JP2020138999A - Polyisocyanate composition - Google Patents

Abstract

To provide a polyisocyanate composition that can achieve both a heat-resistant adhesion property and solvent resistant property, and a handleability.SOLUTION: Provided is a polyisocyanate composition containing a xylylene diisocyanate composition that contains isocyanurate of xylylene diisocyanate, and a hexamethylene diisocyanate composition that contains allophanate of hexamethylene diisocyanate, and in which, for the total amount of hexamethylene diisocyanate composition, allophanate of hexamethylene diisocyanate is 30 mass% or more, for the total amount of the xylylene diisocyanate composition and the hexamethylene diisocyanate composition, the xylylene diisocyanate composition is 80 mass% or more and 95 mass% or less, and the hexamethylene diisocyanate composition is 5 mass% or more and 20 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to a polyisocyanate composition.

Polyurethane resins are usually produced by the reaction of polyisocyanates with active hydrogen group-containing compounds, and are widely used in various industrial fields as, for example, coating materials, adhesive materials, adhesive materials, elastomers, and the like.

As the polyisocyanate used for producing a polyurethane resin, for example, xylylene diisocyanate and its derivative, hexamethylene diisocyanate and its derivative, and the like are known, and it is known that they are mixed and used.

More specifically, it is proposed that, for example, an isocyanurate derivative of xylylene diisocyanate and Takenate D-170N (trimer of hexamethylene diisocyanate, solid content concentration 100%) are mixed and used as a curing agent. (See, for example, Patent Document 1 (Examples 21-26 and 31-35)).

According to such a curing agent, a polyurethane resin having excellent heat resistance and solvent resistance can be obtained.

International pamphlet WO2015 / 133496

On the other hand, the curing agent is required to have handleability in order to improve the productivity of the polyurethane resin. However, by improving the handleability of the curing agent, the heat-resistant adhesion and solvent resistance of the polyurethane resin may decrease.

The present invention is a polyisocyanate composition capable of achieving both heat-resistant adhesion, solvent resistance, and handleability.

The present invention [1] contains a xylylene diisocyanate composition containing an isocyanurate of xylylene diisocyanate and a hexamethylene diisocyanate composition containing an allophanate of hexamethylene diisocyanate. The allophanate of the hexamethylene diisocyanate is 30% by mass or more with respect to the total amount, and the xylylene diisocyanate composition is 80 with respect to the total amount of the xylylene diisocyanate composition and the hexamethylene diisocyanate composition. The hexamethylene diisocyanate composition contains a polyisocyanate composition of 5% by mass or more and 95% by mass or less, and 5% by mass or more and 20% by mass or less.

The present invention [2] includes the polyisocyanate composition according to the above [1], wherein the isocyanurate of the xylylene diisocyanate is modified with an alcohol.

The polyisocyanate composition according to the above [1] or [2], wherein the allophanate of the hexamethylene diisocyanate is 60% by mass or more based on the total amount of the hexamethylene diisocyanate composition. Includes.

In the present invention [4], the hexamethylene diisocyanate composition contains an isocyanurate of hexamethylene diisocyanate, and the allophanate of the hexamethylene diisocyanate is less than 60% by mass with respect to the total amount of the hexamethylene diisocyanate composition. The polyisocyanate composition according to the above [1] or [2], wherein the isocyanurate of the hexamethylene diisocyanate exceeds 40% by mass.

Since the polyisocyanate composition of the present invention is excellent in handleability, the productivity of the polyurethane resin is excellent, and the obtained polyurethane resin has excellent heat resistance and solvent resistance.

The polyisocyanate composition of the present invention contains a xylylene diisocyanate composition and a hexamethylene diisocyanate composition in a predetermined ratio described later.

In the present invention, the xylylene diisocyanate composition (hereinafter, may be referred to as XDI composition) contains isocyanurate of xylylene diisocyanate.

Examples of the xylylene diisocyanate include 1,2-xylylene diisocyanate (o-xylylene diisocyanate (o-XDI)), 1,3-xylylene diisocyanate (m-xylylene diisocyanate (m-XDI)), and 1,4-. Xylylene diisocyanate (p-xylylene diisocyanate (p-XDI)) is mentioned as a structural isomer.

These xylylene diisocyanates can be used alone or in combination of two or more.

Examples of the xylylene diisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and more preferably 1,3-xylylene diisocyanate.

Isocyanurates are variants containing one or more symmetric isocyanurate groups and / or asymmetric isocyanurate groups (iminooxadiazidinedione groups) in the molecule.

The modified product containing a symmetric isocyanurate group (symmetrical isocyanurate modified product) and the modified product containing an asymmetrical isocyanurate group (iminooxadiazinedione modified product) are structural isomers. Therefore, an iminooxadiazine dione modified product may be produced as a by-product during the production of the symmetrical isocyanurate modified product, and a symmetrical isocyanurate modified product may be produced as a by-product during the production of the iminooxadiazine dione modified product. May occur.

The isocyanurate of xylylene diisocyanate can be obtained, for example, by subjecting the xylylene diisocyanate to an isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst.

The isocyanurate-forming catalyst is not particularly limited as long as it is a catalyst that activates isocyanurate-forming, and is, for example, a secondary amine such as triethylamine, tributylamine, triethylenediamine, or a secondary amine copolymer (for example, dialkylamine). , And tertiary amines such as polycondensates of monomers copolymerizable with secondary amines (eg, phenol, formaldehyde, etc.), such as 2-dimethylaminomethylphenol, 2,4,6-tris (eg, 2,4,6-tris). Mannich bases such as dimethylaminomethyl) phenols, such as tetraalkylammonium hydroxides such as tetramethylammonium, tetraethylammonium, tetrabutylammonium and their organic weak salts, such as trialkylaryls such as trimethylbenzylammonium and tributylbenzylammonium. Hydrooxide of ammonium and its organic weakened salts, such as trimethylhydroxypropylammonium (also known as N- (2-hydroxypropyl) -N, N, N-trimethylammonium), trimethylhydroxyethylammonium, triethylhydroxypropylammonium, triethylhydroxy Hydrooxides of trialkylhydroxyalkylammoniums such as ethylammonium and their organic weakened salts, such as metal salts of alkylcarboxylic acids such as acetic acid, caproic acid, octyl acid, myristic acid, naphthenic acid (eg alkali metal salts, magnesium salts). , Tin salt, zinc salt, lead salt, etc.), eg, metal chelate compounds of β-diketone, such as aluminum acetylacetone, lithium acetylacetone, etc., Friedel Crafts catalysts such as aluminum chloride, boron trifluoride, eg. Various organic metal compounds such as titanium tetrabutyrate and tributylantimon oxide, for example, aminosilyl group-containing compounds such as hexamethylsilazane, halogen-substituted organic phosphorus compounds such as tetrabutylphosphonium hydrogen difluoride, and the like can be mentioned.

These isocyanurate-forming catalysts can be used alone or in combination of two or more.

From the viewpoint of production efficiency, the isocyanurate-forming catalyst preferably includes tetraalkylammonium hydroxide and trialkylhydroxyalkylammonium hydroxide, and more preferably tetraalkylammonium hydroxide. Can be mentioned as a tetrabutylammonium hydroxide.

Further, the isocyanurate-forming catalyst may be used as a solid content of 100%, or a catalyst solution in which the isocyanurate-forming catalyst is dissolved in an organic solvent may be used.

Preferably, the isocyanurate-forming catalyst is used as a catalytic solution.

In the catalyst solution, examples of the organic solvent include alcohols (eg, methanol, ethanol, propanol, butanol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), nitriles (eg, acetonitrile, etc.). ), Alkyl esters (eg, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc.), glycol ether esters (eg, methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl Ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc.), ethers (eg, diethyl ether, tetrahydrofuran, dioxane, etc.), polar aprotons (eg, diethyl ether, tetrahydrofuran, dioxane, etc.) , N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, etc.) and the like. The organic solvent can be used alone or in combination of two or more.

Among the organic solvents, glycol ether esters are preferable, and propylene glycol methyl ether acetate is more preferable.

The solid content concentration (content ratio of isocyanurate-forming catalyst) of the catalyst solution is, for example, 60.0% by mass or less, preferably 50.0% by mass or less.

The addition ratio of the isocyanurate-forming catalyst (in terms of solid content) is, for example, 0.001 part by mass or more, preferably 0.005 part by mass or more, for example, 0.1 part by mass with respect to 100 parts by mass of xylylene diisocyanate. Hereinafter, it is preferably 0.05 parts by mass or less.

Then, in this method, the isocyanurate-forming catalyst is added all at once or dividedly to the xylylene diisocyanate at the above-mentioned compounding ratio, and the isocyanurate-forming reaction is carried out by heating.

The reaction conditions for the isocyanurate-forming reaction of xylylene diisocyanate include, for example, an atmosphere of an inert gas such as nitrogen gas, under normal pressure (atmospheric pressure), and a reaction temperature (maximum temperature reached), for example, room temperature (for example, 25 ° C.). ) Or more, preferably 40 ° C. or higher, more preferably 60 ° C. or higher, for example, 100 ° C. or lower, preferably 90 ° C. or lower, and the reaction time is, for example, 30 minutes or longer, preferably 1 hour or longer. More preferably, it is 2 hours or more, for example, 12 hours or less, preferably 10 hours or less, and further preferably 8 hours or less.

Further, in the above reaction, if necessary, a known reaction solvent may be blended in an appropriate ratio.

Then, in the above-mentioned isocyanurate-forming reaction, preferably, a catalyst deactivating agent is added at an arbitrary timing to stop the reaction. The timing of adding the catalyst deactivating agent is, for example, when the conversion rate of the isocyanate group reaches a target value (for example, 10% or more, preferably 20% or more, for example, 40% or less).

Examples of the catalytic deactivator include phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid, paratoluenesulfonic acid, orthotoluenesulfonic acid, benzoylchloride, p-toluenesulfonamide, o-toluenesulfonamide and the like. The catalyst deactivating agent can be used alone or in combination of two or more. The blending ratio of the catalyst deactivating agent is not particularly limited, and is appropriately set according to the purpose and application.

Thereby, isocyanurate of xylylene diisocyanate can be obtained.

Further, in the above-mentioned isocyanurate-forming reaction, known additives such as an antioxidant and a cocatalyst (for example, an organic phosphite ester) can be added, if necessary.

Preferred examples of the additive include antioxidants.

Examples of the antioxidant include a phenol-based antioxidant and a hindered phenol-based antioxidant, and from the viewpoint of hygiene, a hindered phenol-based antioxidant is preferable. Specific examples of the hindered phenolic antioxidant include 2,6-di (tert-butyl) -4-methylphenol and [3- [3- (3,5-di-tert-butyl-4). -Hydroxyphenyl) propanoyloxy] -2,2-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoyloxymethyl] propyl] 3- (3,5-ditert- Butyl-4-hydroxyphenyl) propanoate (Irganox 1010, manufactured by Ciba Japan, trade name), octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, Ciba- Japan, trade name), 3- (4-hydroxy-3,5-diisopropylphenyl) propionic acid octyl ester (Irganox 1135, Ciba Japan, trade name), bis [3- (3-methyl-) 4-Hydroxy-5-tert-butylphenyl) propionic acid] ethylene bisoxybisethylene (Irganox 245, manufactured by Ciba Japan, trade name) and the like can be mentioned.

These antioxidants can be used alone or in combination of two or more.

From the viewpoint of hygiene, the antioxidant preferably includes a hindered phenolic antioxidant other than BHT, and more preferably octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate (Irganox 1076, manufactured by Ciba Japan, trade name) can be mentioned.

The timing of adding the additive is not particularly limited, and it may be added to the xylylene diisocyanate before the isocyanurate-forming reaction, or it may be added to the isocyanurate reaction solution during the isocyanurate-forming reaction. Furthermore, it may be added to the isocyanurate reaction solution after the isocyanurate conversion reaction. Preferably, it is added to the xylylene diisocyanate before the isocyanurate-forming reaction.

The addition ratio of the additive is appropriately set according to the purpose and application.

Further, in the above reaction, alcohol can be blended if necessary. That is, the isocyanurate of xylylene diisocyanate can be modified with alcohol.

Examples of the alcohol include aliphatic alcohols and aromatic alcohols, and preferred examples include aliphatic alcohols.

Examples of the fatty alcohol include monohydric fatty alcohols, divalent fatty alcohols, trivalent fatty alcohols, and tetrahydric or higher fatty alcohols.

Examples of the monohydric aliphatic alcohol include a linear monohydric aliphatic alcohol and a branched monovalent aliphatic alcohol.

Examples of the linear monohydric fatty alcohol include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, and n-decanol. , N-undecanol, n-dodecanol (lauryl alcohol), n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol) , N-Nonadecanol, Eikosanol and the like, linear monohydric fatty alcohols having 1 to 20 carbon atoms and the like.

Examples of the branched monohydric fatty alcohol include isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, isohexanol, isoheptanol, isooctanol, 2-ethylhexanol, isononanol, isodecanol, and 5 -Ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, and other branched alkanols (5-carbon number) Examples thereof include branched monohydric fatty alcohols having 1 to 20 carbon atoms such as 20).

Examples of the divalent aliphatic alcohol include methanediol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-dihydroxy. Linear divalent aliphatic alcohols such as -2-butene, diethylene glycol, triethylene glycol, dipropylene glycol and other linear alkane (C7-20) diols, such as 1,2-propanediol, 1 , 3-butanediol, 1,2-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 3,3-dimethylol heptane, Branched divalent aliphatic alcohols such as 2,6-dimethyl-1-octene-3,8-diol and other branched alkane (C7-20) diols, such as 1,3- or 1,4-. Divalent with 1 to 20 carbon atoms, such as cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, alicyclic divalent aliphatic alcohols such as bisphenol A hydride. Examples include aliphatic alcohols.

Examples of the trivalent aliphatic alcohol include trihydric aliphatic alcohols having 1 to 20 carbon atoms such as glycerin and trimethylolpropane.

Examples of the tetravalent or higher fatty alcohol include tetravalent fatty alcohols having 1 to 20 carbon atoms such as tetramethylolmethane, D-sorbitol, xylitol, and D-mannitol.

Further, as long as the alcohol has one or more hydroxy groups in the molecule, the other molecular structures are not particularly limited as long as the excellent effects of the present invention are not impaired. For example, in the molecule, It can also have an ester group, an ether group, a cyclohexane ring, an aromatic ring and the like. Examples of such alcohols include ethers that are addition polymers (random and / or block polymers of two or more types of alkylene oxides) of the above-mentioned aliphatic alcohols and alkylene oxides (for example, ethylene oxide, propylene oxide, etc.). Examples thereof include group-containing alcohols, ester group-containing alcohols which are addition polymers of the above-mentioned aliphatic alcohols and lactones (for example, ε-caprolactone, δ-valerolactone, etc.).

These alcohols can be used alone or in combination of two or more.

The alcohol preferably includes an aliphatic alcohol, more preferably a monohydric and a divalent aliphatic alcohol, and further preferably a divalent aliphatic alcohol.

Further, as the aliphatic alcohol, preferably, an aliphatic alcohol having 1 to 20 carbon atoms, more preferably, an aliphatic alcohol having 2 to 20 carbon atoms, and further preferably, an aliphatic alcohol having 2 to 8 carbon atoms. , And particularly preferably fatty alcohols having 2 to 6 carbon atoms.

Further, as the aliphatic alcohol, preferably, branched monovalent and divalent aliphatic alcohols can be mentioned, more preferably, branched divalent aliphatic alcohols can be mentioned, and further preferably, the number of carbon atoms is 2. Examples thereof include branched divalent aliphatic alcohols having to 8 to 8, more preferably branched divalent aliphatic alcohols having 2 to 6 carbon atoms, and particularly preferably 1,3-butanediol. Can be mentioned.

The mixing ratio of the alcohol is, for example, 0.1 part by mass or more, preferably 1.0 part by mass or more, more preferably 1.5 parts by mass or more, and more preferably 1.5 parts by mass or more, based on 100 parts by mass of xylylene diisocyanate. For example, it is 10 parts by mass or less, preferably 5.0 parts by mass or less. The equivalent ratio (NCO / OH) of the isocyanate group of the xylylene diisocyanate to the hydroxy group of the alcohol is, for example, 5 or more, preferably 10 or more, more preferably 20 or more, usually 1000 or less, preferably. It is 100 or less, more preferably 50 or less.

Further, as a method for modifying the isocyanurate of xylylene diisocyanate with alcohol, more specifically, for example, first, xylylene diisocyanate is reacted with alcohol, and then isocyanurate-forming reaction in the presence of an isocyanurate-forming catalyst. Then, a method of removing the unreacted xylylene diisocyanate, for example, first, only the xylylene diisocyanate is isocyanurate-ized by the above method, and then the unreacted xylylene diisocyanate is removed, and then obtained. Examples thereof include a method of reacting polyisocyanurate with alcohol.

Preferably, the xylylene diisocyanate is first reacted with an alcohol, and then the isocyanurate-forming reaction is carried out in the presence of an isocyanurate-forming catalyst, and then the unreacted xylylene diisocyanate is removed.

In this method, first, xylylene diisocyanate and alcohol are mixed and reacted.

The reaction between xylylene diisocyanate and alcohol is a urethanization reaction (including an allophanate reaction), and the reaction conditions include, for example, an inert gas atmosphere such as nitrogen gas and a reaction under normal pressure (atmospheric pressure). The temperature is, for example, room temperature (for example, 25 ° C.) or higher, preferably 40 ° C. or higher, and for example, 100 ° C. or lower, preferably 90 ° C. or lower. The reaction time is, for example, 0.05 hours or more, preferably 0.2 hours or more, for example, 10 hours or less, preferably 6 hours or less, and more preferably 3 hours or less.

Further, in the urethanization reaction, for example, a known urethanization catalyst such as amines or an organometallic compound may be added at an appropriate ratio, if necessary.

Examples of amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether and N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, for example, imidazole. Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

Examples of the organic metal compound include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, and dibutyltin dilaurate (dilauric acid). Organic tin compounds such as dibutyltin (IV)), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurylate, dibutyltin dichloride, eg, organic lead compounds such as lead octanoate, lead naphthenate, eg Examples thereof include organic nickel compounds such as nickel naphthenate, for example, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compounds such as copper octeneate, for example, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.

Further, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate and potassium octylate.

These urethanization catalysts can be used alone or in combination of two or more.

Next, in this method, an isocyanurate-forming catalyst is blended with the obtained reaction solution at the above-mentioned blending ratio, and the reaction product of xylylene diisocyanate and alcohol is subjected to an isocyanurate-forming reaction. The reaction conditions for isocyanurate formation are the same as above. Then, after the reaction is completed, the unreacted xylylene diisocyanate is removed by a known removal method such as distillation, if necessary.

As a result, isocyanurate of xylylene diisocyanate (isocyanurate modified with alcohol) is obtained.

Further, for example, when a method is adopted in which only xylylene diisocyanate is isocyanurate, then unreacted xylylene diisocyanate is removed, and the obtained polyisocyanate is reacted with an alcohol (the latter method described above). , Isocyanurate of xylylene diisocyanate reacts with alcohol. This reaction is also a urethanization reaction, and the reaction is carried out under the above-mentioned reaction conditions of the urethanization reaction.

This also gives an isocyanurate of xylylene diisocyanate (isocyanurate modified with alcohol).

Then, in this method, after the completion of the isocyanurate-forming reaction, if necessary, an unreacted xylylene diisocyanate monomer (further, if necessary, a catalyst, a reaction solvent and / or) is added from the obtained reaction mixture. (Catalyst deactivator, etc.) is removed by a known method such as distillation such as thin film distillation (Smith distillation) or extraction.

As a result, an XDI composition containing an isocyanurate of xylylene diisocyanate is obtained.

In such a method, in the urethanization reaction and isocyanurate-forming reaction of xylylene diisocyanate, depending on the reaction conditions, in addition to the isocyanurate of xylylene diisocyanate, other xylylene diisocyanate derivatives (derivates excluding isocyanurate of xylylene diisocyanate). For example, an allophanate of xylylene diisocyanate, a dimer of xylylene diisocyanate (such as biuret), etc.) is obtained as a by-product.

In particular, when the isocyanurate of xylylene diisocyanate is modified by alcohol, allophanate of xylylene diisocyanate is produced as another xylylene diisocyanate derivative.

Further, if necessary, other xylylene diisocyanate derivatives (for example, xylylene diisocyanate allophanate, xylylene diisocyanate dimer (biuret, etc.), etc.) are prepared separately from the isocyanurate of xylylene diisocyanate. Isocyanurate of the above can be mixed with other xylylene diisocyanate derivatives to prepare an XDI composition.

In other words, the XDI composition can contain isocyanurates of xylylene diisocyanates and other xylylene diisocyanate derivatives.

From the viewpoint of heat-resistant adhesion (heat-resistant adhesion retention rate) and solvent resistance of the polyurethane resin (described later), the XDI composition preferably contains isocyanurate of xylylene diisocyanate and allophanate of xylylene diisocyanate.

From the viewpoint of heat adhesion and solvent resistance of the polyurethane resin (described later), the proportion of isocyanurate of xylylene diisocyanate is, for example, 80% by mass or more, preferably 85, based on the total solid content of the XDI composition. By mass or more, more preferably 90% by mass or more, for example, 100% by mass or less, preferably 98% by mass or less, more preferably 95% by mass or less.

Further, the ratio of the other xylylene diisocyanate derivative (preferably allophanate of xylylene diisocyanate) is, for example, 0% by mass or more, preferably 2% by mass or more, based on the total solid content of the XDI composition. It is preferably 5% by mass or more, for example, 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.

The isocyanurate contained in the XDI composition may be either isocyanurate of xylylene diisocyanate which is not essentially modified with alcohol, or isocyanurate of xylylene diisocyanate modified with alcohol. , Preferably, isocyanurate of xylylene diisocyanate modified with alcohol.

The isocyanate that is not essentially modified by alcohol is defined as a derivative that does not positively contain the above-mentioned alcohol as a denaturing agent. For example, an alcohol that is inevitably mixed in during the production of isocyanurate (for example, isocyanurate). , Isocyanurate-forming catalyst solvent (for example, methanol, etc.) and water-based modifying groups (for example, urethane group, urea group, etc.) are allowed to be contained (the same applies hereinafter).

In the XDI composition, the isocyanate group concentration (solid content 100% by mass) is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 18% by mass or more, and for example, 45% by mass or less. It is preferably 40% by mass or less, more preferably 35% by mass or less.

The isocyanate monomer concentration (concentration of unreacted xylylene diisocyanate) of the XDI composition is, for example, 5% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less.

Further, if necessary, the above-mentioned organic solvent can be added to the XDI composition at an appropriate ratio to adjust the solid content concentration.

The solid content concentration of the XDI composition is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 100% by mass or less.

In the present invention, the hexamethylene diisocyanate composition (hereinafter, may be referred to as HDI composition) contains an allophanate of hexamethylene diisocyanate.

Examples of hexamethylene diisocyanate include 1,2-hexamethylene diisocyanate (1,2-hexane diisocyanate), 1,3-hexamethylene diisocyanate (1,3-hexane diisocyanate), and 1,4-hexamethylene diisocyanate (1,4- Hexamethylene diisocyanate), 1,5-hexamethylene diisocyanate (1,5-hexane diisocyanate), 1,6-hexamethylene diisocyanate (1,6-hexane diisocyanate), 2,5-hexamethylene diisocyanate (2,5-hexane diisocyanate) ) Etc. are mentioned as structural isomers.

These hexamethylene diisocyanates can be used alone or in combination of two or more.

Hexamethylene diisocyanate is preferably 1,6-hexamethylene diisocyanate (1,6-hexane diisocyanate).

An allophanate is a modified product containing one or more allophanate groups in the molecule.

The hexamethylene diisocyanate allophanate can be obtained, for example, by subjecting the hexamethylene diisocyanate to a urethanization reaction with an alcohol and then performing an allophanization reaction in the presence of an allophanization catalyst.

More specifically, in this method, first, hexamethylene diisocyanate and an alcohol are urethanized.

Examples of the alcohol include the above-mentioned alcohols (aliphatic alcohols, aromatic alcohols), and preferably the above-mentioned aliphatic alcohols.

Examples of the fatty alcohol include the above-mentioned monohydric fatty alcohol, the above-mentioned divalent fatty alcohol, the above-mentioned trivalent fatty alcohol, and the above-mentioned tetrahydric or higher fatty alcohol. , Preferably a monohydric fatty alcohol, and more preferably a branched monohydric fatty alcohol.

The fatty alcohol is preferably an aliphatic alcohol having 1 to 20 carbon atoms, more preferably an aliphatic alcohol having 2 to 20 carbon atoms, and further preferably an aliphatic alcohol having 2 to 8 carbon atoms. Alcohols may be mentioned, with preference given to aliphatic alcohols having 2 to 6 carbon atoms.

The blending ratio of the alcohol is, for example, 3 parts by mass or more, preferably 3.2 parts by mass or more, more preferably 3.5 parts by mass or more, and for example, 50 parts by mass with respect to 100 parts by mass of hexamethylene diisocyanate. Parts or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

Further, if necessary, the above-mentioned alcohol and, for example, thiols, oximes, lactams, phenols, β-diketones and the like can be used in combination in an appropriate ratio.

The reaction conditions in the urethanization reaction include, for example, an atmosphere of an inert gas such as nitrogen gas and a reaction temperature of, for example, room temperature (for example, 25 ° C.) or higher, preferably 40 ° C. or higher under normal pressure (atmospheric pressure). For example, it is 100 ° C. or lower, preferably 90 ° C. or lower. The reaction time is, for example, 0.05 hours or more, preferably 0.2 hours or more, and for example, 10 hours or less, preferably 6 hours or less.

Further, in the urethanization reaction, a known urethanization catalyst (for example, the amines), the organometallic compound, the potassium salt, etc. may be blended, if necessary. The blending ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and application.

Next, in this method, an allophanation catalyst is added to the reaction solution obtained by the urethanization reaction, and the reaction product of hexamethylene diisocyanate and an alcohol is subjected to an allophanization reaction.

Examples of the allophanate catalyst include an organic carboxylic acid bismuth salt such as bismuth octylate, and an organic carboxylic acid lead salt such as lead octylate.

These allophanation catalysts can be used alone or in combination of two or more.

The allophanation catalyst is preferably a lead organic carboxylic acid salt, and more preferably lead octylate.

The addition ratio of the allophanation catalyst is, for example, 0.001 part by mass or more, preferably 0.002 part by mass or more, and more preferably 0.01 part by mass or more with respect to 100 parts by mass of hexamethylene diisocyanate. For example, it is 0.3 parts by mass or less, preferably 0.05 parts by mass or less, and more preferably 0.03 parts by mass or less.

The reaction conditions for the allophanation reaction include, for example, an atmosphere of an inert gas such as nitrogen gas, under normal pressure (atmospheric pressure), and a reaction temperature of 0 ° C. or higher, preferably 20 ° C. or higher, for example, 160 ° C. or lower. , Preferably 120 ° C. or lower. The reaction time is, for example, 30 minutes or more, preferably 60 minutes or more, and for example, 1200 minutes or less, preferably 600 minutes or less.

Then, in the above allophanation reaction, preferably, a catalyst deactivating agent is added at an arbitrary timing to stop the reaction. The timing of adding the catalyst deactivating agent is, for example, the time when the target value of the conversion rate of the isocyanate group (for example, 1% or more, preferably 5% or more, for example, 20% or less) is reached.

Examples of the catalytic deactivator include phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid, paratoluenesulfonic acid, orthotoluenesulfonic acid, benzoylchloride, p-toluenesulfonamide, o-toluenesulfonamide and the like. The catalyst deactivating agent can be used alone or in combination of two or more. The blending ratio of the catalyst deactivating agent is not particularly limited, and is appropriately set according to the purpose and application.

As a result, an allophanate of hexamethylene diisocyanate can be obtained.

Further, in the above-mentioned urethanization reaction and allophanation reaction, the above-mentioned organic solvent can be blended in an appropriate ratio, if necessary.

Further, in the above-mentioned urethanization reaction and allophanation reaction, known additives such as an antioxidant and a cocatalyst (for example, an organic phosphite ester) can be added, if necessary.

The timing of adding the additive is not particularly limited and may be added to hexamethylene diisocyanate before the urethanization reaction, or may be added to the reaction solution during the urethanization reaction and / or the allophanization reaction. It may be added to the reaction solution after the urethanization reaction and the allophanation reaction.

The addition ratio of the additive is appropriately set according to the purpose and application.

Then, in this method, after the completion of the allophanation reaction, if necessary, unreacted hexamethylene diisocyanate (and, if necessary, a catalyst, a reaction solvent and / or catalyst deactivation) is extracted from the obtained reaction mixture. Agents, etc.) are removed by known methods such as distillation such as thin film distillation (Smith distillation) and extraction.

As a result, an HDI composition containing an allophanate of hexamethylene diisocyanate is obtained.

In such a method, in the hexamethylene diisocyanate urethanization reaction and allophanation reaction, depending on the reaction conditions, in addition to the hexamethylene diisocyanate allophanate, other hexamethylene diisocyanate derivatives (derivatives excluding the hexamethylene diisocyanate allophanate) are used. For example, isocyanurate of hexamethylene diisocyanate, dimer of hexamethylene diisocyanate (such as biuret), etc.) are obtained as by-products.

Further, if necessary, other hexamethylene diisocyanate derivatives (for example, isocyanurate of hexamethylene diisocyanate, dimer of hexamethylene diisocyanate (biuret, etc.), etc.) are prepared separately from the allophanate of hexamethylene diisocyanate. The HDI composition can also be prepared by mixing the allophanate of No. 1 with other hexamethylene diisocyanate derivatives.

In other words, the HDI composition can contain an allophanate of hexamethylene diisocyanate and other hexamethylene diisocyanate derivatives.

From the viewpoint of the handleability of the polyisocyanate composition and the weather resistance of the polyurethane resin (described later), the proportion of hexamethylene diisocyanate allophanate is 30% by mass or more, preferably 35% by mass, based on the total amount of the HDI composition. % Or more, more preferably 38% by mass or more, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 98% by mass or less.

The proportion of the other hexamethylene diisocyanate derivative is, for example, 0% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, based on the total amount of the HDI composition, for example, 70. It is mass% or less, preferably 65 mass% or less, and more preferably 62 mass% or less.

In particular, from the viewpoint of handleability of the polyisocyanate composition, the proportion of hexamethylene diisocyanate allophanate is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 70% by mass or more, based on the total amount of the HDI composition. Is 80% by mass or more, particularly preferably 90% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 97% by mass or less, and particularly preferably 96% by mass. % Or less.

From the viewpoint of handleability of the polyisocyanate composition, the proportion of the other hexamethylene diisocyanate derivative is preferably 1% by mass or more, more preferably 2% by mass or more, and further, with respect to the total amount of the HDI composition. It is preferably 3% by mass or more, particularly preferably 4% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass. It is mass% or less.

On the other hand, from the viewpoint of weather resistance of the polyurethane resin (described later), the HDI composition contains an allophanate of hexamethylene diisocyanate and an isocyanurate of hexamethylene diisocyanate.

In such a case, from the viewpoint of weather resistance of the polyurethane resin (described later) and from the viewpoint of handleability of the polyisocyanate composition, the proportion of hexamethylene diisocyanate allophanate is preferably 35 with respect to the total mass of the HDI composition. Mass% or more, more preferably 38% by mass or more, further preferably 40% by mass or more, particularly preferably 42% by mass or more, preferably less than 60% by mass, more preferably 55% by mass or less. More preferably, it is 50% by mass or less, and particularly preferably 48% by mass or less.

Further, from the viewpoint of weather resistance of the polyurethane resin (described later), the proportion of isocyanurate of hexamethylene diisocyanate preferably exceeds 40% by mass, more preferably 45% by mass, based on the total amount of the HDI composition. The above is more preferably 50% by mass or more, particularly preferably 52% by mass or more, preferably 65% by mass or less, more preferably 62% by mass or less, still more preferably 60% by mass or less, particularly preferably. Is 58% by mass or less.

In the HDI composition, the isocyanate group concentration (solid content 100% by mass) is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 18% by mass or more, and for example, 45% by mass or less. It is preferably 40% by mass or less, more preferably 35% by mass or less.

The isocyanate monomer concentration (concentration of unreacted hexamethylene diisocyanate) of the HDI composition is, for example, 5% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less.

Further, if necessary, the above-mentioned organic solvent can be added to the HDI composition at an appropriate ratio to adjust the solid content concentration.

The solid content concentration of the HDI composition is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 100% by mass or less.

In addition, such an HDI composition can also be obtained as a commercially available product. Examples of such a commercially available product include trade name Takenate D-177N (46% by mass of allophanate of hexamethylene diisocyanate, 54% by mass of isocyanurate of hexamethylene diisocyanate, 100% by mass of solid content concentration, manufactured by Mitsui Chemicals, Inc.). Examples thereof include Takenate D-178NL (96% by mass of allophanate of hexamethylene diisocyanate, 4% by mass of dimer of hexamethylene diisocyanate, 100% by mass of solid content concentration, manufactured by Mitsui Chemicals, Inc.). Commercially available products of these HDI compositions can be used alone or in combination of two or more. When two or more types of commercially available products of the HDI composition are used in combination, the combined use ratio is appropriately set according to the purpose and application.

The polyisocyanate composition can be obtained by blending and mixing the XDI composition and the HDI composition by a known method.

In such a polyisocyanate composition, the proportion of the XDI composition (solid content) is determined from the viewpoint of achieving both the heat adhesion and solvent resistance of the polyurethane resin (described later) and the handleability of the polyisocyanate composition. 80% by mass or more, preferably 85% by mass or more, 95% by mass or less, preferably 90% by mass or less, based on the total amount of the XDI composition (solid content) and the HDI composition (solid content). is there. The ratio of the HDI composition (solid content) is 5% by mass or more, preferably 10% by mass or more, based on the total amount of the XDI composition (solid content) and the HDI composition (solid content). It is 20% by mass or less, preferably 15% by mass or less.

Since such a polyisocyanate composition is excellent in handleability, the productivity of the polyurethane resin is excellent, and the obtained polyurethane resin can have excellent heat-resistant adhesion and solvent resistance.

Therefore, the polyisocyanate composition is preferably used in the production of polyurethane resins.

In the case of producing a polyurethane resin, if necessary, known additives such as plasticizers, blocking inhibitors, heat-resistant stabilizers, light-resistant stabilizers, antioxidants, mold release agents, catalysts, etc. Furthermore, pigments, dyes, lubricants, fillers, hydrolysis inhibitors and the like can be blended in appropriate proportions. These additives may be added at the time of synthesizing the raw material components of the polyurethane resin, may be added at the time of mixing the raw material components, and may be added to the mixture of the raw material components.

The form of the polyurethane resin is not particularly limited, but a two-component curable polyurethane is preferable. In other words, the polyisocyanate component is preferably used as a curing agent for a two-component curable polyurethane.

The two-component curable polyurethane is a resin composition in which a curing agent and a main agent are prepared as independent packages, and they are blended at the time of use to form a polyurethane resin (cured coating film or the like).

As the curing agent in such a two-component curable polyurethane, the above-mentioned polyisocyanate composition is preferably used.

The polyisocyanate composition is prepared as a curing agent by being dissolved in the above-mentioned organic solvent or the like, if necessary.

The main ingredient of the two-component curable polyurethane contains, for example, a polyol component. Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.

The low molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of less than 300, preferably less than 400, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, and the like. 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethyl Pentandiol, 3,3-dimethylolheptan, alcoholic (C7-20) diols, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and theirs. Dihydric alcohols such as mixture, hydride bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol , For example, trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, for example, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, for example, pentahydric alcohols such as xylitol, for example, sorbitol, mannitol. , Hexal alcohols such as alitol, igitol, darsitol, altritor, inositol, dipentaerythritol, for example, heptavalent alcohols such as persetol, for example, octahydric alcohols such as sucrose.

These low molecular weight polyols can be used alone or in combination of two or more.

The high molecular weight polyol is a compound having a number average molecular weight of 300 or more, preferably 400 or more, more preferably 500 or more having two or more hydroxyl groups, and is, for example, a polyether polyol (for example, a polyoxyalkylene polyol, a polytetra). Polyester polyol (for example, adipic acid-based polyester polyol, phthalic acid-based polyester polyol, lactone-based polyester polyol, etc.), polycarbonate polyol, polyurethane polyol (for example, polyether polyol, polyester polyol, polycarbonate polyol, etc.) Polyester modified with isocyanate), epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, vinyl monomer modified polyol and the like.

These high molecular weight polyols can be used alone or in combination of two or more.

These polyol components can be used alone or in combination of two or more.

The polyol component preferably includes a high molecular weight polyol, and more preferably an acrylic polyol.

If necessary, the polyol component is dissolved in the above-mentioned organic solvent or the like and prepared as a main agent.

The two-component curable polyurethane is suitably used as a paint (two-component curable paint), an adhesive (two-component curable adhesive), etc. by blending a curing agent and a main agent at the time of use and mixing and stirring. ..

More specifically, first, the above-mentioned main agent and the above-mentioned curing agent are prepared, and immediately before use, the main agent and the curing agent are mixed to prepare a two-component curable polyurethane resin (paint, adhesive). A two-component curable polyurethane resin is applied to an object to be coated or an adherend.

The blending ratio of the main agent and the curing agent is, for example, 0.5 to 1 as the equivalent ratio (NCO / OH) of the isocyanate groups in the curing agent (polyisocyanate composition) to the hydroxyl groups in the main agent (polyoxide component). The ratio is 5.5, preferably 0.8 to 1.2.

The mixture of the main agent and the curing agent can be obtained by any method such as spray coating, air spray coating, brush coating, dipping method, roll coating method, flow coating method, dry laminating method, wet laminating method, direct coating method and the like. Is applied to the adherend.

The adherend is not particularly limited, and examples thereof include various building materials and various laminated films. More specifically, packaging materials such as plastic films, metal foils and metal vaporized films, civil engineering materials such as FRP and steel materials, and the like can be mentioned.

Then, the mixture of the main agent and the curing agent is dried and cured to obtain a polyurethane resin (cured coating film, adhesive layer, etc.).

Since such a two-component curable polyurethane resin is produced using the polyisocyanate composition of the present invention, it can be obtained with high productivity, and is also excellent in heat adhesion and solvent resistance.

Therefore, the above-mentioned two-component curable polyurethane and polyisocyanate composition are preferably used in various industrial fields.

Specifically, the above-mentioned two-component curable polyurethane resin and polyisocyanate composition can be suitably used in, for example, paints and adhesives.

More specifically, as paints, for example, paints for plastics, paints for automobile exteriors, paints for automobile interiors, paints for electric / electronic materials, paints for optical materials (lenses, etc.), paints for building materials, glass coat paints, etc. Examples thereof include woodwork paints, film coating paints, ink paints, artificial leather paints (coating agents), and can paints (coating agents).

Examples of the plastic paint include paints for housings (mobile phones, smartphones, personal computers, tablets, etc.), paints for automobile parts (automobile interior materials, head lamps, etc.), paints for household electrical appliances, paints for robot materials, etc. Furniture paints, stationery paints, eyewear materials (lenses, etc.) paints, sports parts (golf balls, etc.) paints, bands (watch bands, etc.) paints, electronic equipment optical lens paints (surface coating agents), etc. However, it can be mentioned.

In addition, examples of the above-mentioned paint for automobile exterior include paint for new cars, paint for automobile repair, paint for exterior parts (aluminum wheels, bumpers, etc.) and the like.

Examples of the film coating paint include paints for optical members (optical films, optical sheets, etc.), optical coating materials, textile paints, electronic electrical material paints, food packaging paints, medical film paints, etc. Examples include paints for cosmetic packages, paints for decorative films, and paints for release films.

Examples of the adhesive include industrial adhesives, packaging adhesives, hot melt adhesives, and more specifically, for example, food packaging adhesives, household refill packaging adhesives, and electric appliances. Adhesives for equipment, adhesives for liquid crystal displays (LCD), adhesives for EL displays, adhesives for EL lighting, adhesives for display devices (electronic paper, plasma displays, etc.), adhesives for automobiles, adhesives for home appliances, Examples include adhesives for solar cell backsheets, adhesives for various batteries (lithium ion batteries, etc.), and moisture-curable adhesives.

Further, the above-mentioned two-component curable polyurethane and polyisocyanate composition can be used in, for example, adhesives, overprint varnishes (OP varnishes), inks, sealants, binder resins and the like.

Further, the above-mentioned polyisocyanate composition is not limited to the two-component curable polyurethane, and can be used as a raw material component (isocyanate component) of a polyurethane resin in various industrial fields.

Examples of such polyurethane resins include thermoplastic polyurethane resins (TPUs), thermosetting polyurethane resins, adhesives, aqueous resins, optical resins (lenses, etc.), active energy curable resins, and foam resins (soft foams). (Rigid foam, etc.) Various microcapsules, plastic lenses, artificial and synthetic leather, RIM molded products, slush powder, elastic molded products (spandex), flexible gels, robot materials, mobility materials, healthcare materials, carbon fiber reinforced plastics (CFRP) ) Base resin and the like.

Next, the present invention will be described based on Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, and parameters used in the following description are the compounding ratios corresponding to those described in the above-mentioned "Form for carrying out the invention". Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, and parameters. be able to.

Further, the measurement methods adopted in each production example and each preparation example are described below.

<Ratio of isocyanurates and allophanates in the XDI composition>
The ratio of the xylylene diisocyanate isocyanurate (XDI isocyanurate) contained in the xylylene diisocyanate composition (XDI composition) to the xylylene diisocyanate allophanate (XDI allophanate) was measured by the following method.

That is, about 0.03 g of a sample was collected, and 10 mL of tetrahydrofuran was added and dissolved. Then, the obtained solution was measured by GPC under the following conditions.
(1) Analyzer: HLC-8320GPC (manufactured by Tosoh Corporation)
(2) Detector: Differential refractometer (3) Eluent: Tetrahydrofuran
(4) Separation column: TSKgel G3000HXL (300 x 7.8 mm) + TSKgel G2000HXL (300 x 7.8 mm) + TSKgel G1000HXL (300 x 7.8 mm) 4 connected in series Manufacturer; Tosoh Corporation (5) Measurement Temperature: 40 ° C
(6) Flow velocity: 0.8 mL / min
(7) Sample injection amount: 100 μL
・ System correction (1) Standard substance name: TSK standard polyethylene oxide (manufactured by Tosoh Corporation)
(2) Calibration curve creation method: Create a graph of retention time and molecular weight using TSK standard polyethylene oxide manufactured by TOSOH with different molecular weights.
(3) Injection amount, injection rate: 100 μL, 3 mg / mL.

Then, in the obtained chromatogram (chart), the area of the peak having the holding time between 19.40 minutes and 25.45 minutes as the peak top and the holding time between 26.45 minutes and 27.13 minutes as the peak top. The area ratio (area ratio) of the total area to the area of the peaks to be formed was defined as the content ratio of XDI isocyanurate.

Further, the area ratio (area ratio) of the peak area having the peak top between the holding time of 25.65 minutes and 26.25 minutes with respect to the total peak area was defined as the content ratio of XDI allophanate.

Then, the ratio of isocyanurate and allophanate in the XDI composition was determined from the ratio of these area ratios.

<Ratio of isocyanurate and allophanate in HDI composition>
The ratio of the hexamethylene diisocyanate isocyanurate (HDI isocyanurate) contained in the hexamethylene diisocyanate composition (HDI composition) to the hexamethylene diisocyanate allophanate (HDI allophanate) was measured by the following method.

That is, about 0.03 g of a sample was collected, and 10 mL of tetrahydrofuran was added and dissolved. Then, the obtained solution was measured by GPC under the above conditions.

Then, in the obtained chromatogram (chart), the area of the peak having the holding time between 21.91 minutes and 25.79 minutes as the peak top and the holding time between 26.73 minutes and 27.49 minutes as the peak top. The area ratio (area ratio) of the total area with the area of the peaks to the total peak area was defined as the content ratio of HDI isocyanurate.

Further, the total area of the peak area having the peak top between the holding time of 25.99 minutes and 26.53 minutes and the peak area having the peak top between the holding times of 27.69 minutes and 29.45 minutes. The area ratio (area ratio) to the area of all peaks was defined as the content ratio of HDI allophanate.

Then, the ratio of isocyanurate and allophanate in the HDI composition was determined from the ratio of these area ratios.

Production Example 1 (XDI composition (1))
In a reactor equipped with a thermometer, agitator, a cooling tube, and a nitrogen introduction tube, under a nitrogen atmosphere, 100 parts by mass of XDI and octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( 0.02 parts by mass of a hindered phenolic antioxidant, trade name: Irganox 1076, manufactured by Ciba Japan Co., Ltd.) was mixed at 60 ° C. to 65 ° C.

Next, 2 parts by mass of 1,3-butanediol was added to the mixture at 70 ° C. to 75 ° C. and mixed to cause a urethanization reaction.

Next, a propylene glycol methyl ether acetate solution (solid content concentration 3.7% by mass) of tetrabutylammonium hydrooxide (isocyanurate conversion catalyst, TBAOH (37% methanol solution)) was added to the obtained urethane reaction solution. ..

The amount added was adjusted so that TBAOH (37% methanol solution) was 0.11 parts by mass (0.04 parts by mass as an active ingredient).

Next, while mixing the urethane reaction solution, XDI was subjected to an isocyanurate-forming reaction at 70 ° C. to 75 ° C. until the conversion rate reached 31%.

Next, a propylene glycol methyl ether acetate solution (active ingredient concentration 50% by mass) of dodecylbenzenesulfonic acid (DDBSA, catalytic deactivator) was added to the obtained isocyanurate reaction solution to stop the isocyanurate-forming reaction. ..

The addition amount was adjusted so that the amount of DDBSA added was 0.05 parts by mass (the addition ratio of DDBSA was 500 ppm with respect to the isocyanate reaction solution).

Then, the obtained isocyanurate reaction solution was further stirred at 70 to 75 ° C. for 30 minutes.

Next, the obtained isocyanurate reaction solution was subjected to thin film distillation (pressure: ~ 60 PaA, temperature: 160 ° C., feed amount: 5 g / min) to obtain an XDI composition (1) containing XDI isocyanurate.

The XDI isocyanurate content was 93% by mass and the XDI allophanate content was 7% by mass with respect to the total solid content of the obtained XDI composition (1).

Production Example 2 (XDI Composition (2))
An XDI composition (2) containing XDI isocyanurate was obtained by the same method as in Production Example 1 except that 1,3-butanediol was not blended.

The XDI isocyanurate content was 100% by mass and the XDI allophanate content was 0% by mass with respect to the total solid content of the obtained XDI composition (2).

Preparation Example 1 (HDI Composition (1))
As the HDI composition (1), a commercially available Takenate D-178NL (trade name, HDI allophanate 96% by mass, HDI dimer 4% by mass, solid content concentration 100% by mass, manufactured by Mitsui Chemicals) was prepared.

Preparation Example 2 (HDI Composition (2))
As the HDI composition (2), a commercially available Takenate D-177N (trade name, HDI allophanate 46% by mass, HDI isocyanurate 54% by mass, solid content concentration 100% by mass, manufactured by Mitsui Chemicals) was prepared.

Preparation Example 3 (HDI Composition (3))
Commercially available Takenate D-178NL (trade name, HDI allophanate 96% by mass, HDI dimer 4% by mass, solid content concentration 100% by mass, manufactured by Mitsui Chemicals, Inc.) 100 parts by mass and commercially available Takenate D-177N (trade name, HDI allophanate) The HDI composition (3) was prepared by mixing 46% by mass, 54% by mass of HDI isocyanurate, 100% by mass of solid content concentration, and 257 parts by mass of Mitsui Kagaku).

The HDI allophanate content was 60% by mass and the HDI isocyanurate content was 40% by mass with respect to the total solid content of the HDI composition (3).

Preparation Example 4 (HDI Composition (4))
As the HDI composition (4), a commercially available Takenate D-170N (trade name, HDI allophanate 25% by mass, HDI isocyanurate 75% by mass, solid content concentration 100% by mass, manufactured by Mitsui Chemicals) was prepared.

Examples 1-9 and Comparative Examples 1-7 (polyisocyanate composition and polyurethane resin)
The XDI composition and the HDI composition were mixed according to the formulations shown in Tables 1 and 2 to prepare a polyisocyanate composition. This polyisocyanate composition was used as a curing agent.

Further, as a main agent, a commercially available acrylic polyol (trade name: Olestar Q166, hydroxyl value: 30 mgKOH / g, solid content concentration: 50% by mass, manufactured by Mitsui Chemicals) was prepared.

Then, the curing agent and the main agent are mixed at a ratio such that the equivalent ratio (NCO / active hydrogen group) of the isocyanate group in the curing agent to the active hydrogen group (hydroxyl group, mercapto group, amino group) in the main agent is 1.0. Then, a mixed organic solvent (ethyl acetate: butyl acetate: propylene glycol monomethyl ether acetate = 1: 1: 1 (mass ratio)) was added to adjust the solid content to 50% by mass, and the solid content was adjusted to 50% by mass at 23 ° C. for 5 minutes. Stirred. Then, defoaming was performed by ultrasonic treatment for 10 minutes.

Then, the obtained mixed solution was applied to a base material according to each evaluation (described later) with a 4 mil applicator, heated at 80 ° C. for 30 minutes, and then cured in a thermostatic chamber at 23 ° C. and 55% humidity for 7 days. ..

As a result, a cured film of polyurethane resin was obtained.

<Evaluation>
1. 1. Heat-resistant adhesion (heat-resistant adhesion retention rate)
The adhesion retention rate was evaluated by the cross-cut method in accordance with JIS K5600-5-6 (1999). The adhesion retention rate was evaluated by the JIS classification and the remaining number of 10 × 10 (100) grids. The base material was a steel plate (SPCC, PBN-144 treated).

Then, the adhesion retention rate was evaluated before and after the heat resistance test (110 ° C. for 14 days), and the maintenance rate of the adhesion retention rate [(adhesion retention rate after the heat resistance test (%) / adhesion retention rate before the heat resistance test (%)). ) X100] was evaluated according to the following criteria.

⊚: Maintenance rate 90% or more and 100% or less 〇: Maintenance rate 80% or more and less than 90% Δ: Maintenance rate 50% or more and less than 80% ×: Maintenance rate less than 50% 2. The solvent-resistant cured film was subjected to a rubbing test with cotton wool dipped in methyl ethyl ketone (MEK) under a load of 500 g, the number of reciprocations until the substrate was exposed was measured, and the film was evaluated according to the following criteria. The base material was a steel plate (SPCC, PBN-144 treated).

⊚: 200 times or more 〇: 150 times or more and less than 180 times Δ: 50 times or more and less than 150 times ×: Less than 50 times 3. Handleability The viscosity of the curing agent at 80 ° C. was measured with a temperature-variable cone plate viscometer (cone plate viscometer: Toa Kogyo, CV-1S) and evaluated according to the following criteria. As the cone, a 100-poise cone (angle: 2 °, diameter: 14.5 mm) was used.

⊚: 5,500 mPa ・ s or less 〇: 5,500 mPa ・ s or more and less than 8,000 mPa ・ s Δ: 8,000 mPa ・ s or more and less than 10,000 mPa ・ s ×: 10,000 mPa ・ s or more 4. Weather resistance The cured film was weather-tested with an accelerated weather resistance tester (Suga Tester UV fluorescent lamp weather meter FUV). Specifically, the irradiance 28W / ^{m 2} 4 hours at 60 ° C. 10% RH conditions, and 4 hours dark condensation state under conditions RH 50 ° C. 95%, was repeated.

Then, the ΔE value (yellowing degree with time) after 1000 hours was measured with a color difference meter (SE2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) and evaluated according to the following criteria. The base material was PMMA (polymethyl methacrylate).

⊚: less than ΔE2 〇: ΔE2 or more and less than 3 Δ: ΔE3 or more and less than 5 ×: ΔE5 or more

Claims (4)

A xylylene diisocyanate composition containing an isocyanurate of xylylene diisocyanate and
Containing with a hexamethylene diisocyanate composition containing an allophanate of hexamethylene diisocyanate,
The allophanate of the hexamethylene diisocyanate is 30% by mass or more with respect to the total amount of the hexamethylene diisocyanate composition.
With respect to the total amount of the xylylene diisocyanate composition and the hexamethylene diisocyanate composition
The xylylene diisocyanate composition is 80% by mass or more and 95% by mass or less.
A polyisocyanate composition, wherein the hexamethylene diisocyanate composition is 5% by mass or more and 20% by mass or less. The polyisocyanate composition according to claim 1, wherein the isocyanurate of the xylylene diisocyanate is modified with an alcohol. The polyisocyanate composition according to claim 1 or 2, wherein the allophanate of the hexamethylene diisocyanate is 60% by mass or more with respect to the total amount of the hexamethylene diisocyanate composition. The hexamethylene diisocyanate composition contains an isocyanurate of hexamethylene diisocyanate and contains.
The allophanate of the hexamethylene diisocyanate is less than 60% by mass and the isocyanurate of the hexamethylene diisocyanate exceeds 40% by mass with respect to the total amount of the hexamethylene diisocyanate composition. The polyisocyanate composition according to claim 1 or 2.