JPS58109527A - Polyurethane resin composition - Google Patents

Abstract

PURPOSE:A multi-component, room temperature-curable polyurethane resin composition, comprising an oxidiazinetrione ring-containing isocyanate component, an active hydrogen component and a catalyst component such as a tert. amine. CONSTITUTION:The titled composition is formed from an oxadiazinetrione ring- containing isocyanate component, an active hydrogen component (a compound, MW of about 62-100,000, having at least two active hydrogens) and at least one member selected from the group consisting of a tert. amine (e.g., N,N,N',N'- tetramethylethylenediamine), a tert. phosphine (e.g., triethylphosphine), a quat. ammonium or alkali or alkaline earth metal salt of a weak acid (or hydroxide, alcoholate), e.g., tetramethylammonium acetate, calcium hydroxide, or sodium methylate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel composition for polyurethane resins. More specifically, an incyanate component having an oxadiazinetrione ring, an active hydrogen component, a tertiary amine, a tertiary
The present invention relates to a multi-component room-temperature curable polyurethane resin composition containing class phosphine or quaternary ammonium, a weak acid salt, hydroxide or alcoholade of an alkali metal or alkaline earth metal.

Traditionally, polyurethane resins, such as paints, adhesives, and elastomers, have lower chemical resistance, mechanical properties, stain resistance, adhesion, gloss, abrasion resistance, and better chemical resistance than other synthetic resin paints, adhesives, and elastomers. It has excellent properties such as weather resistance, and is used for wood, metal, and roof tiles.

Concrete, plastic, rubber, paper, flooring.

It is used in a wide range of applications, including waterproofing and sealing materials.

As compositions for these polyurethane resins, multi-component types such as -liquid type and two-liquid type have been proposed, and two-liquid types usually consist of an active hydrogen component as a main ingredient and a polyfunctional polyisocyanate component as a curing agent. It consists of. This curing agent is usually made from diisocyanate, which is reacted with polyol, water, amine, etc. to produce urethane, urea, etc.
Polyisocyanate F having a biuret bond or the like is derived, or a polyisocyanate having an isocyanurate ring is used by performing a trimerization reaction using a catalyst. However, the isocyanate content of such derivatives will be much lower compared to the raw diisocyanate, and therefore a considerably higher amount of curing agent will be required relative to the active hydrogen compound in the base, whereas the curing agent will be added to the base. Since it is relatively expensive, there is a demand for a curing agent that can be cured even in small amounts. In addition, all of these derivatives have high viscosity and may need to be diluted with solvents, so the emergence of high solid content or solvent-free curing agents is desired from the viewpoint of resource conservation and pollution prevention. There is. Furthermore, room temperature curable urethane resin compositions generally require a long time for complete curing, and therefore have drawbacks such as poor workability.

The present invention provides a composition for a solvent-type polyurethane resin, and is also useful as a composition for a solvent-free polyurethane resin. In recent years, many solvent-containing paints, adhesives, and elastomer compositions have been proposed, but these
Compared to solvent-based products, coating properties, drying speed, mechanical performance,
It is inferior in terms of adhesive performance, etc. In the case of a solvent-based composition, an appropriate viscosity can be imparted by adjusting the amount of solvent, but in the case of a solvent-free composition, low molecular weight components are inevitably used as the main ingredient to lower the viscosity. I have no choice but to use . For this reason, the composition requires time to cure and dry, and the physical properties of the cured product are also unsatisfactory.

According to the composition of the present invention, even in the case of a solvent-free type, it is possible to obtain a cured product that has excellent workability, cures in a short time, and has excellent mechanical performance.

The present inventors have demonstrated that the allophane F production reaction from an oxadiazinetrione ring and an active hydrogen compound is a weak acid salt of a tertiary amine, a tertiary phosphine or a quaternary ammonium, an alkali metal or an alkaline earth metal, We found that the process progresses easily even at room temperature in the presence of oxides or alcolades, and as a result of intensive studies to use this as a curing agent for urethane resins, we found that an isocyanate component having an oxadiazinetrione ring was used as a curing agent. This is reacted with an active hydrogen component in the presence of a weak acid salt, hydroxide or alcoholade of a tertiary amine, tertiary phosphine or quaternary ammonium, alkali metal or alkaline earth metal to form a paint.

When making adhesives, efstomers, etc., only a small amount of curing agent is required, and it can be used as a high solids or solvent-free curing agent, and its curing properties are also superior to conventional urethane curing agents. The present invention was completed after realizing that the above-mentioned problems could be solved all at once.

That is, the present invention provides an isocyanate component having an oxadiazinetrione ring, an active hydrogen component, and (a) a tertiary
For multi-component cold-curable polyurethane resins containing a weak acid salt, hydroxide or alcoholade of a tertiary amine, (b) a tertiary phosphine or (C) a quaternary ammonium, an alkali metal or an alkaline earth metal. It is a composition.

The isocyanate component having an oxadiazinetrione ring used in the present invention refers to a compound having both an oxadiazinetrione ring and an incyanate group in the molecule. As a method for synthesizing such a product, specifically, it is obtained by a reaction between isocyanate and carbon dioxide. Examples of such isocyanates include aliphatic, alicyclic, and araliphatic isocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, ω, (Jf-diisocyanato dipropyl ether, 2.6-dicyana t-caproic acid ester,
1.6.11-) Liisocyanatoundecane, bis(isocyanatomethyl)cyclohexane, bis(isocyanato/L/)cyclohexane, 1-isocyanato-3
-isocyanatomethyl-3,5,5-)limethylcyclohexane.

Polyisocyanates such as bis(4-isocyanatocyclohexyl)methane, xylylene diisocyanate, and bis(2-isocyphus)ethyl)benzene are preferably used. These polyisocyanates may be used alone or in mixtures with each other, and monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, ω-chlorohexyl isocyanate, cyclohexyl isocyanate,
It can also be used as a mixture with cyclohexylmethyl isocyanate, pendyl isocyanate, phenylethyl isocyanate, etc.

The reaction between isocyanate and carbon dioxide is carried out in the presence of a catalyst, and tertiary phosphines, arsenic compounds, and hydroquinones can be used as catalysts, and tertiary phosphines are particularly effective.

When an isocyanate having an oxadiazinetrione ring is obtained by the reaction of isocyanate and carbon dioxide, the reaction product can be used as it is or by removing unreacted isocyanate, the oxadiazinetrione ring of the present invention can be obtained. It can be used as an isocyanate component having Usually, various compounds are preferably added to stop the reaction and to stably preserve the product. As the reaction stopper and stabilizer, alkylating agents, acylating agents, acids, ester derivatives, phenols, peroxides, sulfur, polysulfides, metal sulfides, halogens, etc. can be used. In particular, peroxides and sulfur.

The isocyanate component having an oxadiazinetrione ring to which an additive selected from polysulfide, metal sulfide, and halogen is added facilitates the reaction between the oxadiazinetrione ring and isocyanate and the hydroxy group of the active hydrogen component. This is preferable from the point of view of progress.

In addition, when synthesizing an isocyanate component having an oxadiazinetrione ring from polyisocyanate and carbon dioxide, it is necessary to prepare the polyisocyanate and a polyol compound (e.g., ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol) in advance. , hexylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolpropane, polyether polyol, polyester polyol, acrylic polyol, epoxy polyol, etc.) or polyamine compounds (e.g. ethylene diamine, hexamethylene diamine, phenylene diamine, poly An adduct having a terminal NGO group obtained by reacting a polyamine (ether polyamine, polyamide polyamine, etc.) such that NGO groups are in excess can also be used as the polyisocyanate. Furthermore, a polyisocyanate in which part of NGO is blocked with a blocking agent can be used, and a part of these NGO groups can also be dimerized or trimerized.

Furthermore, it is also possible to use isocyanates having oxadiazinetrione rings obtained by the reaction of polyisocyanate and returned acid gas, which are adducted, blocked, or multimerized as described above. Addition, blocking, and multimerization reactions can also be carried out simultaneously when synthesizing the dintrione ring. Further, the above adducts, blocks, multimers, etc. synthesized separately can be mixed with these isocyanates having an oxadiazinetrione ring and used.

Among the isocyanate components having an oxadiazinetrione ring of the present invention as described above, hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-)limethylcyclohexane or bis(isocyanatomethyl) Those derived from (natomethyl)cyclohexane provide particularly excellent compositions in terms of physical properties and curability.

In order to use an isocyanate component having an oxadiazinetrione ring as a curing agent, it is preferable that the average number of functional groups of the oxadiazinetrione ring and isocyanate group in one molecule is about 2 to 10, and the active It is appropriately determined depending on the structure of the hydrogen component, such as the number of functional groups, OH value, molecular weight, etc., the physical properties of the intended resin, and the molecular structure of the curing agent. In addition, if the above-mentioned isocyanate component having an oxadiazinetrione ring contains an isocyaner L monomer, a low-functionality substance, etc. and is not suitable for use as is, an appropriate method such as distillation, extraction, or crystallization may be applied. This is possible by removing the monomers and low-functionality substances. The isocyanate component having an oxadiazinetrione ring obtained in this way can be used as a curing agent as it is, but it is suitable for use after being diluted with an organic solvent, thinner, etc., if necessary. Of course, it is also possible to take a different form.

Active hydrogen components that can be used in the present invention include:
Contains at least 2 active hydrogen atoms and has a molecular weight of 62 to 100
,000, preferably 400 to 50°OOO. More preferably, a polyol having 2 to 50 hydroxyl groups in one molecule and having a molecular weight of 500 to 30,000 is used. In addition to a hydroxyl group, the compound may contain a functional group having active hydrogen, such as a carboxyl group, an amino group, or a thiol group. More specifically, polyester polyols, polyether polyols, polyether ester polyols, polyester amide polyols, acrylic polyols, polyurethane polyols, epoxy polyols, epoxy-modified polyols, polyhydroxyalkanes, oil-modified polyols, castor oil, or mixtures thereof are preferably used. can do.

An example of such a polyene terbolyl is a reaction product of a polyhydric alcohol and a polybasic acid. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol,
Examples include neopentyl glycol, cyclohexane dimetatool, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, glycerol, trimethylolpropane, pentaerythritol, and sorbitol. Examples of polybasic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, and acid anhydrides thereof. can be mentioned. Further, polyester polyols obtained by ring-opening polymerization of lactones such as caprolactone and methylcaprolactone with glycols are also suitable examples.

Examples of polyether polyols are ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Una epoxide compounds such as styrene oxide, epichlorohydrin, phenyl glycidyl ether, allyl glycidyl ether are polymerized in the presence of a catalyst such as boron trifluoride, or these epoxide compounds are used alone or in mixtures, or alternatively with reactive hydrogen atoms. It can be produced by adding it to the included initiator. Reactive hydrogen-containing initiators include, for example, water, polyols such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, amino alcohols such as ethanolamine, polyamines such as ethylenediamine, etc. be.

Examples of polyether ester polyols include those obtained by subjecting the above-mentioned polyether as a raw material to a polyesterification reaction with a polybasic acid, as well as those obtained by wide ring-opening copolymerization of an epoxide compound and an acid anhydride. A compound having both polyether and borie ether segments in one molecule can be mentioned.

Examples of polyesteramide polyols include raw materials having amino groups such as ethylene diamine, propylene diamine, hexamethylene diamine, xylylene diamine, hydrogenated xylylene diamine, ethanolamine, and propatool amine in the above polyesterification reaction. It can be obtained by using

Hydroxyl group-containing polymers, generally referred to as acrylic polyols, are produced by copolymerizing a polymerizable heptamer containing one or more dorxyl groups in one molecule and other polymers that can be copolymerized with this polymer. Can be synthesized. Examples of hydroxyl group-containing monomers include hydroxytrityl acrylate, hydroxypropyl acrylate,
Examples include hydroxybutyl acrylate, trimethylolpropane acrylic acid monoester, their corresponding sulmethacrylic acid derivatives, polyhydroxyalkyl maleate, and fumarate. Examples of copolymerizable monomers include acrylic acid, its methyl, and ethyl esters. , propyl, butyl, 2-ethylhexyl esters, methacrylic acid, maleic acid, fumaric acid, itaconic acid and their corresponding esters as mentioned above; Examples include mercury.

Examples of polyurethane polyols include those having a hydroxyl group at the end, which is a reaction product of a polyol and a polyisocyanate. Examples of polyols include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, cyclohexane dimetatool, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, etc. Examples include polymer polyols such as polyester polyol, polyether polyol, polyester ether polyol, and polyester amide polyol. Examples of polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocypner), 2,6-dicyanatomethyl caproate, 3
-isocyanatomethyl-3,5,5-)limethylcyclohexyl isocyanate), 4,4'-methylenebis(cyclohexyl isocyanate).

1.3- or 1.4-bis(isocyanatomethyl/I
/) Cyclohexane, methylcyclohexane-2,4-
diisocyanate, m- or p-phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate), 2,4- or 2゜6-lylene diisocyanate, 1,3-4 or 1,4-xylylene diisocyanate Dimers of isocyanates (or these polyisocyaners), 3
Examples include polyisocyanates such as polymers.

In addition, a portion of the above polyol may be substituted with ethylenediamine, propylene diamine, hexamethylene diamine, xylylene diamine, bisaminomethylcyclohexane, 3-methyl-3,5,5-)limethylcyclohexylamine, ethanolamine, propatoolamine, etc. Products obtained by replacing and reacting with such amino compounds can also be used as polyurethane polyols.

Examples of epoxy polyols include wire mesh epoxy resins obtained by reacting polyphenol compounds or their nuclear hydrides with epichlorohydrin, and epoxy esters obtained by reacting fatty acids with epoxy resins. Resins and modified epoxy resins obtained by reacting with alkanolamines can also be used. Examples of polyoxyalkanes include saponified vinyl acetate homopolymers or copolymers with other copolymerizable monomers having ethylene bonds, and polybutadiene polyols.

When the composition of the present invention is used as a solvent-free resin composition, among the polyol components (main ingredients), those having a functional group number of 2 to 6. Preferably 2 to 4 and average molecular weight 10.0
00 or less, preferably 400 to 5,000.

Furthermore, not only the hydroxyl group-containing compounds having relatively large molecular weights as described above, but also low molecular weight polyols and low molecular weight polyamines having molecular weights in the range of 62 to 400 can be used alone or in combination. These low molecular weight polyols include, for example, ethylene glycol, propylene glycol, butylene glycol,
These include hexylene glycol, neopentyl glycol, cyclohexane dimetatool, glycerol, trimethylolpropane, pentaerynurritol, diethylene glycol, triethylene glycol, and dipropylene glycol.

In addition, these low molecular weight polyamines include, for example, aliphatic polyamines such as ethylenediamine, propylene diamine, trimethylene diamine, diethylene triamine, tetramethylene diamine, hexamethylene diamine, tolylene diamine, phenylene diamine, etc.
Aromatic polyamines such as 4'-diaminodiphenylmethane, 4,4'-methylenebisorthochloroaniline, 1.2.4-)riaminobenzene, alicyclic polyamines such as pibewodine, cyclohexenediamine, isophorone diamine, xylylene diamine, etc. Examples include aromatic aliphatic polyamines such as amines, hydrofusin, and ammonia.

The ratio of the isocyanate component having an oxadiazinetrione ring and the active hydrogen component is such that the total number of oxadiazinetrione rings and the number of isocyanate groups is usually between 0°1 and 100% relative to the number of active hydrogens in the active hydrogen component. The value is preferably 0.5 to 3, more preferably 0.5 to 3. When used as a paint, it is usually 0.4 to 2, preferably 0.6.
It is best to set it to ~1°4.

The tertiary amine of the present invention includes aromatic and aliphatic tertiary amines, and aliphatic tertiary amines are preferably used. Aliphatic tertiary amines include chain and cyclic amines, and polyamines such as monoamines, diamines, and triamines are used. Suitable examples of such amines include azabicycloalkenes, chain polyamines, cyclic monoamines,
There are partially cyclic polyamines, etc., and these amines have, for example, the general formula [In the formula, R and R' represent an alkylene group having a prime number of 2 to 6] [In the formula, R1 to R4 are hydroxyl or lower alkoxy, respectively. , R is a lower alkylene group, -R'-NR5-R'-(
R' is lower alkylene, RiR-R4 (same meaning) or ")C=NH. Also, kl and R2 or R
3 and R4 together form lower alkylene, -to-o-to-(R
' has the same meaning as above) or -W-NR6e (R' has the same meaning as above, R6 has the same meaning as R-R4)] [In the formula, R is hydroxy/L - or a lower alkyl group optionally substituted with lower alkoxy] [In the formula, R1, R2, and R3 each represent a lower alkyl group optionally substituted with hydroxyl or lower alkoxy] [In the formula, R1 -R2 represents lower alkyl which may be substituted with hydroxyl or lower alkoxy, respectively] These include tertiary amines represented by the following formula.

Specifically, particularly preferred amines include, for example, 1.5
-diazabicyclo(5,4,0)-5-undecene and 1
．． Azabicycloalkenes such as 5-diazabicyclo(4,3°O]-5-nonene, N, N, N', lr-tetramethylethylenediami:/, N, N, V,
N'-7) Lamethyl-1,6-hexanediamine, N
, N-bis(2-dimethylaminoethyl)methylamine, N-(2-dimethylaminoethyl)morpholine, N-
Chain-like and Partially cyclic polyamines, quinuclidine, N, N'-
Examples include cyclic monoamines such as dialkylpiperazines, N-alkylpiperidines, and alkylated derivatives thereof. In addition, 1,2-functional poxyalkane adducts of aliphatic amines are used as MJ-class amines. When the above-mentioned aliphatic amine is used as a catalyst, the curability of the mixture at room temperature is particularly excellent, although the pot life after mixing the components is relatively long. In addition, when a certain amount of forced drying is performed after application, the cured product becomes even more curable. Furthermore, the cured product exhibits particularly excellent properties in terms of weather resistance, gloss, water resistance, and adhesiveness. In addition, salts of organic acids, amino acids, and inorganic acids of the above-mentioned tertiary amines can also be used, and aliphatic tertiary phosphines are used, such as triethylphosphine, tri-n-butylphosphine, dimethylphenyl Phosphine, triphenylhonuphine, diethylcyclohexylphosphine, 1-ethylphosphorane, 1-n-butylhonufolinan, 1,4-diphosphabicyclo(2,2,2]octane,) lis(hydroxyethyl)phosphine, etc.

In addition, weak acid salts of quaternary ammonium include aliphatic,
pK of ammonium with aromatic substituents in water
Examples include salts of acids in which a is greater than 3.

Examples of such weak acids include carboxylic acids such as acetic acid, 2-ethylhexanoic acid, benzoic acid, naphthenic acid, and lactic acid; phenols such as phenol, cresol, and hydroquinone; imidazoles such as imidazole and benzimidazole; succinimide; Examples include imides such as phthalic acid imide, barbylic acid, isocyanuric acid, oxalic acid, cyanic acid, xanthic acid, boric acid, and silicic acid.

As such, for example, tetramethylammonium acetate or trimethyl(2-hydroxyisopropyl)ammonium formate is used. Examples of quaternary ammonium hydroxides include quaternary ammonium hydroxides having aliphatic or aromatic groups, such as tetramethylammonium hydroxide and benzyltrimethylammonium hydroxide.

Examples of the weak acid salts of alkali metals or alkaline earth metals include alkali metal salts or alkaline earth metal salts of the above-mentioned weak acids. Examples of such substances include sodium propionate, potassium 2-ethylhexanoate, calcium naphthenate, sodium fer-
Potassium phthalic acid imide=U can be used. Furthermore, alkali metals or alkaline earth metals,
Hydroxides or alcoholades include hydroxides or alcoholades of metals such as sodium, potassium, lithium, calcium, magnesium, etc., such as sodium methiotate, sodium ethioate, potassium t-butyrate, lithium hydroxide. , sodium hydroxide, calcium hydroxide, and magnesium hydroxide.

of the above tertiary amine, tertiary phosphine or quaternary ammonium, alkali metal or alkaline earth metal,
Weak acid salts, hydroxides, or alcolades act as catalysts for the reaction between the isocyanate component having an oxadiazinetrione ring and the active hydrogen component, and the amount used depends on the base agent, type of curing agent, curing conditions, etc. However, it is usually about 0.001 to 10%, preferably about 0.003 to 5%, based on the weight of the solid content in the base agent and curing agent. In addition, the above amount of addition is sufficient to carry out the reaction of the oxadiazinetrione ring, but for the purpose of adjusting the reactivity of the NCO group in the curing agent, tin, lead, nickel, zinc, titanium, antimony, etc. Known NCOs such as organic compounds, organic acid salts, and inorganic salts of iron, cobalt, bismanium, uranium, cadmium, aluminum, vanadium, mercury, potassium, sodium, zirconium, and other metals.
It is also useful to add compounds that adjust the rate of reaction between groups and OH groups. In addition, pigments, dyes,
Leveling agents, antifoaming agents, anti-sagging agents, fillers, plasticizers, antioxidants, ultraviolet absorbing agents, etc. can be used as appropriate.

The composition of the present invention obtained in this way is usually used as a so-called two-component type consisting of an isocyanate component having an oxadiazinetrione ring and an active hydrogen component, and both components are mixed before use. . At this time, a catalyst such as a tertiary amine may be mixed with either the isocyanate component or the active hydrogen component, but it is preferable to mix it with the active hydrogen component in order to prevent the isocyanate component from deteriorating. preferable. In addition, catalysts such as tertiary amines can be used alone or in a so-called three-component type, in which they are dissolved in a solvent together with a leveling agent, etc., and mixed with an isocyanate component and an active hydrogen component when used. You can also do it. When actually using the composition of the present invention, each component is mixed as it is or in a solution state, and
When applied to a painted or adhesive surface, or injected into a mold, it hardens at room temperature.

The composition of the present invention is useful for painting and adhering wood, metals such as iron and aluminum, puff snacks, rubber, paper, roof tiles, concrete, and the like. Furthermore, the solvent-free adhesive composition is useful as an adhesive for producing multilayer laminate films used as packaging materials for foods and the like. Solvent-free coating compositions are particularly useful for coating areas where solvents cannot be used, such as inside tanks, basements, and ships. The composition of the present invention only requires a small amount of curing agent, about 1/3 to 3/4 of that of conventional urethane curing agents. In addition, the low viscosity of the curing agent makes it suitable for solvent-free or high solids content paints.
It can be used as adhesives, elastomers, etc. Furthermore, the curing properties of the mixture are good despite the relatively long pot life during mixing. Especially after mixing, slightly heat (6
0-100' x 3-60 minutes) has the characteristic that a practically excellent cured product can be obtained.

The resulting paint film has a good texture and excellent weather resistance, and the elastomer has excellent mechanical properties, weather resistance, adhesion,
Excellent wear resistance.

When the composition of the present invention is used as a solvent-free urethane adhesive composition, its viscosity is 100 to 100°C at room temperature to 1°C.
10,000 centipoise, more preferably 100-5
, 000 centivoise, by appropriately selecting the main agent and curing agent, and the usual adhesive processing method can be applied as is.

For example, the composition can be applied to a substrate, such as a film surface, by a solventless laminator.

The solvent-free urethane adhesive composition of the present invention cures faster and has superior adhesive properties than conventional solvent-free urethane adhesive compositions, such as polyethylene terephthalate, nylon, polyethylene, polypropylene, aluminum foil, Extremely high adhesive strength when bonding metal foils such as

It has heat resistance and hot water resistance, and even when the packaging material is filled with food and sealed and subjected to hot water sterilization, there is no separation between the films, providing a packaging material that is good in terms of long-term storage stability of food. be done.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Reference Example/While blowing carbon dioxide gas into 841 g of hexamethylene diisocyanate at 40° C., 1.8 g of lin-n-butylhonufine was added, stirred, and reacted for 6 hours.

Stop the supply of carbon dioxide gas, add 0.3g of sulfur powder, and
After stirring for 0 minutes, the mixture was cooled.

The raw material was removed using a thin film evaporator to obtain 255 g of a pale yellow, slightly viscous liquid. This one is NC
It has an O content of 4.78 meq/g, an oxadiazinetrione content of 2.77 meq/g, a residual amount of 0.4%, and a viscosity at 25°C (Ga-Yf-
) was Y-Z (2,000 cps).

Reference example λ 1.3-bis(isocyanatomethyl)cyclohexane 9
2.1 g of tri-n-butylphosphine was processed into 71 g at 0° C. while blowing carbon dioxide gas, and the reaction was carried out for 7 hours while stirring. The supply of carbon dioxide gas was replaced with nitrogen, 2.7 g of benzoyl peroxide was added, and the mixture was stirred for 80 minutes. When the raw material was removed by evaporation of the product using a thin film distillation apparatus, 165 g of a pale yellow viscous liquid was obtained. This product has an NCo group content of 4°40 meq/g and an oxadiazinetrione content of 2.18.
meq/g Acid residual monomer amount is 0.5%, 70℃
The viscosity was 30,000 cpa.

Reference Example 3 A reaction was carried out for 8 hours in the same manner as in Reference Example λ using 194 g of 1.3-bis(isocyanatomethyl/I/)cyclohexane and 2.0 g of tri-n-butylphosphine, and a reaction was carried out using 2.6 g of benzoyl peroxide. has been stopped. Dissolve the product in 100ml of toluene and add 500ml of n-hexane to this.
was added and mixed well to remove the solvent layer. After repeating this extraction operation three times in total, butyl acetate was added to the extraction residue to obtain a solution with a nonvolatile content of 85%. N of this
The CO content was 2.60 meq/g, and the oxadiazinetrione content was 2.27 meq/g.

10 g of the isocyanate component obtained in Example/Reference Example/ was added to acrylic polyol Acrydic A-850 (OHHIO2
After mixing with 60.5 g of non-volatile content (70% non-volatile content, manufactured by Dainippon Ink Chemical), it was diluted with a mixed solvent of toluene butyl acetate and cellosolve acetate.

To this, 1,5-diazabicyclo(5,4,0)-5-undecene formic acid m601q was added and mixed as a 10% isopropanol solution, and then sprayed onto a mild steel plate to obtain a coating film with a thickness of 50μ. . Table 1 shows the physical properties of the coating film when it was left at room temperature for 7 days. As a comparative example, Duranate N (billet form of hexamethylene diisocyanate, amine equivalent: 208, non-volatile content: 86%, manufactured by Asahi Kasei Corporation)
The physical properties of the coating film obtained by mixing 15 g of Acrydic A-85057, 8 g, diluting with the above solvent, and spray painting are also shown.

Table 1 Example λ After dissolving 20 g of the isocyanate component obtained in Reference Example Y in 20 g of butyl acetate, the polyester polyol
Takerac U-25 ('Off value 140, non-volatile content 7
5% (manufactured by Takeda Pharmaceutical Company)) and further diluted with a mixed solvent of toluene, butyl acetate, and cellosolve acetate. N to this.

N,N'-)limethyl-N'-(hydroxyethyl)ethylenediamine 3doq and diptyltin dilaure)
After each 3W toluene solution was added and mixed, it was spray-painted onto a mild steel plate to obtain a coating film with a thickness of 50 μm. Table 2 shows the physical properties of the coating film when it was left at room temperature for 7 days. As a comparative example, Takene) D-12ON (trimethylolpropane adduct of 1,3-bis(isocyanatomethyl)cyclohexane, amine equivalent 387. Nonvolatile content 75%
.

Takeda Pharmaceutical Industry! [1) 30 g and Takerak U-25
31.1g was mixed and diluted to 17, and the physical properties of the coating film are also shown.

Table 2 Example 3 Synthesis of 5.5 g of the polyisocyanate solution obtained in Reference Example 3 and acrylic polyol (styrene, methyl methacrylate, hydroxyethyl acrylate, ethyl acrylate, butyl acrylate, average molecular weight approximately 13.0)
00. OHHBO2 non-volatile content 50%) sog was mixed. A mixture of each of the catalysts shown in Table 3 was applied onto a glass plate, dried at 80° C. for 30 minutes, and left at room temperature for 3 days. A solvent resistance test (ethyl acetate rubbing) was conducted on the mixture. In addition, the same sample was coated on release paper to form a film, dried and left under the above conditions, and the IR spectrum was measured.
50 cm-1) and oxadiazinetrione group (18
25 cm-1) was determined. As a comparative example, the same test was conducted on coatings and films similarly obtained from 10.3 g of Takene D-12ON and 50 g of the acrylic polyol. The results are shown in Table 3.

Table 3 *DBTL: Dibutyltin diwolate DBU
: 1.5-diazabicyclo(5*4*0]-5
-UndeceneTMHIDA: N,N,N'-)remethyl-'-
(Hydroxyethyl)ethylenediamine TBP:) Liptylphosphine Example/Reference Example/The isoleanate component Log obtained in the polyester polyol Takelac A-606 (OH value 13.
2. After mixing with 200 g of non-volatile content 60%, manufactured by Shikinichi Yakuhin Kogyo, it was diluted with 300 g of ethyl acetate. 1 for this,
5-Diazabicyclo(5,4,0)-5-undecene0
．． 13 g was added and mixed, and this was applied to a nylon film, dried, and a polypropylene film was attached. The coating amount was 3.5 g/m2. 4 of the pasted films
After being left at 0°C for 3 days, the adhesive strength was measured and found to be 1.
000g and 715mm.

Example: 268 g of trimethylolpropane, 134 g of dipropylene glycol/I/1, 292 g of adipic acid, and 200 g of coconut oil fatty acid were mixed, nitrogen gas was blown in, water produced was distilled off, and the mixture was heated to 210-220°C for 10 hours. Heat to acid value 3
,5. A polyester polyol having a hydroxyl value of 215° and a viscosity of 3050 cps was obtained. Polyester polyol with 2
60 g and 132.5 g of the isocyanate component of Reference Example 1 were mixed, and 1.3 g of triptylphomefin and 0.04 g of dibutyltin diurethane were added and mixed, and then coated on a mild steel plate with a percoater to form a film with a film thickness of 50 μm. A coating film was obtained.

When this was left at room temperature for 7 days, the physical properties of the coating film were as follows.

Curing time 5 hours 40 minutes Pencil hardness F Erichsen test 8n+m Goban test 100/100 Impact test % inch x 1000g x 50
cm Bending resistance test 2mm Solvent resistance (Vinegar production) Passed example O - Hydroxyl value obtained by adding propylene oxide to glycerin 530. 106 g of a polyether polyol with a viscosity of 600 cps was mixed with 151 g of the isocyanate component obtained in Reference Example λ, and 1.28 g of N,N,1-)limethyl-V-(hydroxyethyl)ethylenediamine was mixed therewith.
After adding and mixing 0.013 g of Tetopthiru-1,3-diacetoxydistanoxane, the mixture was coated on a mild steel plate using a bar coater to obtain a coating film with a thickness of 50 μm. When this was left at room temperature for 7 days, the physical properties of the coating film were as follows.

Curing time: 10 hours Pencil hardness: H Erichsen test: 8mm Grid test: 100/100 Impact resistance test: W inch molar ratio), polyester glycol (molecular weight t, soo) consisting of diethylene glycol (molecular weight t, soo) 9og and diethylene glycol/I'
66 g of the isocyanate component obtained in Reference Example/ was mixed with 10 g of the mixture at 40° C., and then 0.16 g of 1.5-azabicyclo(5,4,0)-5-undecene was added to prepare an adhesive composition. I got 1. Viscosity at 40℃ is 3,00
It was 0 cps.

Immediately, Composition 1 was applied to a polyester film (PET thickness 12 μm) at a coating amount of 1.5 g/m” using a solvent-free huminator at a temperature of 40° C., and aluminum foil (Al thickness 9 μm) was coated. Next, it was applied to the aluminum surface at a coating amount of 1°5 g/s2, and unstretched polypropylene (CPP thickness 60μ9 surface corona treated) was pasted, and the three layers were cured at 40°C for 3 days. When the normal adhesive strength between A1/CP
m/min, T-type peeling 1III). In addition, a bag with a propylene film interior was made from this laminated film, and the bag was filled with meat sauce (Nissin Seifun ■).
After hot water sterilization was performed at 20° C. for 30 minutes under a pressure of 2 kg/cI [l”, the peeling state between Al/CPP and changes in adhesive strength were examined.

Adhesive strength 920g/15nun Peeling condition No change from before hot water sterilization Example and polyester glycol consisting of isophthalic acid/adipic acid = 3/1 (molar ratio) and ethylene glycol/neopentyl glycol - 2/3 (molar ratio) (molecular weight 600)
After uniformly mixing 100 g of Epikote 1002 (epoxy resin manufactured by Shell Chemical ■) at 90°C, the temperature was lowered to 60°C.
℃ and mixed with 60 g of the isocyanate component obtained in Reference Example/, followed by 0.4 g of potassium 2-ethylhexane.
were added and mixed to obtain adhesive composition 2. The viscosity at 60°C was 2,300 cpa.

Immediately, Composition 2 was treated in the same manner as in Example Z, except that it was laminated at a temperature of 60° C., and an Al/CPP adhesion test was conducted.

Normal adhesive strength 1200 g / 15 + no + adhesive strength after hot water sterilization 1250 g / 15 mm Peeling condition No change from before sterilization Example taxylylene diisocyaner) 18.8 g, yt'! J oxypropylene glycol (molecule i1000) 100g
After reacting 13.4 g of dipropylene glycol at 80° C. for 4 hours to obtain a polyurethane polyol, the temperature was lowered to 60° C. and 40% methanol of trimethylbenzylammonium hydroxide was mixed. Next, 66.1 g of the isocyanate component obtained in Reference Example 2 was mixed to obtain an adhesive composition. The viscosity at 60°C was 5+ OOOc ps.

Immediately, this composition was treated in the same manner as in Example 7 except that it was laminated at a temperature of 60° C., and an adhesion test between A 1 and CP P was conducted.

Normal adhesive strength 800g/15 stamps Adhesive strength after hot water sterilization 750g/15mm Peeling condition No change from before sterilization Comparative example/Solvent-free adhesive Takene) A-259 (Shikinichi Yakuhin Kogyo)
A l/CP was prepared in the same manner as in Example Z except that a polyether polyurethane polyisocyanate adhesive (80°C viscosity 2.000 cps) was laminated at a temperature of 80°C.
An adhesion test between P was conducted.

Normal adhesive strength 300g/15mm Adhesive strength after hot water sterilization 200g/15mm Peeling condition Partially peeled Comparative example λ 98.
3 g of the mixture was reacted at 80° C. for 4 hours to obtain a polyurethane product. The viscosity of this product at 80°C was 2.220. This was treated in the same manner as in Example Z except that it was laminated at a temperature of 80° C., and an adhesion test between A 1 and CP P was conducted.

Normal adhesive strength 7sog/15cm Adhesive strength after hot water sterilization 400 # Peeling condition Partially peeled off Example 10 Acrylic polyol (styrene, methyl methacrylate, hydroxyethyl acrylate, ethyl acrylate, butyl acrylate synthesized, average Molecular weight 12,00
0. OH value 40. 6.0 g of the isocyanate component obtained in Reference Example 1 diluted with 100 g of a mixed solvent of toluene, butyl acetate, and 2-ethoxyethyl acetate was mixed with 50 g of non-volatile content (50%). Add 5% of sodium hydroxide to this
% ethanol solution was added and mixed, and the mixture was spray-painted onto a mild steel plate to obtain a coating film with a thickness of 50 μm.

The physical properties of the coating film when the coated product was left at room temperature (10-25°C) for 7 days were as follows.

Curing time: 2 hours and 40 minutes Pencil hardness: F~H Erichsen test: 8mm Gopin test: 100/100 Impact test: %in or 1000g x 50c
mBending resistance test 2mm Solvent resistance Passing example // Polyester polyol Takelac A-605 (OH
Value 13.2. Non-volatile content 60%, manufactured by Trial Yakuhin Kogyo) 100
g and 5 g of the isocyanate component obtained in Reference Example/ were mixed and diluted with 150 g of ethyl acetate. To this, 10 g of a 1% methanol solution of potassium cyanate was added and mixed, and this was applied to a nylon film, dried, and a polypropylene film was attached. ,"The application amount is 3.5
g/m2. After leaving the bonded film on 201E for 7 days, the adhesive strength was measured and found to be 850g/
15I! It was ll11.

Example/2 Polypropylene glycol 150 with a hydroxyl value of 56.1
g.) 5.1 g of limethylolbroban and 1 g of potassium 2-ethylhexanoate were uniformly mixed to prepare an active hydrogen component. Particularly, 39.2 g of the isocyanate component obtained in Reference Example/1 was mixed, spread on a glass plate treated with mold release, and left at 25°C. After 24 hours, the mixture became an elastomer and could be demolded from the glass plate. After being left at 25°C for further 5 days, the cured product exhibited the following physical properties.

Hardness (Tl5A) 56 Tensile strength kg/cm" 28 Elongation % 310 Example/3゜1551 g of polybutylene adipate diol with a hydroxyl value of 108.5, 135 g of 1.4-butanediol and 167 g of isophoro diisocyanate) was reacted at 80°C for 2 hours in the presence of 0.3 g of diptyltin dilaurate, and 1853 g of methyl ethyl ketone was added and further reacted at 70°C for 6 hours to obtain a polyester polyol having urethane bonds.

The OH value of this product is 18. The viscosity at 25°C is 2.2
It was 10 cps. 100g of the obtained polyester polyol having urethane bonds1 150g of butyl acetate,
) 0.5 g of liptylphosphine and 28 g of the isocyanate component obtained in Reference Example/2 were mixed and sprayed onto soft PVC leather and dried at 40° C. for 5 hours to obtain a 30 μm film. As a comparative example, 100 g of the above-mentioned polyester polyol having urethane bonds, 150 g of butyl acetate, and 35 g of Dulaney N (Biulet form of hexamethylene diisocyanate, amine equivalent 208, non-volatile content 86%, manufactured by Asahi Kasei Kogyo) were mixed, and a soft salt was prepared. The mixture was sprayed on Villezer and dried at 40°C for 5 hours to obtain a 30μ film.

The cured film exhibited the following physical properties.

Isocyanate component reference example/ Duranate N triclean wobbing test o
×Adhesion (cross cut)
○ ○Example/4t.

Polyoxyethylene propylene glycol with an OH value of 56.0 (propylene oxide/ethylene oxide = 90
/10wt) 150g, calcium carbonate 100g, colloidal silica 8g, titanium oxide 20g, carbon 0
．． 0.05 g, N, N, lr-trimethyl-N-(hydroxyethyl)ethylenediamine 0.2 g were kneaded using a Miki roll to obtain a gray paste-like polyol compound. The polyol compound 10 (l) was mixed with 6.0 g of the isocyanate component obtained in Reference Example λ, and the width was 2-Q.
It was filled into concrete F joints with a depth of 1.0 cm and a depth of 1.0 cm.

After 3 days at room temperature, the mixture hardens to a hardness of 20° (, Tl
5A) became Fstomer. It also had good adhesion to concrete and functioned as a sealant. As a comparative example, 100 g of the polyol compound and Takenate D-12ON (1,3-bis(isocyanatomethyl)S/trimethylolpropane adduct of chlorohexane, amine equivalent: 337, non-volatility: 75%, manufactured by Trial Yakuhin Kogyo)13. 5g of the mixture was mixed and similarly filled into concrete joints, but it did not harden even after 5 days.

Example/Polyoxypropylene glycol 1 with a hydroxyl value of 112
00g and 12.5g of methylene diorthochloroaniline were mixed at 90°C for 1 hour to form a uniform solution. Subsequently, 0.5 g of 1.5-diazabicyclo(5,4,0)-5-undecene was mixed at room temperature, and 31 g of the isocyanate component obtained in Reference Example U was mixed and poured into an aluminum mold at 35°C. did.

After 1 hour, a urethane elastomer foam with a specific gravity of 0.85 was obtained.

Example/1. .

Polyoxyethylene propylene triol with a hydroxyl value of 33.5 (propylene oxide/ethylene oxide = 8
0/20wt) 43kg, ethylene glycol 6, O
kg and 0.43 kg of 1.5-diazabicyclo[5,4,0)-5-undecene were mixed to adjust the active hydrogen component, and the mixture was charged into a reaction precipitation molding machine tank, and the temperature was adjusted to 40°C. On the other hand, reference example/polyisocyanate component 40 kg
into the other tank of the reaction injection molding machine and set the temperature to 40
The temperature was adjusted to ℃. The molding machine was adjusted so that the mixing ratio of the active hydrogen component and the polyisocyanate component was 100:35 (by weight), and an aluminum mold (space 3 x 30
0x1000mm). After 3 minutes, the mold was cured to a state where it could be demolded. Molded elastomer has a hardness of 95°
(J Engineering S-A), specific gravity was 0°95.

Claims (2)

[Claims] (1) An isocyanate component having an oxadiazinetrione ring, an active hydrogen component and (at tertiary amine, (
b) g 3 R phosphine or (C) a weak acid salt, hydroxide or alcolade of quaternary ammonium, alkali metal or alkaline earth metal; a multi-component room temperature curable polyurethane resin composition; (2) The composition for polyurethane resin according to claim (1), which does not contain a solvent in which the active hydrogen component has a molecular weight of 10,000 or less.