WO2019039450A1

WO2019039450A1 - Method for producing uretdione-containing resin, uretdione-containing resin, method for producing isocyanate-containing resin, and laminate

Info

Publication number: WO2019039450A1
Application number: PCT/JP2018/030756
Authority: WO
Inventors: 常行手島; 松木　光一郎; 武田　博之
Original assignee: Dic株式会社
Priority date: 2017-08-25
Filing date: 2018-08-21
Publication date: 2019-02-28

Abstract

Provided is a method for producing a uretdione-containing resin A, which comprises a step for reacting an isocyanate compound and an alcohol compound with each other, and which is characterized in that the isocyanate compound contains an isocyanate compound having a uretdione skeleton and the alcohol compound contains a polyol compound. Also provided is the method for producing a uretdione-containing resin A, wherein the molar ratio of the isocyanate groups contained in the isocyanate compound to the alcoholic hydroxyl groups in the alcohol compound is from 1.0:0.8 to 1.0:2.0.

Description

Method for producing uretdione-containing resin, uretdione-containing resin, method for producing isocyanate-containing resin, and laminate

The present invention relates to a method for producing an isocyanate compound.

Demand and applications of flexible packaging are expanding due to its ease. The laminating adhesive used therein is generally cured by a polyol / isocyanate compound, and in particular, is frequently used for high-performance applications such as boiling applications and retort applications. In recent years, in addition to high performance, environmental protection and safety are strongly demanded. In particular, from the viewpoint of reduction of environmental load and improvement of working environment, the demand for non-solvent type adhesive containing no volatile organic solvent It is rising. In particular, solventless adhesives for laminating are highly expected as adhesives for food packaging where safety is required strictly.

The non-solvent type laminating adhesive has many merits such as energy saving and good running cost since there is no need to take into consideration the residual solvent in the laminate film and the drying step is unnecessary.
However, since the coating method of the solventless adhesive at the time of laminating is performed by coating the resin itself in the solventless adhesive with a roll coater, so-called resin when the film after coating of the adhesive and the coater are separated And the filamentous adhesive is transferred to the film, the coated surface is roughened, air is easily caught in the adhesive layer, air bubbles are generated, and the laminate film appearance is degraded. was there. The problem of the decrease in appearance of the laminate film due to the air bubbles became serious as the adhesive itself became high in viscosity.
Therefore, in order to improve the appearance, it is necessary for the solventless adhesive to have a low viscosity composition, and therefore, it is general to design a resin having a molecular weight smaller than that of the solvent type.

On the other hand, when it is intended to lower the molecular weight of the resin in order to lower the viscosity, there is a problem that a large amount of monomers as a raw material remains. For example, in the case of a urethane-based adhesive, a large excess of isocyanate monomer is added and the polyol is reacted to suppress high molecular weight formation to form a low viscosity resin, but the remaining isocyanate monomer becomes a vapor during coating and works Being a cause of the health hazards of the

Therefore, for example, as described in Patent Document 1, there is known a technology for removing residual isocyanate monomer by distilling and removing unreacted isocyanate monomer from a reaction product after urethane.
However, although such a method is effective in suppressing vapor during solventless adhesive coating, the product price increases due to the generation of harmful vapor during distillation and the increase in manufacturing cost due to the distillation process. There was a problem of losing market competitiveness.

Japanese Patent Application No. 4-351412

The problem to be solved by the present invention is a method for producing an isocyanate-containing resin having a small amount of isocyanate monomer which becomes a vapor during coating and causes health problems of workers, and a method for producing a precursor of the isocyanate-containing resin To provide.

As a result of intensive investigations, the present inventors provide a method for producing an isocyanate resin obtained by cleaving a resin having a urethane bond and a uretdione skeleton, and provide a method for producing a resin having the uretdione skeleton. It has been found that the subject of the present invention can be provided.

That is, the present invention relates to a method for producing uretdione-containing resin A, which comprises the step of reacting an isocyanate compound with an alcohol compound,
The process for producing uretdione-containing resin A is provided, wherein the isocyanate compound comprises an isocyanate compound having a uretdione skeleton and the alcohol compound comprises a polyol compound.

The present invention also provides a process for producing an isocyanate-containing resin B, comprising the step of cleaving the uretdione skeleton contained in the uretdione-containing resin A to obtain an isocyanate-containing resin B.

The present invention also provides a composition containing the isocyanate-containing resin B and an alcohol compound. Furthermore, the manufacturing method of urethane resin P which has the process of making isocyanate-containing resin B and an alcohol compound react is provided.

The present invention also provides a laminate comprising a substrate and the urethane resin P layer described above.

The present invention also provides a laminate having an upper layer on the urethane resin P layer described above.

The present invention further provides a method for producing a laminate, comprising the steps of applying the isocyanate-containing resin B described above and an alcohol compound on a substrate, and further reacting the isocyanate-containing resin B and the alcohol compound. provide.

Since the isocyanate-containing resin B obtained in the present invention is obtained by cleaving the precursor uretdione-containing resin A, it becomes a low viscosity isocyanate-containing resin without using a large excess of isocyanate monomer. Therefore, coating can be performed without generating harmful vapor derived from residual isocyanate monomer.

(Uretdione-containing resin A)
The uretdione-containing resin A produced in the present invention is a resin obtained by reacting an isocyanate compound and an alcohol compound, wherein the isocyanate compound contains an isocyanate compound having a uretdione skeleton, and the alcohol compound contains a diol compound. It is characterized by By reacting an isocyanate compound having a uretdione skeleton, the uretdione skeleton is introduced into the resulting resin.

Examples of the isocyanate compound having a uretdione skeleton include diphenylmethane diisocyanate uretdione, tolylene diisocyanate uretdione, hexamethylene diisocyanate uretdione, isophorone diisocyanate uretdione, xylylene diisocyanate uretdione and the like. Preferred are hexamethylene diisocyanate uretdione, isophorone diisocyanate uretdione, and xylylene diisocyanate uretdione, and particularly preferred is hexamethylene diisocyanate uretdione.

The isocyanate compound other than the isocyanate compound having a uretdione skeleton may be any compound having an isocyanate group, and in particular, a polyisocyanate having two or more isocyanate groups is preferable.

As monofunctional isocyanate, methyl isocyanate, butyl isocyanate, hexyl isocyanate, heptyl isocyanate, lauryl isocyanate, stearyl isocyanate, phenyl isocyanate, cyclopropyl isocyanate, phenethyl isocyanate, tosyl isocyanate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, vinyl isocyanate, Allyl isocyanate, 2- (2-acryloyloxyethyloxy) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 1,1-bis (methacryloyloxy) Methyl) ethyl isocyanate etc. That.

Examples of the polyisocyanate include aromatic polyisocyanate, aliphatic or alicyclic polyisocyanate, or modified products thereof.
Examples of the aromatic polyisocyanate include polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate and the like.
Examples of aliphatic polyisocyanates include hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and trimers of these isocyanates. Be
Examples of modified polyisocyanates include trimethylolpropane adduct modified products, isocyanurate modified products, biuret modified products, allophanate modified products and the like.

The polyisocyanate may be a blocked isocyanate. As an isocyanate blocking agent, for example, phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, phenol such as chlorophenol, acetoxy, methyl ethyl ketoxime, oxime such as cyclohexanone oxime, methanol, Alcohols such as ethanol, propanol and butanol, halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol, tertiary alcohols such as t-butanol and t-pentanol, ε-caprolactam And lactams such as .delta.-valerolactam, .gamma.-butyrolactam and .beta.-propyrolactam, and aromatic amines, imides and acetylacetone Acetoacetic ester, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, ureas, diaryl compounds, such as sodium bisulfite may also be mentioned. The blocked isocyanate is obtained by the addition reaction of the above-mentioned isocyanate compound and an isocyanate blocking agent by a conventionally known appropriate method.

The polyisocyanate is preferably an aliphatic polyisocyanate. If it is aliphatic polyisocyanate, it is excellent in the tolerance to the peeling stress by the thermal expansion and contraction difference of laminates at the time of performing a boiling and a retort process, after setting it as a laminate. In particular, isocyanurate-type modified products, burette-type modified products, and allophanate-type modified products are preferable.

One of these isocyanate compounds may be used alone, or two or more of these isocyanate compounds may be used in combination.

The content of the isocyanate compound having a uretdione skeleton in the isocyanate compound is preferably 20 mol% to 80 mol% in the total isocyanate compound. Particularly preferably, it is 60 mol% to 80 mol%.

The alcohol compound may be any compound having an alcoholic hydroxyl group, and particularly preferably a polyol having two or more alcoholic hydroxyl groups.

Monofunctional alcohols include, but are not limited to, alicyclic alcohols, aliphatic alcohols, and aromatic alcohols.

The alicyclic alcohol is not particularly limited as long as it is an alcohol containing one or more saturated or unsaturated carbon rings having no aromaticity. As a saturated or unsaturated carbocyclic ring, monocyclic cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane and cyclododecane; cyclopropene, cyclobutene, cyclo Monocyclic cycloalkenes such as propene, cyclohexene, cycloheptene and cyclooctene; Bicyclic alkanes such as bicycloundecane and decahydronaphthalene; Bicyclic alkenes such as norbornene and norbornadiene; Three such as tricyclodecane, adamantane and steroids And alkanes or alkenes of rings or more. These compounds may or may not have a substituent.

Examples of aliphatic alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octa Monofunctional alcohol having a linear alkyl group such as decanol, nonadecanol, eicosanol, henikosanol, docosanol, tricosanol, tetracosanol, pentacosanol, 2-butanol, isobutanol, tert-butanol, 2-pentanol , 3-pentanol, isopentanol, 2-methyl-1-butanol, 2-methyl-3-butanol, 2,2-dimethyl-1-propanol, tert-pentano 2, 2-hexanol, 3-hexanol, isohexanol, 2-methyl-2-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-ethyl-1-butanol, 3, 3-dimethyl-1-butanol, 2-heptanol, 3-heptanol, 4-heptanol, 5-methyl-1-hexanol, 4-methyl-1-hexanol, 3-methyl-1-hexanol, 2-ethyl-2-hexanol Methyl-1-butanol, isooctanol, 2-ethyl-1-hexanol, isononanol, 3.5.5-trimethylhexanol, isodecanol, isoundecanol, 5-ethyl-2-nonanol, isododedecanol, isotridec Decanol, isotetradecanol, isopentadecanol, isohexdecanol, 2 Monofunctional alcohols having a branched alkyl group such as hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, 2-decyltetradecanol, 2-methylstearyl alcohol, etc. Can be mentioned.

Examples of the aromatic alcohol include benzyl alcohol, methylphenylmethanol, methoxyphenylmethanol, ethylphenylmethanol, ethoxyphenylmethanol, butylphenylmethanol, butoxyphenylmethanol, phenylethanol, methylphenylethanol, methoxyphenylethanol, ethylphenylethanol, Ethoxyphenylethanol, butylphenylethanol, butoxyphenylethanol, phenylpropanol, methylphenylpropanol, methoxyphenylpropanol, ethylphenylpropanol, ethoxyphenylpropanol, butylphenylpropanol, butoxyphenylpropanol, phenylbutanol, methylphenylbutanol, methoxyphenylbutanol , Ethylphenyl butanol, ethoxy phenyl butanol, butyl phenyl butanol, butoxy phenyl butanol, furfuryl alcohol and the like.

Examples of the polyol include aliphatic polyols, polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, polyacrylic polyols, dimer diols and the like.
The hydroxyl value of the polyol is not particularly limited, but 20 to 300 (mg KOH / g) is preferable (for example, according to JIS K 1557-1).

Examples of aliphatic polyols include alkylene diols having 2 to 6 carbon atoms. The alkylene diol having 2 to 6 carbon atoms is, for example, ethylene glycol, propylene glycol, butylene glycol, 1,5-pentanediol, 1,6-hexanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol And diols such as tetraethylene glycol and dipropylene glycol.

Examples of polyether polyols include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, polyethylene glycol / polypropylene glycol block copolymer, propylene glycol propylene oxide adduct, bisphenol A propylene oxide adduct, glycerin propylene oxide adduct, ethylene diamine Examples thereof include propylene oxide adducts, ethylene diamine propylene oxide adducts, sorbitol-based propylene oxide adducts, sucrose-based propylene oxide adducts, and propylene oxide-ethylene oxide random polyethers.

Polycarbonate polyols include those represented by the general formula HO-R-[(OCOOO) -R] n-OH (R is a divalent organic group, n is a number of 1 or more), and R is an alkylene. Groups, arylene groups, aralkylene groups or combinations thereof. n is preferably a number corresponding to the above-mentioned preferred hydroxyl value. Specifically, Duranol G3452, G4672, T5652 (all trade names) manufactured by Asahi Kasei Corp., Benevior NLB (trade name) manufactured by Mitsubishi Chemical, Nipporan 981 manufactured by Tosoh Corporation, Nipporan 980R, Nipporan 982R, Nipporan 963, Nipporan 964 (all are trade names) and the like.

Examples of polyester polyols include reaction products of carboxylic acids (or salts thereof) or dicarboxylic acid anhydrides with polyhydric alcohols, or ring-opening polymers of caprolactone. In the former case, as carboxylic acids, aliphatic dicarboxylic acids such as adipic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentane dicarboxylic acid, aromatic dicarboxylic acids such as phthalic acid, and anhydrides of these dicarboxylic acids, Alternatively, polybasic acids of ester-forming derivatives such as p-hydroxybenzoic acid and p- (2-hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used, either alone or in combination. It can be used in the mixture of the above.

As polyhydric alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene And alkylene diols having 1 to 12 carbon atoms such as glycol and dipropylene glycol. Examples of the latter include ring-opening polymers such as ε-caprolactam, γ-valerolactam, β-propyrolactam and the like.

One of these alcoholic compounds may be used alone, or two or more thereof may be used in combination.

The uretdione-containing resin A of the present invention can be obtained by reacting an isocyanate compound having an isocyanate compound having a uretdione skeleton with an alcohol compound containing a diol compound.
The reaction of isocyanate and alcohol may be carried out, for example, in a temperature range of 20 to 120 ° C. You may use a urethanization catalyst as needed.

In producing the uretdione-containing resin A, the molar ratio of the isocyanate group contained in the isocyanate compound to the alcoholic hydroxyl group of the alcohol compound is preferably 1.0: 0.8 to 1.0: 2.0. When the molar ratio is 1.0: 0.8 or more, the isocyanate compound reacts sufficiently and the problem of vapor due to the residual monomer hardly occurs, and when the molar ratio is 1.0: 2.0 or less, the isocyanate and the alcohol sufficiently react. It is preferably 1.0: 0.8 to 1.0: 1.5, particularly preferably 1.0: 1.0 to 1.0: 1.2.

The uretdione concentration in the uretdione-containing resin A of the present invention is preferably 0.01 to 5.0 mmol / g. At this concentration, since the isocyanate compound B obtained by cleaving the uretdione skeleton becomes a low molecular weight, the viscosity at the time of coating becomes low, and it is possible to suppress the deterioration of the appearance such as air bubbles. It is preferably 0.1 to 2.0 mmol / g, particularly preferably 0.2 to 1.0 mmol / g.

The molecular weight of the uretdione-containing resin A of the present invention is preferably 500 to 1,000,000. If the molecular weight is too low, an isocyanate-containing resin B having a sufficient molecular weight can not be obtained after uretdione cleavage. On the other hand, when the molecular weight is too high, the viscosity becomes high and the production becomes difficult. Preferably, it is 1,000 to 100,000, and particularly preferably 5,000 to 50,000.

(Isocyanate-containing resin B)
The isocyanate-containing resin B produced in the present invention is obtained by cleaving the uretdione skeleton contained in the uretdione-containing resin A. Cleavage reaction of the uretdione skeleton proceeds by heating the urethane resin A to 100 to 160.degree.

A catalyst may be added in the cleavage reaction of the uretdione skeleton. As the catalyst, publicly known ones can be used. Specifically, tin-based catalysts such as dibutyltin dilaurate and stannas octoate, triethylenediamine, triethylamine, N, N, N ', N'-tetramethylpropylenediamine N, N, N ', N'- tetrakis (2-hydroxypropyl) ethylenediamine, N-methylmorpholine, 1,2-dimethylimidazole, 1, 5- diaza-bicyclo (4, 3, 0) nonene-5, 1,8-Diazabicyclo (5,4,0) -undecene-7 (hereinafter referred to as DBU), various amine salt catalysts such as borane salts of these amine catalysts, DBU phenol salts, DBU octoates, DBU carbonates, etc. , Magnesium naphthenate, lead naphthenate, carboxylates such as CH3 COOK +, triethyl phosphite , Trialkyl phosphines such as tribenzylphosphine, alkoxides such as CH3 ONa, zinc organometallic catalysts, and the like.

The molecular weight of the isocyanate-containing resin B of the present invention is preferably 250 to 20,000. If the molecular weight is too low, sufficient performance as an adhesive can not be obtained. On the other hand, when the molecular weight is too high, the viscosity becomes high and the appearance of the laminated film after coating is deteriorated. It is preferably 500 to 10,000, and particularly preferably 1,000 to 5,000.

The viscosity of the isocyanate-containing resin B of the present invention is preferably 100 to 10,000 mPa · s at 80 ° C. When the viscosity is too low, it becomes difficult to obtain a sufficient coating amount as an adhesive. On the other hand, when the viscosity is too high, the appearance of the laminated film after coating is deteriorated. It is preferably 500 to 5,000, and particularly preferably 750 to 2,000.

As the alcoholic compound to be reacted with the isocyanate-containing resin B, the alcoholic compounds listed in the production of the uretdione-containing resin A can be used. The alcoholic compound in this reaction is preferably a polyol having a molecular weight of 200 or more and having two or more alcoholic hydroxyl groups, and in particular, polyether polyol, polycarbonate polyol, polyester polyol and the like are preferable.
Moreover, you may use a urethanization catalyst in this reaction.

(Composition)
The composition of the present invention contains uretdione-containing resin A and an alcoholic compound.
The composition may contain a solvent depending on the use application. Examples of the solvent include organic solvents such as methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol Monomethyl ether acetate etc. are mentioned. The type and amount of solvent used may be selected appropriately depending on the application.

The composition may contain various additives as long as the effects of the present invention are not impaired. Additives include, for example, organic fillers, inorganic fillers, stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.), plasticizers, antistatic agents, lubricants, antiblocking agents, colorants, crystal nucleating agents, An oxygen scavenger (compound having an oxygen scavenging function), a tackifier and the like can be exemplified.

Among the additives, examples of the inorganic filler include inorganic substances such as metals, metal oxides, resins, and minerals, and composites thereof may be used. Specific examples of the inorganic filler include silica, alumina, titanium, zirconia, copper, iron, silver, mica, talc, aluminum flakes, glass flakes and clay minerals. Among these, it is preferable to add a clay mineral for the purpose of improving the gas barrier property, and it is preferable to use a swelling inorganic layered compound among them. Swellable inorganic layered compounds include, for example, hydrous silicates (phylosilicate minerals etc.), kaolinite clay minerals (Halloysite etc.), smectite clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, Saulconite, Stevensite, etc.), vermiculite clay minerals (vermiculite, etc.) can be mentioned. These minerals may be natural clay minerals or synthetic clay minerals.
These various additives may be used alone or in combination of two or more.

Examples of compounds having an oxygen scavenging function include hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, low molecular weight organic compounds that react with oxygen such as gallic acid and pyrogallol, cobalt, manganese, nickel, iron, Transition metal compounds, such as copper, etc. are mentioned.

The tackifier includes xylene resin, terpene resin, phenol resin, rosin resin and the like. By adding a tackifier, the adhesiveness to various film materials immediately after application can be improved. The amount of tackifier added is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.

(Urethane resin P)
Urethane resin P manufactured by this invention is obtained by making isocyanate containing resin B and an alcohol compound react. The above reaction is preferably carried out by heating to room temperature to 120 ° C. Furthermore, it is preferable to complete the reaction over 1 to 5 days after uniformly stirring using various mixers and the like, and passing through forming and coating steps.
The urethane resin P produced from the isocyanate-containing resin B of the present invention can be suitably used as a non-solvent type adhesive because it has a low amount of residual isocyanate monomer and a low molecular weight.

The urethane resin P can be coated on a base film etc. and used as an adhesive. There is no limitation in particular as a coating method, and it may carry out by a well-known method. In the case of a non-solvent type adhesive, the viscosity at room temperature is high and gravure roll coating is often unsuitable, and in that case, coating is performed with a roll coater while heating. When a roll coater is used, it is preferable to coat the adhesive of the present invention while heating to about room temperature to about 120 ° C. so that the viscosity of the adhesive is about 500 to 2500 mPa · s. Moreover, when using as a solvent type adhesive agent, after diluting in a suitable solvent and adjusting to a suitable viscosity, it apply | coats with a gravure roll coating system etc. in many cases.

Another base film etc. can be laminated by a publicly known method to urethane resin P coated by the above-mentioned method to a base film etc., and a layered product can be manufactured.

The urethane resin P of the present invention can be used as an adhesive for various applications requiring heat resistance to polymers, paper, metals and the like. For example, as packaging materials used for packaging of food and beverage, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: linear low density polyethylene film, HDPE: high density polyethylene film) And polyolefin films such as polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, cycloolefin copolymer film and the like. These films can be preferably used with or without a stretching treatment. Films subjected to a stretching process have the advantages of dimensional stability, rigidity and easy coating operation and ease of use.
Although the unstretched film is inferior in rigidity and heat resistance, it can be heat-melted, and has the advantage of being able to seal the four sides to make a packaging bag or the like.

The composition containing the isocyanate-containing resin B according to the present invention can be suitably used as an adhesive, particularly as an adhesive for lamination, since the generation of harmful vapor during coating is suppressed because the amount of residual isocyanate monomer is small. It is.
In addition, the laminate produced using the adhesive of the present invention can be suitably used as a packaging member, particularly as a food packaging member because of its high safety. In addition, since the residual amount of isocyanate monomer is small, it can be particularly suitably used as a packaging member for boiling and / or retorting.

Next, the present invention will be specifically described by way of examples and comparative examples. Examples Unless otherwise noted, "parts" and "%" are on a mass basis.

Production Example 1 Uretdione-Containing Resin A “U-4000 0.8 eq” Production Method In a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, and a condenser, 57.00 parts of uretdione skeleton-containing hexamethylene diisocyanate, polypropylene glycol (molecular weight 4000 700.00 parts and 0.76 parts of triethylamine were charged, and gradually heated to maintain the internal temperature at 80 ° C. The infrared absorption spectrum was measured, and when the absorption of isocyanate disappeared, the reaction was terminated to obtain uretdione-containing resin A “U-4000 0.8 eq” having a viscosity of 23.57 Pa · s at 80 ° C.

Production Example 2 Uretdione-Containing Resin A “U-400 1.0 eq” Production Method In a reaction vessel equipped with a stirrer, a nitrogen gas introduction pipe, and a condenser, 464.00 parts of uretdione skeleton-containing hexamethylene diisocyanate, polypropylene glycol (molecular weight 400 320.00 parts, 60.0 parts of n-butanol and 0.84 parts of triethylamine were charged, and gradually heated to maintain the internal temperature at 80 ° C. The infrared absorption spectrum was measured, and when the absorption of NCO disappeared, the reaction was terminated to obtain uretdione-containing resin A “U-400 1.0 eq” having a viscosity of 18.83 Pa · s.

Production Example 3 Production Method of Isocyanate-Containing Resin B “B1” 700 parts of urethane resin P “U-4000 0.8 eq” obtained in Production Example 1 in a reaction vessel equipped with a stirrer, a nitrogen gas introduction pipe, and a condenser Then, 0.70 parts of tributylphosphine was charged, and gradually heated to maintain the internal temperature at 100 ° C. The infrared absorption spectrum was measured, and when the absorption of uretdione disappeared, the reaction was terminated to obtain a reactant "B1" containing an isocyanate-containing resin B and having a viscosity of 1.92 Pa · s at 80 ° C and a viscosity of 1.92 Pa · s.

Production Example 4 Production Method of Isocyanate-Containing Resin B “B2” 700 parts of urethane resin P “U-400 1.0 eq” obtained in Production Example 1 in a reaction vessel equipped with a stirrer, a nitrogen gas introduction pipe, and a condenser The mixture was gradually heated to maintain the internal temperature at 130.degree. The infrared absorption spectrum was measured, and when the absorption of uretdione disappeared, the reaction was terminated to obtain a reactant "B2" containing an isocyanate-containing resin B and having a viscosity of 1.88 Pa · s at 80 ° C.

Production Example 5 Production Method of Isocyanate-Containing Resin B “B3” Into a reaction vessel equipped with a stirrer, a nitrogen gas introduction pipe and a condenser, 50.00 parts of hexamethylene diisocyanate and 710.00 parts of polypropylene glycol (molecular weight 4000) are charged. The internal temperature was maintained at 80 ° C. by gradually heating. The infrared absorption spectrum was measured, and when the absorption of isocyanate disappeared, the reaction was terminated to obtain a reactant "B3" containing an isocyanate-containing resin B and having a viscosity of 2.83 Pa · s at 80 ° C.

Production Example 6 Production Method of Isocyanate-Containing Resin B “B4” 130.00 parts of hexamethylene diisocyanate and 735.00 parts of polypropylene glycol (molecular weight 4000) are charged in a reaction vessel equipped with a stirrer, a nitrogen gas introduction pipe and a condenser. The internal temperature was maintained at 80 ° C. by gradually heating. The infrared absorption spectrum was measured, and when the absorption of isocyanate disappeared, the reaction was terminated, and a reactant "B4" containing an isocyanate-containing resin B and having a viscosity of 80 ° C and a viscosity of 0.21 Pa · s was obtained.

Production Example 7 Production Method of Alcohol Compound "D1" A polyester reaction container equipped with a stirrer, a nitrogen gas introduction pipe, a snider pipe, and a condenser, 195.00 parts of ethylene glycol, 173.00 parts of diethylene glycol, 110 hexanediol 110 Charge .00 parts, 613.00 parts of isophthalic acid, 64.00 parts of sebacic acid, and 0.10 parts of titanium tetraisopropoxide, and gradually heat so that the upper temperature of the rectification tube does not exceed 100 ° C. Was kept at 240.degree. When the acid value becomes 5.0 mg KOH / g or less, the esterification reaction is finished, and the designed functional group number N = 2, hydroxyl value = 160, theoretical number average molecular weight 700 calculated from hydroxyl value, 80 ° C. viscosity 2.10 Pa An alcohol compound "D1" of s was obtained.

(Method of measuring viscosity of isocyanate compound at 80 ° C)
The viscosity of the isocyanate-containing resin B obtained by the above-mentioned production method was measured using a MCR rheometer manufactured by Anton Paar, under the conditions of a cone plate CP-50, a rotation speed of 5 rpm, and a temperature of 80.degree.

(Method of measuring residual monomer amount after synthesis of isocyanate-containing resin B)
To 1 mL of a solution obtained by diluting 100 mg of isocyanate resin B obtained by the above production method with 5 mL of super dehydrated ethyl acetate, add 10 uL of an internal standard sample prepared by diluting 100 mg of n-tetradecane with 10 mL of super dehydrated ethyl acetate. Do. The amount of residual monomer after synthesis of the isocyanate-containing resin B was measured based on ISO 10283 using GC-2010 manufactured by Shimadzu Corporation.

(Examples 1 and 2, Comparative Examples 1 and 2)
According to the composition of Table 1, isocyanate-containing resin B and an alcohol compound were mixed to obtain an adhesive.

(Method of Manufacturing Laminated Product Using Adhesives of Examples 1 and 2 and Comparative Examples 1 and 2)
The adhesive obtained in Examples 1 and 2 and Comparative Examples 1 and 2 is heated to about 80 ° C., and a 12-μm-thick PET film (polyethylene terephthalate film) is produced using a solventless test coater Polytype roll coater. The coating amount is 3.0 g / m ² on the aluminum surface of a film obtained by laminating Toyobo Co., Ltd. “E-5102” and a 9 μm thick aluminum foil (Toyo Aluminum Co., Ltd. “O material”) After coating, the coated surface is laminated with a 70 μm thick CPP film (non-oriented polypropylene film, manufactured by Toray Film Co., Ltd. “ZK93KM”) at a laminating roll temperature of 50 ° C., PET film-aluminum foil / adhesive layer / A laminate having a CPP film layer configuration was produced. Next, the obtained laminate was subjected to aging at 40 ° C. for 3 days to cure the adhesive to obtain a laminate.

(Adhesive strength evaluation method)
The obtained laminate is cut into a width of 15 mm in parallel with the coating direction, and an atmosphere temperature of 25 ° C., a peeling speed, using an Tenshiron universal tester manufactured by ORIENTEC CO., LTD., Between aluminum foil and a CPP film. Was set to 300 mm / min, and the tensile strength at the time of peeling by a 180 degree peeling method was taken as the adhesive strength. The unit of adhesive strength was N / 15 mm. In the case of film breakage during measurement, F and peak values were described in the results.

(Method for evaluating laminate appearance)
The appearance immediately after lamination of the PET film-aluminum foil / adhesive layer / CPP film laminate coated by the above method was visually observed from the CPP film side, and the laminate appearance was evaluated according to the following.
Less than 10 bubbles in 10 mm × 10 mm laminate: appearance of laminate ○
10 or more bubbles in the laminate 10 mm × 10 mm: laminate appearance ×

Claims

A process for producing uretdione-containing resin A, comprising the step of reacting an isocyanate compound with an alcohol compound,
A method for producing uretdione-containing resin A, wherein the isocyanate compound contains an isocyanate compound having a uretdione skeleton, and the alcohol compound contains a polyol compound.
The method for producing uretdione-containing resin A according to claim 1, wherein the molar ratio of the isocyanate group contained in the isocyanate compound and the alcoholic hydroxyl group of the alcohol compound is 1.0: 0.8 to 1.0: 2.0. .
A uretdione-containing resin A having a uretdione skeleton and a urethane bond, wherein the uretdione concentration in the resin is 0.01 to 5.0 mmol / g.
An isocyanate-containing resin having a step of cleaving the uretdione skeleton contained in the uretdione-containing resin A obtained by the production method according to claim 1 or 2 or the uretdione-containing resin A according to claim 3 to obtain an isocyanate-containing resin B Manufacturing method of B.
The manufacturing method of isocyanate containing resin B of Claim 4 which adds a catalyst further.
A composition comprising the isocyanate-containing resin B obtained in claim 4 or 5 and an alcohol compound.
A method for producing a urethane resin P, comprising the step of reacting the isocyanate-containing resin B obtained in Claim 4 or 5 with an alcohol compound.
Urethane resin P obtained by the manufacturing method of Claim 7.
A laminate comprising a base material and the urethane resin P layer according to claim 8.
The laminate according to claim 8, further comprising an upper layer on the urethane resin P layer.
A method for producing a laminate, comprising the steps of applying the isocyanate-containing resin B obtained in Claim 4 or 5 and an alcohol compound on a substrate, and further reacting the isocyanate-containing resin B and the alcohol compound.
An adhesive comprising the isocyanate-containing resin B obtained in claim 4 or 5.
The adhesive according to claim 12, which is for laminating.
A packaging member comprising the laminate according to claim 9 or 10.
The packaging member according to claim 13, which is for boiling and / or retorting.