyanurate ring, or the like can also be used. Polyphenylmethane polyisocyanate (also known as PAPI), naphthylene diisocyanate, and polyisocyanate-modified products thereof can also be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used.

  As for the reactivity of the polyisocyanate, the aromatic polyisocyanate (a1) has a higher reaction rate than the aliphatic polyisocyanate, and the aromatic polyisocyanate (a1) is used for the purpose of completing aging in a short time. It is preferable to use it.

  In the present invention, the polyisocyanate component (A) comprises a polyisocyanate and a polyol, an isocyanate group in the polyisocyanate, and a hydroxyl group in the polyol because of the viscosity of the bonding resin composition and the ease of adjusting the adhesiveness. More preferably, it is a polyisocyanate obtained by reacting under conditions where the isocyanato group is excessive.

  As the polyol to be reacted with the isocyanate group in the polyisocyanate, known polyols can be used, such as polyether polyol (a2-1), polyester polyol (a2-2), polycarbonate polyol, copolymers thereof, and other glycols. Can be mentioned. The specific compounds described below may be used in combination of two or more.

As the polyether polyol (a2-1), a known polyether polyol can be used. For example, polymers, copolymers, and graft copolymers of alkylene oxides such as propylene oxide, tetrahydrofuran, ethylene oxide, butylene oxide;
Those having two or more hydroxyl groups, such as hexanediol, methylhexanediol, heptanediol, octanediol, or polyether polyols obtained by condensation of a mixture thereof, can be used.
Furthermore, glycols obtained by adding alkylene oxides such as ethylene oxide to bisphenols such as bisphenol A and bisphenol F can be used.

  A known polyester polyol can be used as the polyester polyol (a2-2). Examples of the polyester polyol include a polyester polyol obtained by condensation reaction of a polyfunctional alcohol component and a dibasic acid component.

  Examples of the polyfunctional alcohol component include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3 ′. -Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexane Examples include compounds having two hydroxyl groups such as diol, cyclohexanediol, bisphenol A, and bisphenol F, and three or more hydroxyl groups such as glycerin, trimethylolpropane, and pentaerythritol. The compound which has is mentioned.

  Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.

  Β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, α-methyl-β-propiolactone, etc. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones can also be used.

  Among these, since compatibility and viscosity adjustment are easy, it is preferable to use polyether polyol (a2-1) and / or polyester polyol (a2-2).

  Therefore, the polyisocyanate in the present invention is composed of the isocyanate group in the aromatic polyisocyanate (a1), the polyether polyol (a2-1) and / or the viscosity of the bonding resin composition and the ease of adjusting the adhesiveness. Or the polyisocyanate (A2) formed by making it react with the hydroxyl group in polyester polyol (a2-2) on the isosocyanate group excess conditions is preferable.

  Equivalent ratio (isocyanate group / hydroxyl group) between the isocyanate group in the aromatic isocyanate and the hydroxyl group in the polyether polyol (a2-1) and / or the polyester polyol (a2-2) in preparing the polyisocyanate (A2) Is preferably in the range of 2.0 to 5.0. If it is less than 2.0, the polyisocyanate (A) has a high molecular weight and high viscosity, and the coating performance may deteriorate. If it exceeds 5.0, a large amount of isocyanate that does not react with the polyol remains. The pot life may be reduced.

Next, the polyol component (B) will be described.
The polyol component (B) is used by appropriately mixing a polyol having a hydroxyl group at the terminal.
Known components can be used as the polyol component (B), and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, copolymers thereof, and other glycols. The specific compounds described below may be used in combination of two or more.

  As the polyether polyol, the polyether polyol shown in the above (a2-1) can be used, and the polyester polyol shown in the above (a2-2) can also be used for the polyester polyol.

The polycarbonate polyol has a structure represented by the following general formula (1) in its molecule, and a known polycarbonate polyol can be used.
General formula (1):
− [— O—Z ¹ —O—CO—] _m —
(In the formula, Z ¹ represents a divalent aliphatic or aromatic organic residue having 1 to 12 carbon atoms, and m represents an integer of 1 or more.)

  The polycarbonate polyol can be obtained, for example, by (1) a reaction between glycol or bisphenol and a carbonate ester, or (2) a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

  Specific examples of the carbonic acid ester used in the production method (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

  Examples of the glycol or bisphenol used in the production methods (1) and (2) 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; Bisphenols such as Sphenol A and bisphenol F; Bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenols; and the like can also be used. These compounds can be used as one kind or a mixture of two or more kinds.

  Other glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, butylene glycol, 2-methyl-1,3-propanediol, 3-methyl-1, 5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, Examples include compounds having two hydroxyl groups per molecule, such as octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, dimer acid diol, hydrogenated dimer diol, and cyclohexanedimethanol. .

  Furthermore, compounds having three or more hydroxyl groups per molecule, such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, and methylglucoside can also be used as the polyol (B).

  As the polyol component (B), compatibility is good by using the polyether polyol (a2-1) and / or polyester polyol (a2-2) used in the polyisocyanate (A), Since the viscosity adjustment is easy, polyether polyol (a2-1) and polyester polyol (a2-2) are preferably used.

  Among the polyols described above, it is preferable to use a polyol having a primary hydroxyl group. As shown in the document “Polyurethane Resin Handbook (Nikkan Kogyo Shimbun Co., Ltd. (published in 1987))”, it is a well-known fact that primary hydroxyl groups have a higher reaction rate than water and secondary hydroxyl groups, It is possible to increase the reaction rate with isocyanate and to obtain a laminated sheet-bonding resin composition having excellent curing reactivity. In addition, it has faster curing reactivity than water and efficiently enhances the cohesive strength of the resin composition for laminating sheet bonding, so that the growth of bubbles derived from the decarboxylation reaction generated by the reaction between isocyanate and water is increased. It can also be suppressed by the cohesive strength of the composition.

  Next, the compound (F) containing a urea group will be described.

  In the present invention, the compound (F) containing a urea group includes an amino compound (C) obtained by Michael addition of a polyamine compound (c) and a compound (d) having an unsaturated double bond, and a diisocyanate compound (e ), And the cohesive strength of the laminated sheet bonding resin composition and the affinity with the substrate are adjusted by the high cohesive force due to the urea group and the side chain alkyl group generated by the Michael addition process. It becomes easy to do and can improve adhesive physical property greatly.

  The amount of the urea group-containing compound (F) used is preferably 1 to 60% by weight, more preferably 2 to 50% by weight, and more preferably 2.5 to 30% in the laminated sheet bonding resin composition. Most preferably, the content is% by weight. If the amount is less than 1% by weight, the effect of improving the cohesive strength may not be obtained and a high adhesive strength may not be obtained. If the amount is 60% by weight or more, the viscosity is high due to the hydrogen bonding of the urea group, and the coating Sexuality may worsen.

  Compound (F) is produced by a urealation reaction between the obtained amino compound (C) and the isocyanate compound (e). The ratio of the amino group in the amino compound (C) to the isocyanate group of the isocyanate compound, By using a hydroxyl group-containing compound as a raw material for the polyamine compound, the isocyanate terminal or the hydroxyl terminal can be freely selected. Moreover, it becomes possible to mix and use with a polyol compound (B) by setting it as an isocyanate terminal and making a polyisocyanate component (A) and a hydroxyl group terminal.

  Moreover, it is preferable that the compound (F) containing a urea group reacts with the polyisocyanate component (A) or the polyol component (B). When the reaction is not performed, the compatibility with the cured resin composition for bonding laminated sheets is reduced, and the appearance of coating may be deteriorated or the adhesive force may be reduced. Therefore, it reacts with the compound (F1) having an isocyanate group terminal capable of reacting with the polyol component (B) and the polyisocyanate component (A) through the steps shown in the following reaction process formulas (1) and (2). The compatibility can be improved by using the compound (F2) having a possible hydroxyl terminal. Each method will be described in detail.

<Compound having an isocyanate group terminal (F1)>
The isocyanate group-terminated compound (F1) is prepared by making the isocyanate group contained in the diisocyanate compound (e) excessive with respect to the primary and secondary amino groups contained in the amino compound (C). can do. The equivalent ratio of isocyanate group / amino group is preferably 1.3-2. If it is less than 1.3, the compound (F1) may have a high molecular weight, resulting in high viscosity and low coatability. If it is 2 or more, the unreacted diisocyanate compound (e) remains, Pot life may be reduced.

本発明におけるＸ¹は、ポリアミン化合物（ｃ）と、不飽和二重結合を有する化合物（ｄ）との反応残基であり、Ｙ¹はアミノ化合物（Ｃ）とジイソシアネート化合物（ｅ）との反応残基である。


The example of the reaction process of the compound (F1) which has an isocyanate group terminal is shown below.
(Reaction process formula (1))

X ¹ in the present invention is a reaction residue between the polyamine compound (c) and the compound (d) having an unsaturated double bond, and Y ¹ is a reaction between the amino compound (C) and the diisocyanate compound (e). Residue.

<Compound having a hydroxyl terminal (F2)>
In order to prepare the hydroxyl-terminated compound (F2), a method of reacting an isocyanate group and a polyol in the isocyanate group-containing compound (F1) produced in the above reaction process formula 1 under an excessive amount of hydroxyl groups, ,
As shown in the reaction process formula (2) to be described later, one or more polyamine compounds (c) having one or more hydroxyl groups and one or more compounds obtained by reacting the compound (d) having an unsaturated double bond are reacted. Using the amino compound (C) having a hydroxyl group, the equivalent ratio of isocyanate group / amino group is 0.8 to 1.2, and the hydroxyl group is allowed to remain.

本発明におけるＸ²は、一つ以上の水酸基を有するポリアミン化合物（ｃ）と、不飽和二重結合を有する化合物（ｄ）との反応残基であり、Ｙ²は水酸基を有するアミノ化合物（Ｃ）とジイソシアネート化合物（ｅ）との反応残基である。 The reaction process example of the compound (F2) having a hydroxyl terminal is shown below.
(Reaction process formula (2))

X ² in the present invention is a reaction residue between a polyamine compound (c) having one or more hydroxyl groups and a compound (d) having an unsaturated double bond, and Y ² is an amino compound having a hydroxyl group (C ) And the diisocyanate compound (e).

Next, the amino compound (C) will be described.
The amino compound (C) used in the present invention is a compound having at least one primary or secondary amino group, and Michael addition is performed between the polyamine (c) and the compound (d) having an unsaturated double bond. It is possible to synthesize.

The polyamine (c) can be arbitrarily selected from known ones, and specific examples thereof include:
For example, monoamines having hydroxyl groups such as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl-1,3-propanediol, such as ethylenediamine , Trimethylenediamine, 1,2-propanediamine, 3- (methylamino) propylamine, tetramethylenediamine, pentamethylenediamine, neopentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, hepta Methylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, diethylenetriamine, N3-amine (3- (2-aminoethyl) amino Propylamine), dipropylenetriamine, N, N-bis- (3-aminopropyl) methylamine, triethylenetetramine, N4-amine (N, N′-bis (3-aminopropyl) ethylenediamine), hydrazine, piperazine, Aliphatic polyamines such as N- (2-aminoethyl) piperazine, isophoronediamine, 4,4′-diaminodicyclohexylmethane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, trans-1,4-diamino Cyclohexane, cis-1,2-diaminocyclohexane, 3- (cyclohexylamino) propylamine, 1,3-bis (aminomethyl) cyclohexane, 1,8-diamino-p-menthane, bicyclo [2.2.1] heptane Alicyclic polyamines such as dimethanamine, and phenyle Diamine, tolylene diamine, xylylene diamine, and aromatic polyamines such as 4,4'-diaminodiphenylmethane. Furthermore, 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine , (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine, diamines having a hydroxyl group in the molecule such as aminoethylethanolamine, and dimer amine obtained by converting the carboxyl group of dimer acid to an amino group, A polyoxyalkylene glycol diamine having propoxyamine at both ends and represented by the following formula (1) 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 (1)
(In formula (1), n represents an arbitrary integer of 2 to 4, and m represents an arbitrary integer of 2 to 50.)

Among these polyamines, polyamines having one or more primary amino groups are particularly preferred from the viewpoint of high reactivity of the Michael addition reaction and reaction control of the amino compound (C) produced after the Michael addition reaction with isocyanate. .
Furthermore, ethanolamine, which is a polyamine having one or more primary amino groups and having a hydroxyl group, and 2-amino-2-methyl-1-propanol are particularly preferable because of easy viscosity control.

  As the compound (d) having an unsaturated double bond, any compound having at least one functional group containing an unsaturated double bond that can be Michael-added with the polyamine (c) can be used without particular limitation. More specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, ( Sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, (meth) acrylate n -Hexyl, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n (meth) acrylate Nonyl, (meth) acrylic iso-nonyl, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid (meth) acrylic acid alkyl esters such as iso-stearyl and behenyl (meth) acrylate;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate Benzyl (meth) acrylate, iso-bonyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, (Meth) acrylic acid 2-oxo-1,2-diphenylethyl, (meth) acrylic acid 1- Naphthyl, 2-naphthyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, (meth ) 9-anthrylmethyl acrylate, 2-methyladamantyl-2-yl (meth) acrylate, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyladamantyl-2 (meth) acrylate -Yl, (meth) acrylic acid 2-isopropyladamantyl-2-yl, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl, (meth) acrylic acid 1- (adamantan-1-yl ) -1-ethylethyl, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylpropyl, (meth) acrylic acid -(Adamantan-1-yl) -1-ethylpropyl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.03,7] non-2-yl, (meth) acrylic Acid-5-oxo-4-oxa-tricyclo [5.2.1.03,8] dec-2-yl, dihydro-α-terpinyl (meth) acrylate, (meth) acrylic acid-6-oxo-7 (Meth) acrylic such as oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl Acid cyclic esters;

For example, 5-vinylbicyclo [2.2.1] hept-2-ene, 2,5-bis (allyloxy) norbornane, 5-vinyl-2,3-oxirane norbornane, 2- (2-propenyl) bicyclo [2 2.1] heptane, 5-vinylbicyclo [2.2.1] hept-2-ene, 2-ethenylideneadamantane, 3-allyladamantan-1-ol, 1-allyladamantane-containing cyclic Compounds;

For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meta) 2- (ethoxycarbonyloxy) butyl crylate, 2- (ethoxycarbonyloxy) hexyl (meth) acrylate, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) (meth) acrylate ) Ethyl, 2- (butoxycarbonyloxy) ethyl (meth) acrylate, 2- (butoxycarbonyloxy) butyl (meth) acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, (meth) acrylic Aliphatic (meth) acrylic acid esters having one carbonyl group such as 2- (octyloxycarbonyloxy) butyl acid;

For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylic acid 2-oxobutanoyloctyl, (meth) acrylic acid 2-oxobutanoyldecyl, (meth) acrylic acid 2-oxobutanoyldodecyl, (meth) acrylic acid 3-oxobutanoylethyl, ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylate (Meth) acrylic acid 4-cyanooxobutanoylethyl, (meth) acrylic acid 4-cyanooxobutanoylpropyl, (meth) acrylic acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoyl Ruhexyl, 4-cyanooxobutanoyloctyl (meth) acrylate, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, ( Aliphatic (meth) acrylic acid esters having two carbonyl groups such as 2,3-di (oxobutanoyl) hexyl (meth) acrylate and 2,3-di (oxobutanoyl) octyl (meth) acrylate Kind;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.03,7] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl- 5-oxo-4-oxa-tricyclo [5.2.1.03,8] non-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3.2 .1] having a carbonyl group such as octa-2-yl, (meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl (meth) Acrylic acid cyclic esters;

For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

For example, vinyl acetoacetate, vinyl acetopropionate, vinyl acetoisobutyrate, vinyl acetobutyrate, vinyl acetovalerate, vinyl acetohexanoate, vinyl aceto-2-ethylhexanoate, vinyl aceto-n-octanoate, vinyl acetodecanoate, acetodecane Vinyl acid, vinyl acetooctadecanoate, vinyl acetopivalate, vinyl acetocaprate, vinyl acetocrotonate, vinyl acetosorbate, vinyl propanoyl acetate, vinyl butyryl acetate, vinyl isobutyryl acetate, vinyl palmitoyl acetate, vinyl stearoyl acetate, vinyl pyroyl acetate , Vinyl propanoyl valerate, vinyl butyryl valerate, vinyl isobutyryl valerate, palmitoyl vinyl valerate, stearoyl valerate, pyrvoyl Vinyl Rerin acid, 2-acetoacetoxyethyl vinyl ether, 2-acetoacetoxyethyl butyl vinyl ether, 2-acetoacetoxyethyl hexyl vinyl ether, aliphatic vinyl compounds of having an acyl group such as 2-acetoacetoxyethyl octyl vinyl ether;

For example, vinyl benzoylformate, vinyl benzoyl acetate, vinyl benzoylpropionate, vinyl benzoylbutyrate, vinyl benzoylvalerate, vinyl benzoylhexanoate, vinyl benzoyldodecanoate, 1-naphthoylvinyl acetate, 1-naphthoylpropionate, 1- Naphthoyl vinyl butyrate, 1-naphthoyl vinyl valerate, 1-naphtho vinyl hexanoate, 2-naphtho vinyl acetate, 2-naphtho vinyl propionate, 2-naphtho vinyl butyrate, 2-naphtho vinyl butyrate, 2- Vinyl naphthoyl hexanoate, vinyl nicotinoyl acetate, vinyl nicotinoyl propionate, vinyl nicotinoyl butyrate, vinyl nicotinoyl valerate, vinyl nicotinoyl hexanoate, vinyl nicotinoyl decanoate, nicotine Vinyl dodecanoate, vinyl isonicotinoyl acetate, vinyl isonicotinoyl propionate, vinyl isonicotinoyl butyrate, vinyl isonicotinoyl valerate, vinyl isonicotinoyl hexanoate, vinyl isonicotinoyl decanoate, vinyl isonicotinoyl dodecanoate, 2-furoyl Vinyl acetate, vinyl 2-furoylpropionate, vinyl 2-furoylbutyrate, vinyl 2-furoylvalerate, vinyl 2-furoylhexanoate, vinyl 2-furoyldecanoate, vinyl 2-furoyldodecanoate, 3-furoyl Vinyl acetate, vinyl 3-furoylpropionate, vinyl 3-furoylbutyrate, vinyl 3-furoylvalerate, vinyl 3-furoylhexanoate, vinyl 3-furoyldecanoate, vinyl 3-furoyldodecanoate, vinyl anthraniloyl acetate , Vinyl anthraniloyl propionate, vinyl anthraniloyl butyrate, vinyl anthraniloyl valerate, vinyl anthraniloyl hexanoate, vinyl anthraniloyl decanoate, vinyl anthraniloyl decanoate, 4- (2-t-ethoxycarbonylethyl) Aromatic vinyl compounds having an acyl group, such as oxy) styrene, 4- (2-t-butoxycarbonylethyloxy) styrene, 4- (2-t-butoxycarbonylpropyloxy) styrene;

For example, acetoacetic acid (meth) allyl, acetopropionic acid (meth) allyl, acetoisobutyric acid (meth) allyl, acetobutyric acid (meth) allyl, acetovaleric acid (meth) allyl, acetohexanoic acid (meth) allyl, aceto-2- Ethylhexanoic acid (meth) allyl, aceto-n-octanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetodecanoic acid (meth) allyl, acetooctadecanoic acid (meth) allyl, acetopivalic acid (meth) allyl, acetocaprin Acid (meth) allyl, acetocrotonic acid (meth) allyl, acetosorbic acid (meth) allyl, propanoyl acetate (meth) allyl, butyryl acetate (meth) allyl, isobutyryl acetate (meth) allyl, palmitoyl acetate (meth) allyl, Stearoyl acetate (meth) allyl, (meth) allyl Aliphatic (meth) allyl compounds having an acyl group such as hydrin;

For example, benzoyl formate (meth) allyl, benzoyl acetate (meth) allyl, benzoylpropionate (meth) allyl, benzoylbutyrate (meth) allyl, benzoylvalerate (meth) allyl, benzoylhexanoic acid (meth) allyl, benzoyldodecanoic acid (Meth) allyl, 1-naphthoylacetic acid (meth) allyl, 1-naphthoylpropionic acid (meth) allyl, 1-naphthoylbutyric acid (meth) allyl, 1-naphthoylvaleric acid (meth) allyl, 1-naphthoylhexane Acid (meth) allyl, 2-naphthoylacetic acid (meth) allyl, 2-naphthoylpropionic acid (meth) allyl, 2-naphthoylbutyric acid (meth) allyl, 2-naphthoylvaleric acid (meth) allyl, 2-naphthoyl Aromatic (meth) allyl having an acyl group such as hexanoic acid (meth) allyl Ethylenically unsaturated monomers of the carbonyl group-containing compound, and the like;

For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, (meth ) Acrylic acid dimer, maleic acid, fumaric acid, monomethyl maleic acid, monomethyl fumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, Angelic acid, senetic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (Meth) acryloyloxyethyl succine Or repeating a polylactone-based (meth) acrylic acid ester having a carboxyl group at the terminal by ring-opening addition of a lactone ring such as mono (meth) acrylic acid ω-carboxypolycaprolactone ester or alkylene oxide such as ethylene oxide or propylene oxide Carboxyl group-containing aliphatic α, β-unsaturated double bond group-containing carboxylic acids such as esters of alkylene oxide addition-type succinic acid and (meth) acrylic acid having a carboxyl group at the terminal, and acid anhydrides thereof Kind;

For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, Carboxylic acids such as cinnamic acid, 7-amino-3-vinyl-3-cephem-4-carboxylic acid and the like, and carboxylic acids containing alicyclic and aromatic rings containing aromatic groups and aromatic rings, and acid anhydrides thereof Kind;

For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxy (meth) acrylate Butyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy (meth) acrylate Octyl, (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxylauryl, (meth) acrylic acid ethyl-α- (hydroxymethyl), monofunctional (meth) acrylic acid glycerol, or (meth) acrylic Acid glycidyl laurate, (meth) acrylic Fatty acid ester (meth) acrylate such as glycidyl oleate, glycidyl stearate (meth) acrylate, or polylactone (meth) acrylate having a hydroxyl group at the end by ring-opening addition of lactone ring, or ethylene Hydroxyl group-containing aliphatic (meth) acrylic acid such as alkylene oxide addition system (meth) acrylic acid ester having a hydroxyl group at the terminal after repeated addition of alkylene oxide such as oxide and propylene oxide, and (meth) acrylic acid 2-hydroxyethyl phosphate Esters;

For example, (meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid cyclohexyl glycidyl ether, (Meth) acrylic acid phenylglycidyl ether, (meth) acrylic acid 2-hydroxy-3-phenoxymethyl, (meth) acrylic acid 2-hydroxy-3-phenoxyethyl, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl , 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxy (meth) acrylate Ethyl phthalate, (me ) 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2- Hydroxyl-containing alicyclic or aromatic (meth) acrylic acid esters such as hydroxypropyl) benzene;

For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy- 3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotri Hydroxyl-containing benzotriazole-based (meth) acrylic acid esters such as azoles;

For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl group-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy 4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxy Ethoxy}]-S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-hydroxyl group such as S-triazine Containing triazine-based (meth) acrylic acid esters;

For example, glucose ring system (meth) acrylate esters such as glycosyl methyl (meth) acrylate, glycosyl ethyl (meth) acrylate, glycosyl propyl (meth) acrylate, glycosyl butyl (meth) acrylate;

For example, repeated addition of hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyoctyl vinyl ether, hydroxydecyl vinyl ether, hydroxydodecyl vinyl ether, hydroxyoctadecyl vinyl ether, glyceryl vinyl ether, or alkylene oxide such as ethylene oxide or propylene oxide Hydroxyl group-containing aliphatic vinyl ethers such as alkylene oxide addition vinyl ethers having a hydroxyl group at the terminal end;

For example, 1,2-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 2-hydroxy-3-phenoxymethyl monovinyl ether, 2-hydroxy-3-phenoxy Ethyl monovinyl ether, 2-hydroxy-3-phenoxypropyl monovinyl ether, 2-hydroxy-3-phenoxybutyl monovinyl ether, 2-hydroxy-3-phenoxydecyl monovinyl ether, 2-hydroxy-3-phenoxyoctadecyl monovinyl ether, 2- Vinyl ethers having a hydroxyl group-containing alicyclic or aromatic ring such as (4-benzoyl-3-hydroxyphenoxy) ethyl monovinyl ether;

For example, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 2-methyl-3- Hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4, Hydroxyl group-containing aromatic vinyl compounds such as 6-trihydroxystyrene and 2-hydroxy-6-vinylnaphthalene;

For example, (meth) allyl alcohol, isopropenyl alcohol, dimethyl (meth) allyl alcohol, hydroxyethyl (meth) allyl ether, hydroxypropyl (meth) allyl ether, hydroxybutyl (meth) allyl ether, hydroxyhexyl (meth) allyl ether , Hydroxyoctyl (meth) allyl ether, hydroxydecyl (meth) allyl ether, hydroxydodecyl (meth) allyl ether, hydroxyoctadecyl (meth) allyl ether, glyceryl (meth) allyl ether, or alkylene oxides such as ethylene oxide and propylene oxide Hydroxyl group-containing aliphatic (meth) allyl alcohols such as alkylene oxide addition system (meth) allyl ether having a hydroxyl group at the terminal of repeating addition of Or (meth) allyl ethers;

For example, 1,2-cyclohexanedimethanol mono (meth) allyl ether, 1,3-cyclohexanedimethanol mono (meth) allyl ether, 1,4-cyclohexanedimethanol mono (meth) allyl ether, o- (meth) allyl Phenol, m- (meth) allylphenol, p- (meth) allylphenol, 2-hydroxy-3-phenoxymethyl mono (meth) allyl ether, 2-hydroxy-3-phenoxyethyl mono (meth) allyl ether, 2- Hydroxy-3-phenoxypropyl mono (meth) allyl ether, 2-hydroxy-3-phenoxybutyl mono (meth) allyl ether, 2-hydroxy-3-phenoxydecyl mono (meth) allyl ether, 2-hydroxy-3-phenoxy Octadecyl mono (meth) allyl Ether, 2- (4-benzoyl-3-hydroxyphenoxy) Echirumono (meth) having an alicyclic or aromatic ring of the hydroxyl group-containing and allyl ether (meth) allyl ethers;

For example, α, β-unsaturated compounds having a plurality of hydroxyl groups such as propenediol, butenediol, heptenediol, octenediol, glycerol di (meth) acrylate, o-di (meth) allylbisphenol A;

For example, hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. Of (meth) acrylamides;

For example, other monomers having a hydroxyl group and an alkenyl group such as vinyl alcohol;

For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, (meth) acrylic acid 2-chloro-2-propenyl, (meth) acrylic acid 3-chloro-2-propenyl, (meth) acrylic acid-o-2-propenylphenyl, (meth) acrylic acid 2- (2 -Propenyloxy) ethyl, 2- (propenyl lactyl (meth) acrylate, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7 -Further containing unsaturated groups such as dimethylocta-2,6-dien-1-yl, rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate, etc. (Meth) acrylic acid esters;

For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate , (Meth) acrylic propenoic acid 2-perf Orodeshiruechiru, (meth) (meth) acrylic acid perfluoroalkyl esters such as 2-perfluoro-hexadecyl acrylate;

For example, N-methylaminoethyl (meth) acrylate, N-tributylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, ( (Meth) acrylic acid N, N-diethylaminomethyl, (meth) acrylic acid pentamethylpiperidinyl, (meth) acrylic propenoic acid tetramethylpiperidinyl, 2,4-diamino-6,2-methylpropenoyloxyethyl- amino group-containing (meth) acrylic acid esters such as s-triazine;

For example, glycidyl (meth) acrylate, (meth) acrylic (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid (3-methyl-3-oxetanyl) methyl, (meth) acrylic acid tetrahydrofurfuryl, (meta ) Acrylic acid-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-4-ethyl-2-oxotetrahydropyran- 4-yl, (meth) acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2,2-dimethyl -5-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-5-oxotetra Drofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-4,4-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5, 5-dimethyl-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl, (meth) acrylic acid-5-oxotetrahydrofuran-2-ylmethyl, (meth) acrylic acid-3 Oxygen-containing heterocycle-containing (meth) acrylic acid esters such as 1,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl and (meth) acrylic acid-4,4-dimethyl-5-oxotetrahydrofuran-2-ylmethyl;

For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyldipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrime Kishishiran, 3- (meth) acryloyloxy propyl triethoxysilane, 3- (meth) acryloyl alkoxysilyl group-containing (meth) acrylic acid esters such as propyl tripropoxysilane;

For example, sulfomethyl (meth) acrylate, 2-sulfoethyl (meth) acrylate, 2-sulfopropyl (meth) acrylate, 3-sulfopropyl (meth) acrylate, 2-sulfobutyl (meth) acrylate, (meth) 4-sulfobutyl acrylate, 2-sulfobutyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, sulfooctyl (meth) acrylate, sulfodecyl (meth) acrylate, sulfolauryl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters containing a sulfonyl group such as sulfostearyl acrylate;

For example, (meth) acrylic acid cyclic esters containing a sulfonyl group such as (meth) acrylic acid sulfophenoxyethyl, (meth) acrylic acid sulfocyclohexyl, (meth) acrylic acid sulfobenzyl;

For example, (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate, (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) ) Metal salts and ammonium salts of (meth) acrylic acid esters containing sulfonyl groups such as acryloyloxyethyltrimethylammonium-p-toluenesulfonate and (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate;

For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, ( (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, phenyl-2- (meth) acryloyloxyethyl phosphate, (meth) acrylic acid Phosphonic acid group-containing (meth) acrylic acid esters such as acid phosphooxyethylene oxide (ethylene oxide addition moles: 4 to 10) and (meth) acrylic acid acid phosphooxypropylene oxide (propylene oxide addition moles: 4 to 10) Kind;

For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic acid esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalyl hydroxypivalate (commonly called manda) di (meth) acrylate, hydroxypivalyl hydroxypivalyl hydroxypivalate dicaprolactonate, di (meth) acrylic acid 1 , 6- Xanthdiol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol di, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1 , 7-heptanediol, 1,8-octanediol di (meth) acrylate, 1,2-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, di (meth) 1,2-decanediol acrylate, 1,10-decanediol di (meth) acrylate, 1,2-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, di ( 1,2-dodecanediol (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,2-tetradecaneio di (meth) acrylate Di (meth) acrylic acid 1,16-hexadecanediol, di (meth) acrylic acid 1,2-hexadecanediol, di (meth) acrylic acid 2-methyl-2,4-pentanediol, di (meth) acrylic 3-methyl-1,5-pentanediol acid, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-pentane di (meth) acrylate Diol, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethylol di (meth) acrylate Octane, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, di (meth) acrylate 2-methyl-1,8-octanediol diyl, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-di (meth) acrylate Pentanediol, di (meth) acrylic acid 1,2-hexanediol, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1, 7-heptanediol, di (meth) acrylic acid 1,8-octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodeca Diol, di (meth) acrylic acid 1,2-dodecanediol, di (meth) acrylic acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) acrylic acid 1,16 -Hexadecanediol, 1,2-hexadecanediol di (meth) acrylate, 2-methyl-2,4-pentane di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, Di (meth) acrylic acid 2-methyl-2-propyl-1,3-propanediol, di (meth) acrylic acid 2,4-dimethyl-2,4-pentanediol, di (meth) acrylic acid 2,2- Diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, dimethylodi (meth) acrylate Ruoctane, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2-di (meth) acrylate Ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,2-adamantanediol di (meth) acrylate, 1,3 di (meth) acrylic acid -Adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate, di (meta ) Tricyclodecane dihydroxymethyl acrylate, di (meth) acrylate tricyclodecane dihydroxymethyl dicaprolactonate, di Tetraethylene oxide adduct of meth) acrylic acid-2,2-bis (hydroxyphenyl) propane, tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, di (meth) acryl Tetraethylene oxide adduct of acid-4,4'-sulfonyldiphenol, di (meth) acrylic acid-water-added tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) propane, di (meth) acrylic acid- Tetraethylene oxide adduct of water-added 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-2,2-bis (hydroxyphene) Nyl) propane tetraethylene oxide adduct-dicaprolactonate, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) methane tetraethylene oxide adduct-dicaprolactonate, etc. Acrylic esters;

For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, 1,1,1-trishydroxymethylethane tri (meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, Tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone modified tris- (2-acryloyl Oxyethyl) isocyanurate, tri (meth) trifunctional (meth) acrylic acid esters such as acrylic acid and pentaerythritol;

For example, tetra (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid ethoxylated pentaerythritol, tetra (meth) acrylic acid ditrimethylolpropane, hexa (meth) acrylic acid dipentaerythritol, tetra (meth) acrylic acid 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, tetra ( (Meth) acrylic acid di-2,2-dimethylpropane-1,3- All, tetra (meth) acrylate ditrimethylolbutane, tetra (meth) acrylate ditrimethylolhexane, tetra (meth) acrylate ditrimethyloloctane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1, 3-propanediol, hexa (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol , Hepta (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylic acid tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meta ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate Polyfunctional (meth) acrylic acid esters such as real sharp emission oxide;

For example, ethyl vinyl ether, 1-propyl vinyl ether, 2-propyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, iso-butyl vinyl ether, tert-butyl vinyl ether, n-amyl vinyl ether, n-hexyl, 2-ethylhexyl vinyl ether, n -Aliphatic vinyl ethers such as octyl vinyl ether, iso-octyl vinyl ether, n-nonyl vinyl ether, iso-nonyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether;

For example, cyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro 2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H -Vinyl ethers having a cyclic structure such as sodium pyran-2-carboxylate;

For example, fluorine-containing vinyl monomers such as perfluorovinyl, perfluoropropene, perfluoro (propyl vinyl ether), vinylidene fluoride;

For example, (meth) allylchlorosilane, (meth) allyltrimethoxysilane, (meth) allyltriethoxysilane, (meth) allylaminotrimethylsilane, diethoxyethylvinylsilane, trichlorovinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tripropoxy Alkoxysilyl group-containing ethylenically unsaturated monomers such as vinylsilane and vinyltris (2-methoxyethoxy) silane;

For example, alkenyl group-containing sulfonic acids such as vinyl sulfonic acid, 2-propenyl sulfonic acid, 2-methyl-2-propenyl sulfonic acid, and vinyl sulfuric acid;

For example, metal salts and ammonium salts such as ammonium vinyl sulfonate, sodium vinyl sulfonate, potassium vinyl sulfonate, sodium vinyl alkyl sulfosuccinate;
For example, 2-methyl-2-propenyl sulfonate ammonium salt, ammonium 2-methyl-2-propenyl sulfonate, sodium 2-methyl-2-propenyl sulfonate, potassium 2-methyl-2-propenyl sulfonate, and ammonium salts;

For example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t- Butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- ( Aromatic vinyl monomers such as 1-ethoxyethoxy) -α-methylstyrene, 1-butylstyrene, 1-chloro-4-isopropenylbenzene;

For example, vinyl phenyl pentyl ether, vinyl phenyl hexyl ether, vinyl phenyl heptyl ether, vinyl phenyl octyl ether, vinyl phenyl nonyl ether, vinyl phenyl decyl ether, vinyl phenyl undecyl ether, vinyl phenyl dodecyl ether, vinyl phenyl tridecyl ether, vinyl Phenyl tetradecyl ether, vinyl phenyl pentadecyl ether, vinyl phenyl hexadecyl ether, vinyl phenyl heptadecyl ether, vinyl phenyl octadecyl ether, vinyl phenyl nonadecyl ether, vinyl phenyl eicosyl ether, vinyl phenyl henecosyl ether, vinyl phenyl doco Sil ether, vinyl phenyl methyl butyl ether, vinyl phenyl Rupentyl ether, vinyl phenyl methyl hexyl ether, vinyl phenyl methyl heptyl ether, vinyl phenyl methyl octyl ether, vinyl phenyl methyl nonyl ether, vinyl phenyl methyl decyl ether, vinyl phenyl methyl undecyl ether, vinyl phenyl methyl dodecyl ether, vinyl phenyl methyl Tridecyl ether, vinyl phenylmethyl tetradecyl ether, vinyl phenyl methyl pentadecyl ether, vinyl phenyl methyl hexadecyl ether, vinyl phenyl methyl heptadecyl ether, vinyl phenyl methyl octadecyl ether, vinyl phenyl methyl nonadecyl ether, vinyl phenyl methyl eicosyl Ether, vinyl phenyl methyl henecosyl ether, vinyl Aromatic vinyl ether-based monomers having a long-chain alkyl groups such as E methylpropenylmethyl docosyl ether;

For example, isopropenyl phenylmethyl butyl ether, isopropenyl phenyl methyl pentyl ether, isopropenyl phenyl methyl hexyl ether, isopropenyl phenyl methyl heptyl ether, isopropenyl phenyl methyl octyl ether, isopropenyl phenyl methyl nonyl ether, isopropenyl phenyl methyl decyl ether, Isopropenyl phenylmethyl undecyl ether, isopropenyl phenyl methyl dodecyl ether, isopropenyl phenyl methyl tridecyl ether, isopropenyl phenyl methyl tetradecyl ether, isopropenyl phenyl methyl pentadecyl ether, isopropenyl phenyl methyl hexadecyl ether, isopropenyl phenyl Methyl heptadecyl ether, Isopropenyl phenyl having a long chain alkyl group such as isopropenyl phenyl methyl octadecyl ether, isopropenyl phenyl methyl nonadecyl ether, isopropenyl phenyl methyl eicosyl ether, isopropenyl phenyl methyl heneicosyl ether, isopropenyl phenyl methyl docosyl ether Type monomers;

For example, hexyl 4-vinylbenzoate, octyl 4-vinylbenzoate, nonyl 4-vinylbenzoate, decyl 4-vinylbenzoate, dodecyl 4-vinylbenzoate, tetradecyl 4-vinylbenzoate, hexadecyl 4-vinylbenzoate , Octadecyl 4-vinylbenzoate, eicosyl 4-vinylbenzoate, docosyl 4-vinylbenzoate, hexyl 4-isopropenylbenzoate, octyl 4-isopropenylbenzoate, nonyl 4-isopropenylbenzoate, 4-isopropenyl Decyl benzoate, 4-isopropenylbenzoic acid dodecyl, 4-isopropenylbenzoic acid tetradecyl, 4-isopropenylbenzoic acid hexadecyl, 4-isopropenylbenzoic acid octadecyl, 4-isopropenylbenzoic acid eicosyl, 4-isopropenylbenzoic acid Docosil How long vinylbenzoic acid ester having a chain alkyl group or isopropenyl benzoic acid ester monomers;

For example, tetra (ethylene oxide) vinyl phenyl ether, methyl tetra (ethylene oxide) vinyl phenyl ether, ethyl tetra (ethylene oxide) vinyl phenyl ether, propyl tetra (ethylene oxide) vinyl phenyl ether, n-butyl tetra (ethylene oxide) vinyl phenyl ether , N-pentyltetra (ethylene oxide) vinyl phenyl ether, tetra (propylene oxide) vinyl phenyl ether, methyl tetra (propylene oxide) vinyl phenyl ether, ethyl tetra (propylene oxide) vinyl phenyl ether, propoxy tetra (propylene oxide) vinyl phenyl ether N-butyltetra (propylene oxide) vinyl phenyl ether, n Pentaxytetra (propylene oxide) vinyl phenyl ether, poly (ethylene oxide) vinyl phenyl ether, methyl poly (ethylene oxide) vinyl phenyl ether, ethyl poly (ethylene oxide) vinyl phenyl ether, poly (propylene oxide) vinyl phenyl ether, methyl poly (propene Oxide) vinyl phenyl ether, ethyl poly (propylene oxide) ethenyl phenyl ether, poly (ethylene oxide) vinyl benzyl ether, methyl poly (ethylene oxide) vinyl benzyl ether, ethyl poly (ethylene oxide) ethenyl benzyl ether, poly (propylene oxide) vinyl Benzyl ether, methyl vinyl poly (propylene oxide) vinyl benzyl Ether, ethyl poly (propylene oxide) vinyl benzyl ether, poly (ethylene oxide) vinyl phenyl ethyl ether, methyl poly (ethylene oxide) vinyl phenyl ethyl ether, ethyl poly (ethylene oxide) vinyl phenyl ethyl ether, poly (oxypropylene) vinyl phenyl ethyl ether Vinyl phenyl ether monomers having a long-chain polyalkylene oxide moiety such as methyl poly (propylene oxide) vinyl phenyl ethyl ether, ethyl poly (propylene oxide) vinyl phenyl ethyl ether;

For example, poly (ethylene oxide) isopropenyl phenyl ether, methyl poly (ethylene oxide) isopropenyl phenyl ether, ethyl poly (ethylene oxide) isopropenyl phenyl ether, poly (propylene oxide) isopropenyl phenyl ether, methyl poly (propylene oxide) isopropenyl phenyl Ether, ethyl poly (propene oxide) isopropenyl phenyl ether, poly (ethylene oxide) isopropenyl benzyl ether, methyl poly (ethylene oxide) isopropenyl benzyl ether, ethyl poly (ethylene oxide) isopropenyl benzyl ether, poly (propylene oxide) isopropenyl benzyl Ether, methyl poly (propylene oxide) Isopropenyl-based monomers having a polyalkylene oxide moiety, such as propenyl benzyl ether;

For example, mono-long chain alkyl ester monomers of dicarboxylic acid such as vinyl phenylnonyl succinate, vinyl phenyl methyl decyl hexahydrophthalate, vinyl phenyl ethyl dodecyl terephthalate;

For example, monopolyalkylene oxide esters of dicarboxylic acids such as vinyl phenyl poly (ethylene oxide) succinate, vinyl phenyl methyl poly (ethylene oxide) hexahydrophthalate, vinyl phenyl ethyl poly (ethylene oxide) terephthalate;
Polyalkylene oxides such as methyl 4-vinylbenzoate poly (ethylene oxide), ethyl polyvinylbenzoate poly (ethylene oxide), methyl 4-isopropenylbenzoate poly (propylene oxide), ethyl polyisopropylenylbenzoate poly (propylene oxide) Vinyl benzoate or isopropenyl benzoate monomers having a moiety;

For example, alkenyl group-containing sulfonic acids such as styrene sulfonic acid, 2-propenyloxybenzene sulfonic acid, 2-methyl-2-propenyl sulfonic acid, 2-methyl-2-propenyloxybenzene sulfonic acid;

For example, ammonium styrene sulfonate, monomethyl ammonium styrene sulfonate, dimethyl ammonium styrene sulfonate, trimethyl ammonium styrene sulfonate, tetramethyl ammonium styrene sulfonate, ethyl ammonium styrene sulfonate, diethyl ammonium styrene sulfonate, styrene sulfonic acid Styrene sulfones such as triethylammonium, tetraethylammonium styrenesulfonate, propylammonium styrenesulfonate, dipropylammonium styrenesulfonate, tripropylammonium styrenesulfonate, butylammonium styrenesulfonate, pentylammonium styrenesulfonate or hexylammonium styrenesulfonate Ammonium salts of acids;
For example, metal salts of styrene sulfonic acid such as sodium styrene sulfonate, potassium styrene sulfonate, lithium styrene sulfonate, magnesium styrene sulfonate, zinc styrene sulfonate, and iron styrene sulfonate;
For example, metal salts and ammonium salts of alkenyl group-containing vinyloxybenzenesulfonic acid such as ammonium vinyloxybenzenesulfonate, sodium vinyloxybenzenesulfonate, potassium vinyloxybenzenesulfonate;
For example, 2-methyl-2-propenyloxybenzenesulfonate ammonium, 2-methyl-2-propenyloxybenzenesulfonate sodium, 2-methyl-2-propenyloxybenzenesulfonate potassium and the like 2-methyl-2-propenyloxybenzenesulfonate Benzenesulfonic acid metal salts and ammonium salts;

For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) ( Meta) Rilamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (meth) acrylamide, 2,3,3-trichloro (meth) acrylamide, N-[(R) -1 -Phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, (Z) -N-methyl-3 -(Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, N- [2- (1H-imidazol-5-yl) ) Ethyl] (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (meth) acrylamide, crotonamide, maleinamide, fumarami , Mesaconamide, citraconic amide, itaconic amide, 3-phenyl-2-propenamide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N′-dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-vinylmethanamide Aliphatic or aromatic (meth) acrylamides such as N-vinylacetamide;

For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-iso Roxymethyl (meth) acrylamide, N-isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxy Octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide N-butoxyoctyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) Acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhexyl (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl- 2-methoxyethyl (meth) acrylamide, N- (oxetane-2-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N, N-di (methoxymethyl) (Meth) acrylamides containing N-alkoxy groups such as (meth) acrylamide and N, N-di (ethoxymethyl) (meth) acrylamide;

For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;

For example, cyclic amide group-containing (meth) acrylamides such as 4-acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam;

For example, nitrile group-containing ethylenically unsaturated monomers such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconnitrile, (meth) acrylic acid 2-cyanoethyl, etc. Kind;

For example, a nitrogen atom-containing heterocyclic vinyl-based monomer such as 2-vinylpyridine, 4-vinylpyridine, 2-vinylpiperazine, N-vinylimidazole, 4-vinylpiperazine, 2,4-diamino-6-vinyl-s-triazine, etc. Mers;

For example, maleimide derivatives such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide;

For example, vinyl esters of carboxylic acids such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl pivalate, vinyl palmitate, vinyl stearate;

For example, saturation of acetic acid (meth) allyl, propionic acid (meth) allyl, butyric acid (meth) allyl, capric acid (meth) allyl, lauric acid (meth) allyl, allyl octylate, coconut oil fatty acid allyl, pivalate allyl, etc. (Meth) allyl esters of carboxylic acids;

For example, glycidyl group-containing vinyl esters such as glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monooxirane, 1,3-butadiene monooxirane;

For example, vinyl compounds such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol;

For example, dienes such as allene, 1,2-butadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

For example, cis-diallyl succinate, diallyl 2-methylidene succinate, vinyl (E) -but-2-enoate, (Z) -octadeca-9-enoate, (9Z, 12Z, 15Z) -octadeca-9, Ethylenically unsaturated monomers containing polyfunctional unsaturated bonds such as vinyl 12,15-trienoate;

For example, ethylene, propylene, 1-butene, 2-butene, 2-methylpropene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratoacontene, 1-hexatriacontene, 1-octatriacontene, 1-tetraconten And alkenes such as polybutene-1, polypentene-1, poly-4-methylpentene-1, and the like.

  Further, for example, a copolymerizable α, β-unsaturated group-containing compound monomer obtained by reacting the above-mentioned glycidyl group-containing vinyl ester with a fatty acid, the above-mentioned halogenated alkylstyrenes and a long-chain alcohol , A copolymerizable α, β-unsaturated group-containing compound monomer obtained by reacting at least one alcoholic hydroxyl group-containing compound selected from poly (ethylene oxide) and poly (ethylene oxide) monoalkyl ether, etc. Is also included in the compound (d). Further, it is a so-called macromonomer, a so-called macromonomer having a polymer moiety having a weight average molecular weight (Mw) of 200 to 2,000,000 and a high molecular weight α, β-unsaturated group having an ethylenically unsaturated double bond. May be. In particular, it is not limited to these. These may use only 1 type or may use multiple types together.

  Since the polyamine (c) is easily Michael-added with the unsaturated group of the compound having an electron-withdrawing group, the compound (d) is preferably a (meth) acryloyl group-containing compound, and particularly the acryloyl group-containing compound is Michael. From the viewpoint of the efficiency of the addition reaction, it is more preferable. In the case where the acryloyl group-containing compound is an acrylic acid alkyl ester, it is more preferable because the adhesion to the polyolefin substrate is improved due to the effect of lowering the surface tension derived from the alkyl group.

  The functional group ratio (double bond / amino group) between the amino group in the polyamine (c) and the unsaturated double bond amount in the compound (d) is preferably from 0.1 to 1.0, more preferably 0.2 to 0.8 is more preferable. If it is less than 0.1, the substrate affinity effect due to the side chain generated by Michael addition may not be obtained. If it exceeds 1.0, excess compound (d) remains, resulting in a decrease in adhesive strength. May occur.

  As a synthesis method of the amino compound (C) in which the compound (d) is subjected to the Michael addition reaction with the polyamine (c), a known method relating to the Michael addition reaction can be used as it is. When compound (d) is a (meth) acryloyl group-containing compound, particularly an acryloyl group-containing compound, the reaction proceeds at 10 to 100 ° C., but the reaction is accelerated in the presence of an unsaturated compound having a hydroxyl group. Although depending on the type of the compound (d) used, a reaction temperature of 40 to 80 ° C. is preferred. An excessively high reaction temperature is not preferable because the ester bond and ester amide exchange reaction of (d) occur.

When the compound (d) does not have an electron-withdrawing group such as a (meth) acryloyl group, the compound (d) is reacted in the presence of an alcohol such as an alcohol solvent or an unsaturated compound having a hydroxyl group. By using in combination, the reaction can be advanced. As reaction temperature at this time, 60-100 degreeC is preferable from a viewpoint of reaction rate.
The reaction time varies depending on the type of compound (d) used, but is completed in 30 minutes to 8 hours.

  As the diisocyanate compound (e), the compounds exemplified for the polyisocyanate (A) can be used, and by using the aromatic polyisocyanate (a1), the compatibility with the polyisocyanate (A) can be increased. Possible and more preferred.

  The temperature of the urea reaction is preferably 100 ° C. or lower. More preferably, it is 70 degrees C or less. When the reaction rate is high even at 70 ° C. and the reaction cannot be appropriately controlled, 50 ° C. or less is more preferable. When the temperature is higher than 100 ° C., it is difficult to control the reaction rate, and it may be difficult to obtain a compound (F) containing a urea group having a target weight average molecular weight and structure.

  Next, the resin composition for joining laminated sheets will be described.

The resin composition for joining laminated sheets is characterized by including the polyisocyanate component (A), the polyol component (B), and the compound (F) containing a urea group, and satisfying the following (1) and (2). .
(1) 1-60 parts by weight of the compound (F) containing a urea group is contained in the total amount of the resin composition for bonding laminated sheets.
(2) The compound (F) is obtained by reacting an amino compound (C) obtained by Michael addition reaction of a polyamine compound (c) and a compound (d) having an unsaturated double bond with a diisocyanate compound (e). It is the compound which becomes.

  0.5-2.5 are preferable, as for the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate equivalent and a hydroxyl group in the resin composition for laminated sheet joining, 0.66-2.00 are preferable, and 1.0-1. 7 is most preferred. If it is less than 0.5, the hydroxyl group is present in excess of the isocyanate group, so the effect of improving the cohesive force due to the increase in molecular weight may not be obtained. If it is 2.5 or more, the isocyanate group is excessively larger than the hydroxyl group. In some cases, foaming due to a decarboxylation reaction due to a reaction with moisture in the atmosphere is remarkably generated and the appearance is deteriorated, or the curing reaction of the resin composition for joining laminated sheets may take time. In addition, when the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate equivalent in the polyisocyanate component (A) and the hydroxyl group in the polyol (B) is 1.0 to 1.7, the resin composition for bonding laminated sheets is It is easy to adjust the cohesive force and curing reaction rate.

  The following solvent can be used for the resin composition for joining laminated sheets of the present invention. As the solvent that can be used in the present invention, known solvents can be used, and examples thereof include ethyl acetate, toluene, methyl ethyl ketone, and other hydrocarbon solvents.

  In the resin composition for joining laminated sheets of the present invention, the amount of the solvent used is preferably 1% by weight or less with respect to the whole composition, and is preferably not substantially contained. By using a solvent, a drying process is required, and there may be a problem from the viewpoint of working environment or safety. In particular, it is preferable not to use a solvent containing a hydroxyl group, a carboxylic acid group, an amino group, or the like and capable of reacting with an isocyanate group in the polyisocyanate (A).

  The resin composition for joining laminated sheets according to the present invention can be used in combination with other resins, for example, an acrylic resin, an epoxy resin, and the like, if necessary. Furthermore, additives such as organic / inorganic pigments, fillers, colorants, ultraviolet absorbers, antioxidants, antifoaming agents, light stabilizers and the like may be blended depending on the application. Moreover, in order to further improve the adhesive performance, an adhesion assistant such as a silane coupling agent, phosphoric acid, a phosphoric acid derivative, or an acid anhydride can be used. In addition, known catalysts, additives and the like can be used to control the curing reaction.

The method of using the resin composition for joining laminated sheets of the present invention is obtained by mixing a polyisocyanate component (A), a polyol component (B) and a compound (F) containing a urea group, and joining the laminated sheets with a solventless laminator. The resin composition is applied to the surface of the sheet-like substrate. The coating amount of the laminated sheet bonding resin composition is appropriately selected according to the type of substrate, coating conditions, and the like, but is usually 1.0 to 5.0 g / m ² , preferably 1.5. ˜4.5 g / m ² .
Thereafter, the adhesive surface of the sheet-like base material and another sheet-like base material are bonded together, and aged and cured at room temperature or under heating. In the case of the resin composition for joining laminated sheets of the present invention, the time required for aging is about 1 day in 30 atmospheres. Moreover, in the case of the resin composition for joining laminated sheets of the present invention, sufficient adhesive performance can be exhibited even when the environmental humidity during coating to aging is high.

The resin composition for joining laminated sheets of the present invention is preferably performed at a temperature as low as possible within a range in which fluidity can be ensured, and specifically, preferably blended at 25 to 80 ° C. By reducing the temperature, it is possible to reduce the curing reaction rate of the isocyanate, and the pot life is improved.
The melt viscosity at 50 ° C. immediately after mixing the polyisocyanate component (A), polyol component (B), and urea group-containing compound (F) is preferably 50 to 10,000 mPa · s, more preferably 100 to 5000 mPa · s. s.

In the present invention, “immediately after mixing” means within 1 minute after uniform mixing, and the melt viscosity is a value determined by a B-type viscometer. When the melt viscosity at 50 ° C. exceeds 10,000 mPa · s, coating becomes difficult and it is difficult to ensure good workability, and coating is possible by increasing the coating temperature and decreasing the viscosity. Even if the temperature is raised to 100 ° C., a good coating appearance may not be obtained.
When a material having a low melting point such as polyethylene or polypropylene is applied at 100 ° C. or higher, the film may be stretched at the time of coating or laminating, resulting in misalignment. In the worst case, the film breaks, Lamination may not be possible. On the other hand, when the melt viscosity at 50 ° C. is less than 50 mPa · s, the initial cohesive force is weak, so that sufficient adhesion performance cannot be obtained, or the coating film is not coated when the laminated sheet bonding resin composition is applied to the substrate. The thickness may not be uniform, resulting in poor appearance, or the laminated sheet bonding resin composition may ooze out from the end face after winding.

A laminated body can be obtained by laminating a sheet-like base material using the resin composition for joining laminated sheets of the present invention.
As the sheet-like substrate, a plastic film such as polyester, polyamide, polyethylene, or polypropylene, a metal vapor deposition film obtained by vapor deposition of aluminum, silicon oxide, aluminum oxide, or the like, or a metal foil such as stainless steel, iron, copper, or lead is used. Such a combination of substrates may be a plastic film or a plastic film and a metal vapor deposition film or a metal foil.

  The obtained laminate of the present invention can be made into a packaging material through a heat sealing step. The heat sealing method can be performed by a known method. For example, in the case of an unstretched polypropylene film, a packaging material can be prepared by hot pressing within a range of 100 ° C. to 160 ° C. for several seconds. I can do it.

  Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise indicated,% and part in Examples and Comparative Examples are based on mass.

<Hydroxyl equivalent, hydroxyl value>
The hydroxyl equivalent is expressed in g / mol, and the hydroxyl value is expressed in mg of KOH per 1 g of polymer polyol, and measured by acetylation using pyridine and acetic anhydride. The measurement conditions are in accordance with JIS K1557-1.

<Amine equivalent, amine value>
The amine equivalent was expressed in g / mol, and the amine value was expressed in mg of KOH in a 1 g sample. The sample was dissolved in 30 g of ethanol and titrated by an indicator titration method using a hydrochloric acid standard solution.

<Isocyanate equivalent>
The isocyanate equivalent is expressed in g / mol, and the isocyanate group present in the sample was reacted by adding an excess of dibutylamine in toluene to produce the corresponding urea, and then using a hydrochloric acid standard solution, the indicator was used. Back titration was performed by a titration method and measured. The measurement conditions are based on JIS K7301.
《Molecular weight》
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Showa Denko GPC (gel permeation chromatography) “Shodex GPC System-21”. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. The sample was dissolved in tetrahydrofuran, and measurement was carried out using tetrahydrofuran as a developing solvent at a flow rate of 0.6 ml / min and a column temperature of 40 ° C. A calibration curve using monodispersed polystyrene as a standard substance is prepared, and the molecular weight of polyisocyanate (A) and polyol (B) is measured by polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw). did.

(Synthesis Example 1)
36.3 parts of polypropylene glycol having a number average molecular weight of about 1000 (hydroxyl value 112), 15.4 parts of triol having a number average molecular weight of about 400 obtained by adding polypropylene glycol to glycerin (hydroxyl value 390), 2,4-diphenylmethane diisocyanate 50 parts of a 4,4'-diphenylmethane diisocyanate is charged into a reaction vessel, and the mixture is heated under a nitrogen gas stream and heated at 70 ° C. to 80 ° C. for 3 hours to carry out a urethanation reaction. A polyether resin having an isocyanate group Got. The isocyanate equivalent was 276 g / mol. Hereinafter, this resin is referred to as polyisocyanate (A-1) (Synthesis Example 1).

[Synthesis Examples 2 and 3]
The synthesis was carried out in the same manner as in Synthesis Example 1 except that the raw materials and the charged parts described in Table 1 were used, to obtain polyisocyanates (A) of copolymers (A-2) and (A-3).

Raw material name (a1-1): 2,4-diphenylmethane diisocyanate (a1-2): 4,4-diphenylmethane diisocyanate HDI: hexamethylene diisocyanate HDI burette: hexamethylene diisocyanate burette modified (a2-1-1) ): Polypropylene glycol having a number average molecular weight of 1000 (hydroxyl value 112, secondary hydroxyl group)
(A2-1-2): Polypropylene glycol having a number average molecular weight of 2000 (hydroxyl value 56.6, secondary hydroxyl group)
(A2-1-3): Triol (hydroxyl value 390, secondary hydroxyl group) having a number average molecular weight of about 400 obtained by adding polypropylene glycol to glycerin
(A2-2-1): Polyester polyol obtained by copolymerizing 2-methyl-1,3-propanediol having a number average molecular weight of 1000 and adipic acid (hydroxyl value 112, primary hydroxyl group)
(A2-2-2): Polyester resin copolymerized with ethylene glycol / 2,2-dimethyl-1,3-propanediol / adipic acid / terephthalic acid having a number average molecular weight of 1000 (hydroxyl value 100, primary hydroxyl group)

(Synthesis Example 4)
100 parts of isophthalic acid, 355 parts of adipic acid, and 244 parts of ethylene glycol are charged into a reaction vessel, heated to 150 ° C. to 240 ° C. with stirring under a nitrogen gas stream, and reacted at 240 ° C. for 6 hours to carry out the esterification reaction. went. When the acid value reached 1.8 (mg KOH / g), the reaction temperature was adjusted to 200 ° C., the inside of the reaction vessel was gradually reduced in pressure, and the reaction was carried out at 1.3 kPa or less for 30 minutes to give an acid value of 0.6 (mg KOH / g ), A hydroxyl group equivalent of 353 (mol / g) and a number average molecular weight of 900, a polyester resin having primary hydroxyl groups at both ends was obtained. Hereinafter, this polyol is referred to as a polyol (b-1).

(Synthesis Examples 5 and 6)
Synthesis was performed in the same manner as in Synthesis Example 4 except that the raw materials and preparation parts described in Table 2 were used to obtain polyols (b-2, 3) having primary hydroxyl groups.

(Synthesis Example 7)
After charging 15 parts of ethylenediamine into a reaction vessel and adding dropwise 85 parts of 2-ethylhexyl acrylate over 1 hour at 40 ° C. under a nitrogen gas stream, the mixture is heated at 70-80 ° C. for 3 hours with stirring to perform a Michael addition reaction. , 100 parts of an amino group-containing compound (C) were obtained. Subsequently, 83 parts of tolylene diisocyanate was charged into the reaction vessel, and 100 parts of the amino group-containing compound (C) was added dropwise at 40 ° C. over 1 hour under a nitrogen gas stream to carry out a urea reaction to contain urea groups. Compound (F) was obtained. The isocyanate equivalent was 450 g / mol and the number average molecular weight was 1600. Hereinafter, this resin is referred to as (F-1).

(Synthesis Examples 8 to 10)
The synthesis was carried out in the same manner as in Synthesis Example 7 except that the raw materials and the charged parts described in Table 3 were used, to obtain a compound (F) (F-2, 3, 4) containing a urea group.

Example 1
100 parts of (A-1) obtained in Production Example 1 and 10 parts of (F-1) obtained in Production Example 7 were mixed and dissolved by heating at 50 ° C. for 10 minutes while stirring under a nitrogen gas stream. Next, 60 parts of the polyol (B-1) obtained in Synthesis Example 4 and 5 parts of methylpropanediol were charged into a container and mixed at 50 ° C. for 1 minute to obtain a solvent-free laminated sheet resin composition (S-1). Got. It was 3200 mPa * s when the melt viscosity in 50 degreeC of this laminated sheet joining resin composition was measured when 1 minute passed after uniform mixing. The equivalent ratio of isocyanate groups to hydroxyl groups of the resin composition for laminated sheets was 1.69. Regarding the obtained solvent-free laminated sheet bonding resin composition (S-1), the pot life, laminate appearance, adhesive strength, and isocyanate residual amount were evaluated by the following methods.

<Evaluation method of pot life>
About the obtained resin composition for laminated sheet joining, it left still in a 50 degreeC water bath for 15 minutes and 30 minutes, and measured on 20 rpm for 2 minutes conditions using a B-type viscosity meter (made by Tokyo Keiki Co., Ltd.). The pot life was evaluated on a four-point scale.
A: “Viscosity increase rate up to 30 minutes is less than 5 times” No problem in practical use.
○: “The viscosity increase rate up to 15 minutes is less than 5 times and the viscosity increase rate in 30 minutes is less than 10 times.” No problem in practical use.
Δ: “Risk increase rate up to 15 minutes is less than 10 times and fluidity in 30 minutes” No problem in practical use.
X: “No fluidity in 30 minutes” practically problematic.
In Example 1, the rate of increase in viscosity at 15 minutes was 3.8 times, and the rate of increase in viscosity at 30 minutes was 8 times, which was good.

[Production of laminate]
The solvent-free laminated sheet resin composition (S-1) obtained in each of the above Examples or Comparative Examples adjusted to 50 ° C. was subjected to a solvent-free test on the surface of a PET (polyethylene terephthalate) film (thickness: 12 μm). It was coated at 50 ° C. with a coater (coating amount: 2.0 g / m 2), and a vapor-deposited surface of an aluminum-deposited unstretched polypropylene film (VMPP, thickness: 25 μm) was layered on the coated surface. A laminate was obtained.
These pre-laminated bodies were cured for 1 day or 2 days in an environment of 30 ° C. and humidity of 20% RH or 80% RH to prepare a laminated body. About each obtained laminated body, the external appearance and adhesive force of the laminated body were observed and measured in the following way.

<Method for evaluating laminate appearance>
The state after curing of the obtained laminate was visually observed and evaluated in three stages.
○: “There is no yuzu skin-like pattern or speckled pattern or white turbidity due to foaming on the vapor deposition surface, and the resin composition layer for bonding laminated sheets is uniform.”
[Delta]: “Yuzu skin-like pattern, speckled pattern due to foaming and white turbidity are slightly observed on the vapor-deposited surface” at a level with no problem in use.
×: “A lot of yuzu skin-like patterns and speckled patterns due to foaming and white turbidity were observed on the vapor deposition surface”.
In addition, Example 1 was very good with no yuzu skin-like pattern, spotted pattern due to foaming, or cloudiness.

(Adhesive strength)
The laminate was cut to a length of 300 mm and a width of 15 mm to obtain a test piece. Using an Instron type tensile tester, the sample was pulled at a peeling rate of 300 mm / min in an environment of 25 ° C., and the T-type peeling strength (N / 15 mm) between PET / VMCP was measured. This test was performed 5 times, and the average value was obtained.
The peel strength of the obtained laminate was evaluated in four stages.
A: “Peel strength is 2N or more and good peel strength”
A: “Peel strength is 1.5N or more and less than 2N” is a level that does not cause a problem in use.
Δ: “Peel strength is 1N or more and less than 1.5N” is a level that does not cause a problem in use.
X: “Peel strength is less than 1N”, which is problematic in use.

In Example 1, the peel strength was 1.3 N under the condition of curing at 30 ° C. and 20% RH for one day.

<Reactive compound reactivity evaluation method>
About the obtained laminated body, the reaction rate of the isocyanate group after 1-day and 2-day curing was evaluated on 30 degreeC and 20% RH conditions. IR measurement is performed using Spectrum One manufactured by PerkinElmer, Inc., and the peak height ratio between the absorption spectrum of the isocyanate group (2270-2250 cm ⁻¹ ) and the absorption spectrum of the ester bond C═O stretching vibration (1750-1725 cm ⁻¹ ). The reaction rate of reactive compounds before and after curing was evaluated. A specific formula was obtained as follows and evaluated in four stages. Reaction rate (%) = (absorption of isocyanate group after curing / C = O absorption spectrum after curing) / (absorption of isocyanate group before curing / C = O absorption spectrum before curing) × 100
◎: “The reaction rate of isocyanate group is 80% or more after 1 day of curing, and no absorption of isocyanate group is observed after 2 days of curing. Curing reactivity is very good.”
○: “The reaction rate is 60% or more after 1 day of curing, and the reaction rate is 90% or more after 2 days of curing, and the curing reactivity is good.”
Δ: “Reaction rate 40% or more and 60% or less after one day of curing, reaction rate 75 to 90% after two days of curing, and curing reactivity is slightly insufficient”.
X: “After 2 days of curing, the reaction rate is less than 75% and the curing reactivity is insufficient.” There is a practical problem.
In Example 1, the reaction rate was 88% 1 day after curing, and the absorption spectrum of the reactive functional group was not observed after 2 days after curing, and the curing reactivity was very good.

(Examples 2 to 7)
In the same manner as in Example 1, laminated resin-bonding resin compositions (Examples 2 to 7) were obtained. Table 4 shows the results of the same evaluation as in Example 1.
MPO: 2-methyl-1,3-propanediol

(Comparative Examples 1-4)
In the same manner as in Example 1, laminated resin-bonding resin compositions (Comparative Examples 1 to 4) were obtained. The results of the same evaluation as in Example 1 are shown in Table 5.

  As shown in Table 4, the laminated sheet bonding resin compositions of the examples have excellent coating performance, and the state of the laminated sheet bonding resin composition layer on the vapor deposition surface is good, and the adhesive strength It turns out that it is also excellent. In particular, Examples 5 and 6 are less affected by environmental humidity during curing, and can exhibit equivalent or better adhesion performance with a short curing period. This is considered due to the fact that the adhesive performance was able to be expressed early due to the high cohesive force of the compound (F) containing a urea group. Furthermore, the high polarity of the compound (F) containing a urea group is expected to have high hygroscopicity, and during curing, expression of high cohesive force is promoted by the urea bond generated by the reaction between isocyanate and water. It is considered that the laminated sheet-bonding resin composition has excellent curability.

  By optimizing the use amount of the compound (F) containing a urea group, it is possible to adjust the viscosity before the curing reaction of the laminated sheet bonding resin composition and the cohesive force after the curing reaction, which is suitable for coating. And it turns out that adjustment of NCO residual amount and cohesion force after curing is possible (Examples 5 to 7). Further, when the isocyanate and water react with each other, a decarboxylation reaction occurs and bubbles are generated. The appearance may deteriorate due to the generated bubbles, but by using the compound (F) containing a urea group that has a high cohesive force, the cohesive force of the laminated sheet bonding resin composition layer can be efficiently increased. Therefore, expansion of bubbles can be suppressed and the appearance can be kept good.

  On the other hand, Comparative Example 1 showed the result when the compound (F) containing a urea group was not used, but it was found that the cohesive force was insufficient and the adhesiveness was poor. Moreover, when the compound (F) containing a urea group is used excessively as in Comparative Examples 2 to 4, since the hydrogen bond of the urea group is strong, the viscosity is high and the coatability may be poor. Even when the coating is performed, as in Comparative Example 3, when the pot life is poor and the appearance is poor, as in Comparative Example 4, the hygroscopicity of the compound (F) containing a urea group is high, The result was that the isocyanate and water in a hot and humid environment accelerated the reaction and lowered the adhesiveness.

By changing the ratio of (A), (B), and (F) in the resin composition for bonding laminated sheets, the resin composition for bonding laminated sheets according to the present invention is matched to the same or different materials. It is used to join various films.
For example, it is suitably used for joining a multilayer laminate of a plastic material and a metal processing material. Of course, it is also suitably used for joining plastic films and metal films. In addition, by adding a predetermined amount of the urea group-containing compound (F) in the laminated sheet bonding resin composition, high adhesive strength due to strong cohesive force due to the urea group and short-term aging can be equivalent or better. It can be suitably used as a bonding resin composition for laminated sheets that can exhibit adhesive performance and is less affected by humidity due to an aging environment.

In addition, the effect of the present invention in which the compound (F) containing a urea group is used to improve the cohesive force can be applied to all resin compositions using urethane-based reactions. For example, it can be used for pressure-sensitive adhesive compositions, coating agents, inks, and the like.

Claims (7)

A resin composition for joining laminated sheets, comprising a polyisocyanate component (A), a polyol component (B), and a compound (F) containing a urea group, and characterized by the following (1) and (2).
(1) The compound (F) containing a urea group is contained in an amount of 1 to 60 parts by weight with respect to the total amount of the laminated sheet bonding resin composition.
(2) The compound (F) is obtained by reacting an amino compound (C) obtained by Michael addition reaction of a polyamine compound (c) and a compound (d) having an unsaturated double bond with a diisocyanate compound (e). Is a compound.   2. The laminated sheet bonding material according to claim 1, wherein an equivalent ratio (isocyanate group / hydroxyl group) of an isocyanate group and a hydroxyl group in the resin composition for bonding a laminated sheet is 0.5 to 2.5. Resin composition. The polyisocyanate component (A) is
An isocyanate group in the aromatic polyisocyanate (a1);
The polyisocyanate (A2) obtained by reacting a hydroxyl group in the polyether polyol (a2-1) and / or the polyester polyol (a2-2) with an isocyanato group-excess condition. The resin composition for bonding laminated sheets as described.   The resin composition for joining laminated sheets according to any one of claims 1 to 3, wherein the resin composition for joining laminated sheets contains substantially no organic solvent.   The laminated body formed by laminating | stacking at least 2 sheet-like base material using the resin composition for laminated sheet bonding in any one of Claims 1-4.   A packaging material using the laminate according to claim 5. The process 1 which apply | coats the resin composition for laminated sheet bonding in any one of Claims 1-4 to a 1st sheet-like base material, and forms a resin layer,
Step 2 of superimposing a second sheet-like substrate on the resin layer;
A method for producing a laminate comprising the step 3 of curing the resin layer.