CN114031744B

CN114031744B - Bis (isocyanatomethyl) cyclohexane compositions, modified compositions thereof, and methods of making

Info

Publication number: CN114031744B
Application number: CN202111435659.6A
Authority: CN
Inventors: 朱付林; 尚永华; 李建峰; 王鹏; 曹吉祥; 李强; 姜腾飞; 黄真真; 黎源
Original assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd; Wanhua Chemical Ningbo Co Ltd
Priority date: 2021-11-29
Filing date: 2021-11-29
Publication date: 2023-12-19
Anticipated expiration: 2041-11-29
Also published as: CN114031744A

Abstract

The present invention relates to a bis (isocyanatomethyl) cyclohexane composition, a bis (isocyanatomethyl) cyclohexane modified composition, a resin and an elastomer prepared from the bis (isocyanatomethyl) cyclohexane composition or the bis (isocyanatomethyl) cyclohexane modified composition, a two-component curable resin raw material comprising the bis (isocyanatomethyl) cyclohexane composition or the bis (isocyanatomethyl) cyclohexane modified composition, and a method for preparing the bis (isocyanatomethyl) cyclohexane composition. The bis (isocyanatomethyl) cyclohexane composition comprises bis (isocyanatomethyl) cyclohexane and 0.5 to 600ppm chloromethyl isocyanatomethyl cyclohexane represented by the following structural formula 1. Resins and elastomers prepared from the bis (isocyanatomethyl) cyclohexane composition or the bis (isocyanatomethyl) cyclohexane modified composition have excellent discoloration resistance,

Description

Bis (isocyanatomethyl) cyclohexane compositions, modified compositions thereof, and methods of making

Technical Field

The present invention relates to a bis (isocyanatomethyl) cyclohexane composition, a bis (isocyanatomethyl) cyclohexane modified composition, a resin and an elastomer prepared from the bis (isocyanatomethyl) cyclohexane composition or the bis (isocyanatomethyl) cyclohexane modified composition, and a two-component curable resin raw material comprising the bis (isocyanatomethyl) cyclohexane composition or the bis (isocyanatomethyl) cyclohexane modified composition, and a method for preparing the bis (isocyanatomethyl) cyclohexane composition.

Background

Bis (isocyanatomethyl) cyclohexane is an aliphatic isocyanate, and has been used as a raw material for polyurethane resins in various industrial products, particularly in optical materials or elastomer materials.

Chinese patents CN103641989, CN108752240, CN106674056, etc. report a method for preparing bis (isocyanatomethyl) cyclohexane by reacting cyclohexanediamine or a salt thereof with phosgene, however, for polyurethane resins, excellent discoloration resistance is required depending on the purpose and use. However, in the polyurethane resin produced from bis (isocyanatomethyl) cyclohexane described in the above patent document, sufficient discoloration resistance may not be ensured.

Accordingly, the present invention provides a bis (isocyanatomethyl) cyclohexane composition, a bis (isocyanatomethyl) cyclohexane modified composition, and a polyurethane resin raw material, each of which can stably produce a resin having excellent discoloration resistance.

Disclosure of Invention

The object of the present invention is to provide a bis (isocyanatomethyl) cyclohexane composition, and resins and elastomers prepared therefrom have excellent discoloration resistance.

According to a first aspect of the present invention there is provided a bis (isocyanatomethyl) cyclohexane composition comprising bis (isocyanatomethyl) cyclohexane and 0.5 to 600ppm, preferably 0.5 to 300ppm chloromethyl isocyanatomethyl cyclohexane of formula 1:

According to a second aspect of the present invention, there is provided a bis (isocyanatomethyl) cyclohexane modified composition obtained by modifying the above bis (isocyanatomethyl) cyclohexane composition, which comprises at least 1 functional group of the following (a) to (i),

(a) An isocyanurate group,

(b) A uretdione group, which is a group,

(c) A biuret group,

(d) A urethane group,

(e) A ureido group, a hydroxyl group,

(f) An iminooxadiazinedione group, which is,

(g) An allophanate group, a radical of an allophanate,

(h) A uretonimine group, a group of which is shown in the specification,

(i) Carbodiimide groups.

According to a third aspect of the present invention, there is provided a resin which is a reaction product of the bis (isocyanatomethyl) cyclohexane ingredient in the above-mentioned bis (isocyanatomethyl) cyclohexane composition or the bis (isocyanatomethyl) cyclohexane modifier ingredient in the bis (isocyanatomethyl) cyclohexane modifier composition and an active hydrogen group-containing ingredient.

Preferably, the resin is an optical material, more preferably an optical lens.

Examples of the active hydrogen group-containing component include a polyol component (a component mainly containing a polyol having 2 or more hydroxyl groups), a polythiol component (a component mainly containing a polythiol having 2 or more mercapto groups (thiol groups)), and/or a polyamine component (a compound mainly containing a polyamine having 2 or more amino groups).

According to a fourth aspect of the present invention, there is provided an elastomer which is the reaction product of the bis (isocyanatomethyl) cyclohexane ingredient in the above-described bis (isocyanatomethyl) cyclohexane composition or the bis (isocyanatomethyl) cyclohexane modifier ingredient in the bis (isocyanatomethyl) cyclohexane modifier composition and an active hydrogen group-containing ingredient.

Preferably, the active hydrogen group-containing component is one or both of a high molecular weight polyol and a low molecular weight polyol selected from the group consisting of a low molecular weight polyol having a molecular weight of 60 to 400, a low molecular weight polyamine having a molecular weight of 60 to 400, and a high molecular weight polyol having a number average molecular weight of 401 to 10000.

According to a fifth aspect of the present invention, there is provided a two-component curable resin raw material comprising the bis (isocyanatomethyl) cyclohexane composition and/or the bis (isocyanatomethyl) cyclohexane modifier composition according to the present invention, and an active hydrogen group-containing component.

Preferably, the two-component curable resin raw material is a coating raw material.

According to a sixth aspect of the present invention there is provided a process for preparing a bis (isocyanatomethyl) cyclohexane composition according to the present invention, the process comprising the steps of:

An isocyanating step of isocyanating cyclohexyldimethylamine or its hydrochloride with phosgene to produce bis (isocyanatomethyl) cyclohexane and chloromethylisocyanatomethyl cyclohexane, thereby producing a reaction product containing bis (isocyanatomethyl) cyclohexane and chloromethylisocyanatomethyl cyclohexane;

and a separation step of purifying the reaction material to prepare a bis (isocyanatomethyl) cyclohexane composition, wherein the content of chloromethylisocyanatomethyl cyclohexane in the bis (isocyanatomethyl) cyclohexane composition is 0.5 to 600ppm, preferably 0.5 to 300ppm.

Preferably, the solution concentration of the cyclohexyldimethylamine solution or the hydrochloride thereof is 3.0 mass% or more, preferably 5.0 mass% or more, for example, 30 mass% or less, preferably 20 mass% or less;

preferably, the molar ratio of phosgene to cyclohexyldimethylamine or its hydrochloride is 4 or more, more preferably 5 or less; preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

The method according to the invention, wherein the total content of iron and nickel in the cyclohexyldimethylamine or salt thereof is less than 100ppm.

The process according to the invention, wherein the aforementioned isocyanation process can be carried out batchwise or continuously, preferably continuously.

Advantageous effects

The bis (isocyanatomethyl) cyclohexane composition according to the present invention comprises bis (isocyanatomethyl) cyclohexane and chloromethylisocyanatomethyl cyclohexane, wherein the chloromethylisocyanatomethyl cyclohexane content is 0.5 to 600ppm, preferably 0.5 to 300ppm. The bis (isocyanatomethyl) cyclohexane composition of the present invention, and resins and elastomers produced from the bis (isocyanatomethyl) cyclohexane composition, are excellent in discoloration resistance.

Drawings

FIG. 1 is a flow chart of an apparatus for preparing a bis (isocyanatomethyl) cyclohexane composition according to an embodiment of the present invention;

wherein, 1-salifying kettle, 2-scrubber, 3-photochemical one kettle, 4-photochemical two kettles, 5-photochemical three kettles, 6-dephosgene tower, 7-desolventizing tower, 8-tar remover and 9-rectifying tower.

Detailed Description

1. Bis (isocyanatomethyl) cyclohexane compositions

The bis (isocyanatomethyl) cyclohexane composition of the present invention is a substantially single compound containing 97% by mass or more, preferably 99% by mass or more of bis (isocyanatomethyl) cyclohexane as a main component (i.e., bis (isocyanatomethyl) cyclohexane), but is defined as a bis (isocyanatomethyl) cyclohexane composition because it contains chloromethylisocyanatomethyl cyclohexane represented by the following structural formula (1) as a subcomponent.

Hereinafter, the bis (isocyanatomethyl) cyclohexane composition is referred to as H6XDI composition, the bis (isocyanatomethyl) cyclohexane is referred to as H6XDI, and the chloromethyl isocyanatomethyl cyclohexane is referred to as CIC.

The H6XDI composition of the present invention includes the following isomers: 1, 2-bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatomethyl) cyclohexane (1, 3-H6 XDI), 1, 4-bis (isocyanatomethyl) cyclohexane.

As a preferred embodiment, the bis (isocyanatomethyl) cyclohexane of the present invention is preferably 1, 3-bis (isocyanatomethyl) cyclohexane and/or 1, 4-bis (isocyanatomethyl) cyclohexane, more preferably 1, 3-bis (isocyanatomethyl) cyclohexane.

CIC is produced as a byproduct in the production of H6XDI, described later. The CIC includes ortho CIC, meta CIC, and para CIC as structural isomers. The structural isomers of these CIC may be contained in 1 or 2 or more in the H6XDI composition.

With regard to the CIC content, it is 0.5 to 600ppm relative to the total mass of the H6XDI composition. The CIC content can be determined by analysis by gas chromatography.

When the CIC content is within the above range, yellowing of the resin produced from the H6XDI composition can be suppressed.

Bis (isocyanatomethyl) cyclohexane can be produced by the isocyanation of cyclohexyldimethylamine, for example, by the phosgenation method.

As the raw material cyclohexyldimethylamine (BAC), 1, 2-cyclohexyldimethylamine (1, 2-BAC), 1, 3-cyclohexyldimethylamine (1, 3-BAC) and 1, 4-cyclohexyldimethylamine (1, 4-BAC) are mentioned as structural isomers.

Specific examples of the phosgenation method include a method in which cyclohexyldimethylamine is directly reacted with phosgene (hereinafter, sometimes referred to as a cold-hot two-stage phosgenation method), a method in which hydrochloride obtained by reacting cyclohexyldimethylamine with hydrochloric acid (hydrogen chloride) is reacted with phosgene in an inert solvent (hereinafter, sometimes referred to as a phosgenation method of amine hydrochloride), and the like, and preferred examples thereof include a phosgenation method of amine hydrochloride.

2. Preparation method of bis (isocyanatomethyl) cyclohexane

A process for preparing a bis (isocyanatomethyl) cyclohexane composition according to the present invention, said process comprising the steps of:

a salifying step of mixing cyclohexyldimethylamine with hydrogen chloride to produce cyclohexyldimethylamine hydrochloride;

an isocyanation step of reacting cyclohexyldimethylamine hydrochloride with phosgene to produce bis (isocyanatomethyl) cyclohexane and chloromethylisocyanatomethyl cyclohexane;

A separation step of separating and purifying the reaction substance to prepare a bis (isocyanatomethyl) cyclohexane composition;

wherein the total content of iron and nickel in the cyclohexyldimethylamine hydrochloride is less than 100ppm.

The salt-forming step of the present invention is to mix BAC with hydrogen chloride in the presence of an inert solvent to produce BAC hydrochloride.

Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane, halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene, nitrogen-containing compounds such as nitrobenzene, N-dimethylformamide, N-dimethylacetamide, and N, N' -dimethylimidazolidinone, ethers such as dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether, ketones such as heptanone, diisobutyl ketone, methyl isobutyl ketone, and methyl ethyl ketone, fatty acid esters such as ethyl acetate, butyl acetate, amyl acetate, and ethoxyethyl acetate, and aromatic carboxylic acid esters such as methyl salicylate, dimethyl phthalate, dibutyl phthalate, and methyl benzoate. The inert solvent may be used alone or in combination of 2 or more.

The inert solvent is preferably a halogenated aromatic hydrocarbon, more preferably chlorobenzene or dichlorobenzene.

Hydrogen chloride gas was introduced into the inert solvent, and then an inert solvent amine solution containing BAC was added. Then, the hydrogen chloride gas and the amine solution were stirred and mixed.

The BAC content in the amine solution is not particularly limited, and is, for example, 3.0 mass% or more, preferably 5.0 mass% or more, for example, 30 mass% or less, preferably 20 mass% or less.

The salt forming temperature in the salt forming step is, for example, 0 ℃ or higher, preferably 10 ℃ or higher, for example, 160 ℃ or lower, preferably 150 ℃ or lower, and more preferably 140 ℃ or lower.

The salt formation pressure (gauge pressure) in the salt formation step may be normal pressure or a pressure condition, and is preferably 0.01MPaG or more, more preferably 0.02MPaG or more, for example, 1.0MPaG or less, preferably 0.5MPaG or less, more preferably 0.4MPaG or less, for the pressure.

Thereby, BAC hydrochloride is produced from BAC and hydrogen chloride (salt forming reaction), and a slurry containing BAC hydrochloride is produced.

The total content of iron and nickel in BAC hydrochloride can be controlled by controlling the total content of BAC, inert solvent and hydrogen chloride, and also can be controlled by adopting an inert solvent washing mode, and the total content is less than 100ppm. The conventional BAC process, obtained by nitrile reduction, will have a small residual amount of nickel catalyst.

The mass of the washing solvent is 1:1 or more, 10:1 or less, preferably 2:1 or more, 8:1 or less relative to the mass of BAC.

The total iron and nickel content of the BAC hydrochloride is excessive and catalyzes the formation of subsequent chlorides of carbonyl chloride or hydrogen chloride with BAC hydrochloride or acid chloride species, mainly comprising chloromethyl isocyanatocyclohexane. The total content of iron and nickel in BAC hydrochloride is controlled.

Next, in the isocyanate process, carbonyl chloride is supplied to a slurry containing BAC hydrochloride, and the BAC hydrochloride is reacted with the carbonyl chloride (isocyanate reaction, phosgenation).

The supply ratio of phosgene is, for example, 4mol or more, preferably 5mol or more, for example, 40mol or less, preferably 30mol or less, and more preferably 20mol or less, based on 1mol of BAC or its hydrochloride.

The reaction time in the isocyanate-based step is, for example, 2hr or more, preferably 4hr or more, for example, 25hr or less, preferably 20hr or less.

The reaction temperature in the isocyanate process is, for example, 90℃or higher, preferably 100℃or higher, more preferably 120℃or higher, for example, 190℃or lower, preferably 180℃or lower, more preferably 170℃or lower.

The reaction pressure (gauge pressure) in the isocyanate-based step is preferably normal pressure or elevated pressure, for example, higher than atmospheric pressure (0 MPaG), more preferably 0.0005MPaG or higher, still more preferably 0.001MPaG or higher, still more preferably 0.003MPaG or higher, particularly preferably 0.01MPaG (10 kPaG) or higher, particularly preferably 0.02MPaG (20 kPaG) or higher, most preferably 0.03MPaG (30 kPaG) or higher, for example, 0.6MPaG or lower, preferably 0.5MPaG or lower, and more preferably 0.3MPaG or lower.

Alternatively, the isocyanation process may be accomplished by batch or continuous reactions. In the continuous operation, the slurry (BAC hydrochloride) produced in the stirring tank is continuously fed from the stirring tank to a reaction tank different from the stirring tank, the BAC hydrochloride is reacted with phosgene in the reaction tank, and the reaction solution (reaction substance) is continuously taken out from the reaction tank.

Thus, BAC hydrochloride reacts with phosgene to produce H6XDI as a main component. In addition, CIC is produced as a by-product, and is the reaction of iron and nickel in BAC hydrochloride to catalyze the formation of carbonyl chloride or hydrogen chloride with BAC hydrochloride or acid chloride species, so the CIC content is related to the amount of carbonyl chloride, the reaction concentration, and the total iron and nickel content in the hydrochloride.

Next, as necessary, the reaction solution (reaction mixture) is subjected to a degassing step, a desolventizing step, and a tar removal step. In the deaeration step, the residual phosgene, hydrogen chloride generated as a by-product, and other gases are removed from the reaction solution (reaction mixture) by a known deaerator. In the solvent removal step, the inert solvent is distilled off from the reaction solution by a known distillation column. In the tar removal step, tar components are removed from the reaction solution by a known tar remover. The reaction substance from which tar components were removed in the tar removal step was referred to as an intermediate substance.

The intermediate material may be purified, if necessary, by an industrial separation technique such as distillation and crystallization, without any particular limitation.

In the case of purification by rectification, the rectification column may be a plate column or a packed column.

Specifically, the theoretical plate number of the rectifying column (packed column) is, for example, 2 or more, preferably 5 or more, for example, 60 or less, preferably 40 or less. The pressure at the top of the rectifying column is, for example, 0.1kPaA or more, preferably 0.15kPaA or more, for example, 4kPaA or less, preferably 2.5kPaA or less.

The reflux ratio at the top of the rectifying column is, for example, 0.01 or more, preferably 0.1 or more, for example, 60 or less, preferably 40 or less.

The ratio of CIC can be adjusted to the above range by rectification. The content of CIC in the H6XDI composition may also be adjusted by adding CIC to the H6XDI composition.

The method for producing the H6XDI composition described above can be carried out, for example, by using the apparatus flow chart shown in FIG. 1. As shown in fig. 1, the present invention mainly comprises a salt forming tank 1 and a hydrochloride washing apparatus 2, and in an isocyanate unit described later, three-step continuous isocyanate processing (performed in a first photochemical tank 3, a second photochemical tank 4 and a third photochemical tank 5 in this order) is performed, and the amounts of H6XDI and CIC produced are adjusted by appropriately adjusting the total contents of iron and nickel in the above-mentioned hydrochloride and the supply ratio of phosgene. And a phosgene removal tower 6 and a solvent removal tower 7 are arranged behind the photochemical kettle, carbonyl chloride and solvent are removed from the reaction liquid to obtain a H6XDI crude product, the crude product passes through a tar remover 8 to obtain an intermediate product, and then the intermediate product is separated by a rectifying tower 9 to obtain the product.

Finally, in the rectification separation described later, the CIC content in the H6XDI composition is adjusted by appropriately adjusting the overhead reflux ratio and the like.

Specifically, first, an inert solvent is charged into a salt-forming vessel. Then, hydrogen chloride gas was continuously introduced into the bottom of the salt-forming tank through a hydrogen chloride line at the above-described supply ratio. The amine solution in which BAC is dissolved in an inert solvent is continuously supplied to the bottom of the salt-forming tank through an amine line. Then, the inside of the salt forming tank was maintained at the above-described salt forming temperature and salt forming pressure, and the hydrogen chloride gas and the amine solution were stirred and mixed by stirring blades (salt forming step). Thereby, a slurry containing BAC hydrochloride was produced.

And then the hydrochloride slurry is conveyed to a washing device through a hydrochloride conveying pipeline, and is washed and replaced by an inert solvent, so that the total content of iron and nickel in the hydrochloride is controlled. The slurry containing BAC hydrochloride was then continuously transported by way of an insert tube to the top of the autoclave via a hydrochloride transport line. That is, while continuously supplying hydrogen chloride gas and an amine solution to the salt formation vessel, a slurry containing H6BAC hydrochloride was continuously taken out of the salt formation vessel and transferred to the washing apparatus and the photochemical vessel.

Next, phosgene was continuously supplied to the tops of the first, second and third kettles in the above-described supply ratio as an insert pipe. Then, the slurry and phosgene were stirred and mixed while maintaining the inside of the one pot at the above-mentioned reaction temperature and reaction pressure (step 1 isocyanate-forming step). Thus, BAC hydrochloride reacts with phosgene to produce H6XDI as a main component and CIC as a by-product.

Then, the reaction solution was transferred to the photochemical two-pot through an overflow pipe. That is, while continuously supplying the slurry and phosgene to the first photochemical reactor, the primary photochemical liquid is continuously taken out from the first photochemical reactor and transferred to the second photochemical reactor.

Next, the primary reaction substance and phosgene are stirred and mixed in the photochemical two-pot while maintaining the inside of the photochemical two-pot at the above-mentioned reaction temperature and reaction pressure (step 2 isocyanate-forming step).

Similarly, the photochemical three-pot is also used for carrying out phosgenation reaction (the isocyanate chemical process of the 3 rd step) while inputting the secondary reaction substance.

Thus, the salt forming step and the isocyanate processing step are continuously performed.

Then, a reaction solution containing H6XDI, CIC, an inert solvent, and the like is produced. The sum of residence times in the three-stage isocyanate process is within the above-mentioned range.

Next, the above-mentioned photochemical reaction liquid is continuously fed to the central portion of the dephosgene column through a reaction material feed line. The photochemical liquid is separated into a gas containing phosgene, hydrogen chloride, and the like, and a liquid deaerated substance containing H6XDI, CIC, inert solvents, and the like, by a deaeration column (deaeration step).

Next, the deaerated matter is continuously fed into the column of the desolventizing column through the deaerated matter feed line. Then, the inert solvent was distilled off from the degassed material using a desolventizing column (desolventizing step) to obtain a crude H6XDI product.

Next, the H6XDI crude product was continuously fed to the upper portion of the detarrier through the crude feed line. Then, the tar component is removed from the desolventizing substance by a tar remover to obtain an intermediate product (tar removing step).

Next, the intermediate product is continuously fed into the column of the rectifying column through the intermediate product material feed line. Then, under the above-mentioned conditions of the rectification step (bottom temperature, top pressure, bottom reflux ratio, top reflux ratio and residence time), the light component is distilled off from the intermediate quality, and the H6XDI composition is recovered from the lower portion of the middle column.

Thus, the H6XDI composition can be continuously produced.

3. H6XDI modified composition

The H6XDI composition is modified according to need by a known method to obtain a modified H6XDI composition, and the modified H6XDI composition is suitably used as a polyisocyanate component and an active hydrogen group-containing component as a raw material for a polyurethane resin.

The H6XDI modified composition can be produced by modifying a H6XDI composition, and contains at least 1 functional group of the following (a) to (i).

(a) An isocyanurate group,

(b) An allophanate group, a radical of an allophanate,

(c) A biuret group,

(d) A urethane group,

(e) A ureido group, a hydroxyl group,

(f) An iminooxadiazinedione group, which is,

(g) A uretdione group, which is a group,

(h) A uretonimine group, a group of which is shown in the specification,

(i) Carbodiimide groups.

That is, the H6XDI modified composition contains H6XDI modified to contain functional groups (a) to (i) and CIC.

More specifically, the H6XDI modified composition containing the functional group (isocyanurate group) of (a) above contains a trimer of H6XDI, and is obtained, for example, by reacting the H6XDI composition in the presence of a known isocyanurate catalyst to isocyanurate H6 XDI.

The H6XDI modified composition containing the functional group (allophanate group) of the above (b) contains an allophanate modified product of H6XDI, and is obtained, for example, by further reacting the H6XDI composition with an alcohol in the presence of a known allophanatization catalyst.

The H6XDI modified composition containing the functional group (biuret group) of the above (c) contains a biuret modified product of H6XDI, and is obtained, for example, by reacting the H6XDI composition with water, a tertiary alcohol (for example, t-butanol, etc.), a secondary amine (for example, dimethylamine, diethylamine, etc.), etc., and then further reacting the resultant in the presence of a known biuretization catalyst.

The H6XDI modified composition containing the functional group (urethane group) of the above (d) contains a polyol modified product of H6XDI, and is obtained, for example, by reacting the H6XDI composition with a polyol component (e.g., trimethylolpropane, etc.).

The H6XDI modified composition containing the functional group (ureido) of (e) above contains a polyamine modified product of H6XDI, and is obtained, for example, by reacting the H6XDI composition with water, a polyamine component or the like.

The modified H6XDI composition containing the functional group (iminooxadiazinedione group) of (f) above contains an iminooxadiazinedione modification (asymmetric trimer) of H6XDI, and is obtained, for example, by reacting an H6XDI composition in the presence of a known iminooxadiazinedione catalyst to carry out iminooxadiazinedione on H6 XDI.

The H6XDI modified composition containing the functional group (uretdione group) of (g) above contains an uretdione modified product of H6XDI, and is obtained, for example, by a method of heating the H6XDI composition at about 90℃to 200℃or by reacting H6XDI in the presence of a known uretdione catalyst to carry out uretdione.

The H6XDI modified composition containing the functional group (uretonimine group) of the above (H) contains a uretonimine modified product of H6XDI, and is obtained, for example, by reacting the H6XDI composition in the presence of a known carbodiimidization catalyst to form a carbodiimide group and then adding H6XDI to the carbodiimide group.

The H6XDI modified composition containing the functional group (carbodiimide group) of (i) above contains a carbodiimide modified product of H6XDI, and can be obtained, for example, by reacting a H6XDI composition in the presence of a known carbodiimidization catalyst.

The H6XDI modified composition may contain at least 1 kind of functional groups (a) to (i) described above, or may contain 2 or more kinds. Such H6XDI modified compositions can be produced by appropriately combining the reactions described above. In addition, the H6XDI modified composition may be used alone or in combination of 2 or more.

4. Resin composition

The resin (polyurethane resin) which is the reaction product of the polyisocyanate component of the H6XDI composition and/or H6XDI modified composition and the active hydrogen group-containing component can be applied to all uses for which the polyurethane resin can be used.

Specifically, the resin can be suitably used as a resin for ink, transfer foil, adhesive, gel, elastomer, foam, adhesive, one-component curable sealing material, RIM molded article, micro-foam polyurethane, various microcapsules, optical material, aqueous resin, thermosetting resin, active energy ray (e.g., electron beam, ultraviolet ray, etc.) curable resin, artificial and synthetic leather, setting powder (slush powder), robot member, moving member, health care (healthcare) material, base resin of Carbon Fiber Reinforced Plastic (CFRP), transparent rubber, transparent hard resin, waterproof material, film, sheet, tube, plate, speaker, sensor, organic EL member, solar power generating member, robot (android) member, wearable member, sporting goods, leisure goods, medical goods, nursing goods, housing member, acoustic member, lighting member, lamp, outdoor unit, package, vibration isolation and vibration absorbing member, sound absorbing member, daily use, sundry goods, buffer, shock absorbing member, OA, stress absorbing material for automobile, and health care device, and the like.

Examples of the active hydrogen group-containing component include a polyol component (a component mainly containing a polyol having 2 or more hydroxyl groups), a polythiol component (a component mainly containing a polythiol having 2 or more mercapto groups (thiol groups)), a polyamine component (a compound mainly containing a polyamine having 2 or more amino groups), and the like.

Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.

The low molecular weight polyol is a compound having 2 or more hydroxyl groups and a number average molecular weight of 60 or more and less than 400.

Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, and 1, 2-butanediolAlcohols, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, C _7～22 Alkane diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1, 5-pentanediol, C _17～20 Alkane-1, 2-diol, isosorbide, 1, 3-or 1, 4-cyclohexanedimethanol, mixtures thereof, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 1, 4-dihydroxy-2-butene, 2, 6-dimethyl-1-octene-3, 8-diol, diols such as bisphenol A, triols such as glycerol, trimethylol propane, tetraols such as tetramethylol methane (pentaerythritol), diglycerol, pentaols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altrose, inositol, dipentaerythritol, heptaols such as avocado sugar alcohol, octaols such as sucrose, and the like.

In addition, a polyalkylene oxide having a number average molecular weight of 60 or more and less than 400 (a random and/or block copolymer containing 2 or more alkylene oxides) obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide using the above-mentioned alcohol as an initiator is also contained in the low molecular weight polyol.

The high molecular weight polyol is a compound having 2 or more hydroxyl groups and a number average molecular weight of 400 or more, for example 10000 or less, preferably 5000 or less. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, polysiloxane polyol, fluorine polyol, and vinyl monomer modified polyol.

Examples of the polyether polyol include polyoxyalkylene (C2-3) polyols, polytetramethylene ether glycol, polytrimethylene ether glycol and the like. Examples of the polyoxyalkylene (C2-3) alkylene polyols include addition polymers of C2-3 alkylene oxides such as ethylene oxide and propylene oxide (random and/or block copolymers containing 2 or more alkylene oxides) using the above-mentioned low molecular weight polyols as an initiator. Further, as the polyoxyalkylene (C2-3) group, specifically, polyethylene glycol, polypropylene glycol, polyethylene polypropylene copolymer and the like can be mentioned.

Examples of the polytetramethylene ether glycol include a ring-opened polymer (polytetramethylene ether glycol) obtained by cationic polymerization of tetrahydrofuran, and amorphous polytetramethylene ether glycol obtained by copolymerizing a polymerized unit of tetrahydrofuran with the above diol.

In addition, plant-derived polytetramethylene ether glycol prepared from tetrahydrofuran produced from plant-derived materials such as furfural is also included.

Examples of the polytrimethylene ether glycol include polyols produced by polycondensation of plant-derived 1, 3-propanediol.

Examples of the polyester polyol include polycondensates obtained by reacting the above low molecular weight polyol (preferably a diol) with a polybasic acid (preferably a dibasic acid) under known conditions.

Examples of the polybasic acid include saturated aliphatic dicarboxylic acids (having 11 to 13 carbon atoms) such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1-dimethyl-1, 3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, and the like, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and the like, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, naphthalene dicarboxylic acid, and the like, alicyclic dicarboxylic acids such as hexahydrophthalic acid, and the like, other carboxylic acids such as dimer acid, hydrogenated dimer acid, HET acid, and the like, and anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12 to C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and the acid halides derived from these carboxylic acids, such as oxalyl dichloride, adipoyl dichloride, and sebacoyl dichloride, and the like.

Examples of the polyester polyol include a vegetable oil-based polyester polyol obtained by condensation reaction of the low molecular weight polyol described above with a hydroxycarboxylic acid such as a vegetable oil fatty acid containing a hydroxyl group (for example, a castor oil fatty acid containing ricinoleic acid, a hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) under known conditions.

Examples of the polyester polyol include a polycaprolactone polyol obtained by ring-opening polymerization of a lactone such as epsilon-caprolactone or gamma-valerolactone using the low molecular weight polyol (preferably a diol) as an initiator, a polycaprolactone polyol, and a lactone polyester polyol obtained by copolymerizing the above diol with the above polyol.

Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the low molecular weight polyol (preferably a diol) as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the diol with the ring-opening polymer.

The polyurethane polyol may be a polyester polyol, a polyether polyol and/or a polycarbonate polyol obtained by reacting the polyester polyol, polyether polyol and/or polycarbonate polyol obtained by the above method with the above polyisocyanate (including xylylene diisocyanate; the same applies hereinafter) in a ratio of hydroxyl groups to isocyanate groups equivalent to (OH/NCO) of more than 1.

Examples of the epoxy polyol include those obtained by reacting the low molecular weight polyol described above with a polyfunctional halohydrin such as epichlorohydrin or β -methyl epichlorohydrin.

Examples of the vegetable oil polyol include vegetable oil containing hydroxyl groups such as castor oil and coconut oil. Examples thereof include castor oil polyols, and ester-modified castor oil polyols obtained by reacting castor oil polyols with polypropylene polyols.

Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

Examples of the acrylic polyol include a copolymer obtained by copolymerizing an acrylic ester having a hydroxyl group with a copolymerizable vinyl monomer copolymerizable with the acrylic ester having a hydroxyl group.

Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, and the like. Preferable examples include 2-hydroxyethyl (meth) acrylate.

Examples of the copolymerizable vinyl monomer include (meth) acrylic acid alkyl esters (carbon number 1 to 12) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and the like, styrene, vinyltoluene, and α -methylstyrene, for example

Aromatic vinyl monomers, vinyl cyanide such as (meth) acrylonitrile, vinyl monomers containing a carboxyl group such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, or alkyl esters thereof, alkane polyol poly (meth) acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and vinyl monomers containing an isocyanate group such as 3- (2-isocyanate-2-propyl) - α -methylstyrene.

The acrylic polyol can be obtained by copolymerizing an acrylic ester containing a hydroxyl group and a copolymerizable vinyl monomer in the presence of an appropriate solvent and a polymerization initiator.

The acrylic polyol includes, for example, a polysiloxane polyol and a fluorine polyol.

As the polysiloxane polyol, for example, an acrylic polyol obtained by blending a vinyl-containing polysiloxane compound such as γ -methacryloxypropyl trimethoxysilane as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol can be mentioned.

Examples of the fluorine polyol include an acrylic polyol obtained by blending a vinyl group-containing fluorine compound such as tetrafluoroethylene and chlorotrifluoroethylene as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol.

The vinyl monomer-modified polyol can be obtained by reacting the high molecular weight polyol with the vinyl monomer such as the alkyl (meth) acrylate.

These polyol components may be used singly or in combination of 2 or more.

4.1 optical Material

A preparation method of optical resin is to mix and polymerize the H6XDI composition according to the invention and a polythiol compound to obtain an optical material.

The polythiol compound of the present invention is selected from the group consisting of methyl dithiol, 1, 2-ethanedithiol, 1-propanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 2-propanedithiol, 1, 6-hexanedithiol, 1,2, 3-propanetrithiol, 1-cyclohexanedithiol, 1, 2-cyclohexanedithiol, 2-dimethylpropane-1, 3-dithiol, 3, 4-dimethoxybutane-1, 2-dithiol, 2-methylcyclohexane-2, 3-dithiol, 1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl thiomalate), 2, 3-dimercapto-1-propanol (2-mercaptoacetate) 2, 3-dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1, 2-dimercaptopropylmethyl ether, 2, 3-dimercaptopropylmethyl ether, 2-bis (mercaptomethyl) -1, 3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylol propane bis (2-mercaptoacetate), trimethylol propane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), aliphatic polythiol compounds such as tetrakis (mercaptomethyl) methane;

1, 2-dimercaptobenzene, 1, 3-dimercaptobenzene, 1, 4-dimercaptobenzene, 1, 2-bis (mercaptomethyl) benzene, 1, 3-bis (mercaptomethyl) benzene, 1, 4-bis (mercaptomethyl) benzene, 1, 2-bis (mercaptoethyl) benzene, 1, 3-bis (mercaptoethyl) benzene, 1, 4-bis (mercaptoethyl) benzene, 1,2, 3-trismercaptobenzene, 1,2, 4-trismercaptobenzene, 1,3, 5-trismercaptobenzene, 1,2, 3-tris (mercaptomethyl) benzene, 1,2, 4-tris (mercaptomethyl) benzene, 1,3, 5-tris (mercaptomethyl) benzene, 1,2, 3-tris (mercaptoethyl) benzene, 1,2, 4-tris (mercaptoethyl) benzene, 1,3, 5-tris (mercaptoethyl) benzene, 2, 5-toluene dithiol, 3, 4-dithiol, 1, 3-bis (2, 3-diphenyl) propane, 2-diphenyl-dithiol, 2-diphenyl propane, 2-diphenyl-dithiol, poly (1, 2-diphenyl) propane, poly (mercapto-propane, etc.;

aromatic polythiol compounds having a sulfur atom other than a mercapto group, such as 1, 2-bis (mercaptoethylthio) benzene, 1, 3-bis (mercaptoethylthio) benzene, 1, 4-bis (mercaptoethylthio) benzene, 1,2, 3-tris (mercaptomethylthiothio) benzene, 1,2, 4-tris (mercaptomethylthiothio) benzene, 1,3, 5-tris (mercaptomethylthiothio) benzene, 1,2, 3-tris (mercaptoethylthio) benzene, 1,2, 4-tris (mercaptoethylthio) benzene, 1,3, 5-tris (mercaptoethylthio) benzene, and the like, and alkyls thereof;

Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1, 2-bis (mercaptomethylthio) ethane, 1, 2-bis (2-mercaptoethylthio) ethane, 1, 2-bis (3-mercaptopropyl) ethane, 1, 3-bis (mercaptomethylthio) propane, 1, 3-bis (2-mercaptoethylthio) propane, 1, 3-bis (3-mercaptopropylthio) propane, 1,2, 3-tris (mercaptomethylthio) propane 1,2, 3-tris (2-mercaptoethylthio) propane, 1,2, 3-tris (3-mercaptopropylthio) propane, 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithiaundecane, bis (mercaptomethyl) -3,6, 9-trithio-1, 11-undecanedithiol, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, aliphatic polythiol compounds having a sulfur atom other than a mercapto group such as tetrakis (3-mercaptopropylthiomethyl) methane, bis (2, 3-dimercaptopropyl) sulfide, bis (1, 3-dimercaptopropyl) sulfide, 2, 5-dimercapto-1, 4-dithiane, 2, 5-dimercaptomethyl-2, 5-dimethyl-1, 4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, and esters of mercaptoacetic acid and mercaptopropionic acid thereof;

Hydroxymethyl thioether bis (2-mercaptoacetate), hydroxymethyl thioether bis (3-mercaptopropionate), hydroxyethyl thioether bis (2-mercaptoacetate), hydroxyethyl thioether bis (3-mercaptopropionate), hydroxypropyl thioether bis (2-mercaptoacetate), hydroxypropyl thioether bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1, 4-dithiane-2, 5-diol bis (2-mercaptoacetate), 1, 4-dithiane-2, 5-diol bis (3-mercaptopropionate), ethylene disulfide bis (2-mercaptoacetate), ethylene disulfide bis (2-mercaptopropionate), diethyl disulfide bis (2-mercaptopropionate), aliphatic polythiol compounds having a sulfur atom and an ester bond in addition to a mercapto group, such as bis (2-mercaptoethyl) 4, 4-dithiodibutyrate, bis (2, 3-dimercaptopropyl) thionodipropionate, bis (2, 3-dimercaptopropyl) dithiodiacetate, and bis (2, 3-dimercaptopropyl) dithiodipropionate;

Heterocyclic compounds containing a sulfur atom in addition to a mercapto group, such as 3, 4-thiophenedichiol and 2, 5-dimercapto-1, 3, 4-thiodiazole;

compounds containing a hydroxyl group other than a mercapto group, such as 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, glycerol bis (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2, 4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3, 4-dimercapto-2-propanol, 1, 3-dimercapto-2-propanol, 2, 3-dimercapto-1-propanol, 1, 2-dimercapto-1, 3-butanediol, pentaerythritol tris (3-mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (mercaptoacetate), dipentaerythritol penta (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, and 1-hydroxyethylthio-3-mercaptoethylthio benzene;

1, 3-tetra (mercaptomethylthio) propane, 1, 2-tetra (mercaptomethylthio) ethane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiane 1, 5-tetra (mercaptomethylthio) -3-thiapentane, 1, 6-tetra (mercaptomethylthio) -3, 4-dithio-hexane 2, 2-bis (mercaptomethylthio) ethanethiol, 2- (4, 5-dimercapto-2-thiapentyl) -1, 3-dithiolane, 2-bis (mercaptomethyl) -1, 3-dithiolane, 2, 5-bis (4, 4-bis (mercaptomethylthio) -2-thiabutyl) -1, 4-dithiane 2, 2-bis (mercaptomethylthio) -1, 3-propane dithiol, 3-mercaptomethylthio-1, 7-dimercapto-2, 6-dithioheptane, 3, 6-bis (mercaptomethylthio) -1, 9-dimercapto-2, 5, 8-trithianonane, 4, 6-bis (mercaptomethylthio) -1, 9-dimercapto-2, 5, 8-trithianonane, 3-mercaptomethylthio-1, 6-dimercapto-2, 5-dithiohexane, 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiocyclobutane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3, 3-bis (mercaptomethylthio) -1-thiopropyl) 3, 7-dithiononane, tris (2, 2-bis (mercaptomethylthio) ethyl) methane, tris (4, 4-bis (mercaptomethylthio) -2-thiobutyl) methane, tetrakis (2, 2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4, 4-bis (mercaptomethylthio) -2-thiobutyl) methane, 3,5,9,11-tetrakis (mercaptomethylthio) -1, 13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexa (mercaptomethylthio) -1, 19-dimercapto-2,6,8,12,14,18-hexa-nonadecane, 9- (2, 2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,6,8,10,12,16-hexaheptadecane, 3,4,8, 9-tetrakis (mercaptomethylthio) -1, 11-dimercapto-2, 5,7, 10-tetrathiaundecane, 3,4,8,9,13,14-hexa (mercaptomethylthio) -1, 16-hexamercapto-3, 6-dimercapto-pentadecane-1, 17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8, 9-tetrakis (mercaptomethylthio) -1, 11-dimercapto-2, 5,7, 10-tetrathiaundecane, 3,4,8,9,13,14-hexa (mercapto) -1, 16-dimercapto-hexamercapto-3, 3-bis (mercaptomethylthio) -3, 3-dimercapto-pentadecane-6-dimercapto-3-methyltetramercapto-3-6-dimercapto-pentadecane 4- {3, 5-bis (mercaptomethylthio) -7-mercapto-2, 6-dithiaheptylthio } -6-mercaptomethylthio-1, 3-dithiane, 1-bis {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -3, 3-bis (mercaptomethylthio) propane, 1, 3-bis {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -1, 3-bis (mercaptomethylthio) propane, 1- {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -3- {2, 2-bis (mercaptomethylthio) ethyl } -7, 9-bis (mercaptomethylthio) -2,4,6, 10-tetrathiaundecane 1- {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -3- {2- (1, 3-dithiacyclobutyl) } methyl-7, 9-bis (mercaptomethylthio) -2,4,6, 10-tetrathiaundecane, 1, 5-bis {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -3- {2- (1, 3-dithiabutylyl) } methyl-2, 4-dithiapentane, 4, 6-bis [3- {2- (1, 3-dithiabutylyl) } methyl-5-mercapto-2, 4-dithiapentylthio ] -1, 3-dithiane, 4, 6-bis {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -1, 3-dithiane, 4- {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -6- {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -1, 3-dithiane, 3- {2- (1, 3-dithiacyclobutyl) } methyl-7, 9-bis (mercaptomethylthio) -1, 11-dimercapto-2, 4,6, 10-tetrathiaundecane, 9- {2- (1, 3-dithiacyclobutyl) } methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,6,8,10,12,16-hexaheptadecane 3- {2- (1, 3-dithiacyclobutyl) } methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3, 7-bis {2- (1, 3-dithiabutylyl) } methyl-1, 9-dimercapto-2, 4,6, 8-tetrathianonane, 4- {3,4,8, 9-tetrakis (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecyl } -5-mercaptomethylthio-1, 3-dithiacyclopentane, 4, 5-bis {3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiahexylthio } -1, 3-dithiacyclopentane, 4- {3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio } -5-mercaptomethylthio-1, 3-dithiolane, 4- { 3-bis (mercaptomethylthio) -methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithiooctyl } -5-mercaptomethylthio-1, 3-dithiolane, 2- [ bis {3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio } methyl ] -1, 3-dithiocyclobutane, 2- {3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio } mercaptomethylthiomethyl-1, 3-dithiocyclobutane 2- {3,4,8, 9-tetra (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecylthio } mercaptomethylthiomethyl-1, 3-dithio-tane, 2- { 3-bis (mercaptomethylthio) methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithiooctyl } mercaptomethylthiomethyl-1, 3-dithio-tane, 4, 5-bis [1- {2- (1, 3-dithio-butyl) } -3-mercapto-2-thi-propylthio ] -1, 3-dithio-lane, 4- [1- {2- (1, 3-dithiol-butyl) } -3-mercapto-2-thiiranyl ] -5- {1, 2-bis (mercapto-methylthio) -4-mercapto-3-thiobutanethiol } -1, 3-dithiolane, 2- [ bis {4- (5-mercapto-1, 3-dithiolane) thio ] methyl-1, 3-dithiolane, 4- {4- (5-mercapto-methylthio-1, 3-dithiolane) thio } -5- [1- {2- (1, 3-dithiol-butyl) } -3-mercapto-2-thiiranyl ] -1, 3-dithiolane, their oligomers and the like compounds having a dithioacetal (dithioacetal) or dithioketal (dithioketal) backbone;

Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1, 5-tetrakis (mercaptomethylthio) -2, 4-dithiolane, bis (4, 4-bis (mercaptomethylthio) -1, 3-dithiobutyl) (mercaptomethylthio) methane, tris (4, 4-bis (mercaptomethylthio) -1, 3-dithiobutyl) methane, 2,4, 6-tris (mercaptomethylthio) -1,3, 5-trithiocyclohexane, 2, 4-bis (mercaptomethylthio) -1,3, 5-trithiocyclohexane, 1, 3-tetrakis (mercaptomethylthio) -2-thiopropane, bis (mercaptomethyl) methylthio-1, 3, 5-trithiocyclohexane tris ((4-mercaptomethyl-2, 5-dithiocyclohexyl-1-yl) methylthio) methane, 2, 4-bis (mercaptomethylthio) -1, 3-dithiolane, 2-mercaptoethylthio-4-mercaptomethyl-1, 3-dithiolane, 2- (2, 3-dimercaptopropylthio) -1, 3-dithiolane, 4-mercaptomethyl-2- (1, 3-dimercapto-2-propylthio) -1, 3-dithiolane, tris (2, 2-bis (mercaptomethylthio) -1-thiaethyl) methane, compounds having a trithio-orthoformate (ortho trithioformate) skeleton such as tris (3, 3-bis (mercaptomethylthio) -2-thiapropyl) methane, tris (4, 4-bis (mercaptomethylthio) -3-thiabutyl) methane, 2,4, 6-tris (3, 3-bis (mercaptomethylthio) -2-thiapropyl) -1,3, 5-trithiocyclohexane, tetrakis (3, 3-bis (mercaptomethylthio) -2-thiapropyl) methane, and oligomers thereof;

Compounds having a tetrathiocarbonate skeleton such as 3,3 '-bis (mercaptomethylthio) -1, 5-dimercapto-2, 4-dithiolane, 2' -bis (mercaptomethylthio) -1, 3-dithiolane, 2, 7-bis (mercaptomethyl) -1,4,5,9-tetrathiaspiro [4,4] nonane, 3, 9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and oligomers thereof.

However, the polythiol compound is not limited to the above-mentioned compounds. The above-mentioned compounds may be used alone or in combination of 2 or more.

Of the above-mentioned compounds, at least 1 polythiol compound selected from the group consisting of 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, bis (mercaptomethyl) -3,6, 9-trithia-1, 11-undecanedithiol, pentaerythritol tetrakis (3-mercaptopropionate), 1, 3-tetrakis (mercaptomethylthio) propane and 2-mercaptoethanol is particularly preferably used.

Preferably, the method for producing the optical resin is carried out in the presence of a polymerization catalyst, and the polymerization catalyst is preferably an organotin compound, and examples thereof include dialkyltin halides (dialkyltin halide) such as dibutyltin dichloride and dimethyltin dichloride; tin dialkyldicarboxylates such as dimethyldiacetate, dibutyltin dioctanoate, dibutyltin dilaurate and the like.

In the above-mentioned method for producing an optical resin, various additives such as a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler, and a mold release agent are optionally added according to the purpose.

Optical materials formed from polyurethane-based resins are generally manufactured by injection polymerization. Specifically, a polythiol compound and an isocyanate compound are mixed, and a suitable auxiliary agent is optionally added. When necessary, the mixed solution (polymerizable composition) is defoamed by an appropriate method, and then injected into an injection mold for an optical material, and is usually heated gradually from a low temperature to a high temperature to polymerize. Then, the optical material is obtained by demolding.

When the CIC content in the H6XDI composition for optical material is 0.5 to 600ppm, an optical material can be stably produced from the H6XDI composition for optical material. And can suppress discoloration of the optical material.

The resin according to the present invention is an optical lens. Namely, an optical lens prepared using the composition according to the present invention.

4.2, elastomer

Examples of the elastomer include thermoplastic polyurethane elastomer (TPU), thermosetting polyurethane elastomer (TSU), and millable polyurethane elastomer.

The elastomer comprises a soft segment formed by the reaction of H6XDI with a high molecular weight polyol, and a hard segment formed by the reaction of H6XDI with a low molecular weight polyol and/or a low molecular weight polyamine.

Such an elastomer can be produced, for example, by reacting a polyisocyanate component, a high molecular weight polyol (component containing an active hydrogen group), and a low molecular weight polyol and/or a low molecular weight polyamine (component containing an active hydrogen group). Namely, a polyisocyanate component, a high molecular weight polyol, and a low molecular weight polyol and/or a low molecular weight polyamine are elastomer raw materials.

The high molecular weight polyol used as the elastomer raw material includes, for example, the above-mentioned polyester polyol (for example, polycaprolactone polyol, adipic acid-based polyester polyol (polyester polyol using adipic acid as a polybasic acid)), the above-mentioned polycarbonate polyol, and the above-mentioned polytetramethylene ether glycol (for example, polytetramethylene ether glycol), and preferably includes adipic acid-based polyester polyol.

The low molecular weight polyol used as the raw material of the elastomer may be, for example, ethylene glycol or 1, 4-butanediol, and preferably 1, 4-butanediol.

Examples of the low molecular weight polyamine used as the raw material of the elastomer include the low molecular weight polyamine described above.

The elastomer can be produced by a known method such as a one-shot method or a prepolymer method.

The method for producing the elastomer may be, for example, bulk polymerization or solution polymerization.

In the method for producing an elastomer, a known urethane catalyst such as an amine or an organometallic compound (for example, an organotin compound, preferably dibutyltin dichloride or the like) may be added to the elastomer raw material, if necessary. Further, if necessary, a plasticizer, an antiblocking agent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a yellowing inhibitor, an antioxidant, a mold release agent, a pigment, a dye, a lubricant, a nucleating agent, a filler, a hydrolysis inhibitor, and the like may be blended in an appropriate ratio to the elastomer.

Thus, an elastomer can be produced. Such an elastomer is excellent in discoloration resistance.

The color difference (. DELTA.b) of the elastomer in the xenon lamp irradiation test (240 hours) is, for example, 1.0 or more, for example, less than

3.0, preferably 2.6 or less. The color difference of the elastomer in the xenon lamp irradiation test can be measured by the method described in examples described later.

4.3 use of two-component resin raw materials

The two-component resin raw material containing the isocyanate component of the H6XDI composition and/or the H6XDI modified composition as the agent A and the component containing the active hydrogen group as the agent B can be suitably used for applications such as coating materials, adhesives and the like, and two-component curable sealing materials. Such a two-component resin raw material is a raw material in which an agent a (curing agent) and an agent B (main agent) prepared separately are blended immediately before use.

The coating material is a two-component curable resin material for forming a coating layer, and contains an agent A (curing agent) and an agent B (main agent). The coating may contain paint, adhesive, etc.

When the coating material is used as a coating material, examples thereof include a coating material for plastics, a coating material for automobile exterior trim, a coating material for automobile interior trim, a coating material for electric and electronic materials (lenses, etc.), a coating material for building materials, a coating material for glass coating, a coating material for carpentry, a coating material for film coating, an ink coating, a coating material for artificial leather (coating agent), a coating material for cans, etc.

For example, the agent a preferably contains, as a polyisocyanate component, for example, an H6 XDI-modified composition (hereinafter referred to as a coating H6 XDI-modified composition) comprising: a modified H6XDI composition containing the functional group (isocyanurate group) of (a) and/or a modified H6XDI composition containing the functional group (urethane group) of (d). The agent a may contain other aromatic isocyanate, aliphatic isocyanate, or aromatic aliphatic isocyanate, as required.

For example, the agent B contains the high molecular weight polyol described above as an active hydrogen group-containing component. The high molecular weight polyol (hereinafter referred to as a coating high molecular weight polyol) as a coating raw material includes, for example, the above-mentioned acrylic polyol, the above-mentioned polyester polyol, and the above-mentioned fluorine polyol.

In addition, if necessary, a urethane catalyst, a water-repellent agent, an antifoaming agent, a surfactant, a slip imparting agent, a surface conditioner, an antioxidant, a weather-resistant stabilizer, a pigment, a dye, a filler, a resin powder, and the like may be blended in the agent B in an appropriate ratio.

As a method for forming the coating material, for example, the agent a and the agent B are mixed, and the mixed solution is applied to an object to be coated by a known method to be cured.

Thereby, a coating material can be formed. Such a coating material is excellent in discoloration resistance.

The color difference (Δb) of the coating layer in the wet heat durability test (2000 hours) is, for example, 0.5 or more, for example, 2.2 or less, preferably 2.0 or less, and more preferably 1.7 or less. The color difference of the coating layer in the wet heat durability test can be measured by the method described in examples described later.

According to the present invention, discoloration of a resin manufactured from the H6XDI composition can be suppressed by controlling the CIC content in the bis (isocyanatomethyl) cyclohexane composition to 0.5 to 600 ppm.

The invention will be further illustrated with reference to the following examples, which are not intended to limit the same. Unless otherwise specified, "parts" and "%" are based on mass.

1. Measurement method

Content of Compound CIC

First, a standard curve (external standard method) was prepared from the area values of the obtained gas chromatogram by analyzing the CIC synthesized below with a purity of 99mol% as a standard substance by gas chromatography under the following conditions. The retention time of CIC was 13.5 minutes.

Content of bis (isocyanatomethyl) cyclohexane (H6 XDI)

The H6XDI having a purity of 99mol% synthesized as described later was used as a standard substance, and was analyzed by gas chromatography under the following conditions by an internal standard method.

Instrument: agilent 7890

(1) Chromatographic column: DB-5 (30 m.times.0.25 mm.times.0.25 μm); (2) sample injection amount: 0.5. Mu.L; (3) split ratio: 1/30; (4) sample inlet temperature: 250 ℃; (5) column flow rate: 1.5mL/min; (6) temperature programming: maintaining 1min at 100deg.C, heating to 280 deg.C at 10deg.C/min, and maintaining for 20min; (7) FID detector temperature: 280 ℃; (8) hydrogen flow rate: 40mL/min, air flow rate: 400mL/min.

The iron and nickel content of the hydrochloride is determined by ICP-OES analysis;

instrument: thermo Scientific ICAP 7200ICP-OES

(calculation of the value of the yellow index (Y.I. value) of the optical Material)

The yellowness index of the lenses was determined according to national standard GB/T-2409-1980.

Optical materials of examples and comparative examples described below were formed into round flat plastic lenses having a thickness of 9mm and a diameter of 75mm, and tristimulus values x, y, and z were measured using a spectrophotometer. Y.i. was calculated using the following formula.

The following relationship exists: the smaller the y.i. value, the better the hue of the plastic lens, and the larger the y.i. value, the worse the hue.

(weather resistance test of elastomer)

Next, injection molding was performed using an injection molding machine (model: NEX-140, machine type) at a screw speed of 100rpm and a barrel temperature of 150 to 235℃under conditions of a mold temperature of 20℃for 10 seconds, an injection speed of 60mm/s and a cooling time of 45 seconds.

The obtained sheet (thickness: 2 mm) was cured at a constant temperature and humidity of 23℃and a relative humidity of 55% for 7 days to obtain elastomer sheets of each of examples and comparative examples described later.

Then, the b value (b 1, initial value) of the elastomer sheet was measured by a colorimeter, and then a xenon lamp irradiation test was performed. After 240 hours, the b value (b 2) of the elastomer sheet was measured in the same manner as described above. The color difference Δb (= |b2-b1|) of the elastomer sheet in the xenon lamp irradiation test (240 hours) was calculated.

For the xenon irradiation test, a super xenon climatic test chamber (Vibang apparatus) was used, and the temperature of the black panel was 89℃and the relative humidity was 50%, and the irradiance of the xenon was 100W/m ² (irradiation wavelength 300 to 400 nm).

(color difference (discoloration and coloring) in the wet and hot durability test of coating)

The b value (b 1, initial value) of the polyethylene terephthalate substrate on which the coatings of each example and each comparative example described later were formed was measured by a colorimeter (3 nh NR10QC). Next, the sample was kept at 85 ℃ and a relative humidity of 85% for 2000 hours using a thermo hygrostat (high-speed rail instrument). The b value (b 2) of the sample after 2000 hours was measured in the same manner as described above. The color difference Δb of the coating in the wet heat test (= |b2-b 1|) was calculated.

2. Preparation of various standard substances

CIC represented by the above chemical formula (1) was synthesized according to the synthesis route shown by the following reaction scheme.

To a mixed solution of 323.3mg (2 mmol) of 3- (chloromethyl) cyclohexylmethylamine and 7.0ml of chlorobenzene, phosgene was introduced, and the reaction was then carried out at 130℃and stopped when the reaction solution was clear. Cooled to room temperature, chlorobenzene was distilled off to obtain a concentrated solution, and 225.2mg (1.2 mmol) of 3-chloromethyl isocyanatomethyl cyclohexane CIC) was obtained.

¹ H-NMR(400MHz，CDCl3)δ3.40-3.21(m,4H)、1.75-1.27(m,10H)

¹³ C-NMR(100MHz，CDCl3)δ123.2、54.6、51.4、38.2、34.1、31.5、31.2、31.0、20.1。

3. Production of bis (isocyanatomethyl) cyclohexane compositions

Examples 1 to 7

The H6XDI composition was produced using the procedure shown in FIG. 1. Specifically, 800 parts by mass of chlorobenzene was charged into a salt-forming pot shown in fig. 1. Next, the salt forming temperature in the salt forming tank was adjusted to 25 ℃, and the salt forming pressure (gauge pressure) in the salt forming tank was adjusted to 0.04MPaG.

Subsequently, HCl gas was continuously fed from a hydrogen chloride feed line to the salt-forming tank at a feed rate of 76 parts by mass/hr, and an amine solution having a 1,3-BAC concentration of 10% by mass was continuously fed from an amine feed line to the salt-forming tank at a feed rate of 1000 parts by mass/hr, while a slurry containing 1,3-BAC hydrochloride was fed to the photo-forming tank through a hydrochloride feed line via a washing device.

Next, phosgene was continuously introduced into the first, second and third kettles at the feed rates shown in table 1. The reaction temperatures, residence times, and phosgene supply ratios to 1mol of 1,3-BAC hydrochloride in the three reaction tanks are shown in Table 1.

Thus, 1,3-BAC hydrochloride was reacted with phosgene to produce 1,3-H6XDI, and a reaction substance containing 1,3-H6XDI was produced. In addition, a part of the unreacted phosgene is condensed by a condenser into an photochemical kettle.

Next, the photochemical reaction liquid was continuously fed into the dephosgene column. The reaction mass is then degassed in a dephosgene column. Next, the deaerated matter is discharged from the deaeration tower through a deaerated matter transfer line, and continuously transferred to the deaeration tower. Thus, 195 parts by mass of a crude product having a concentration of 1,3-H6XDI of 95% by mass was prepared.

Next, the crude product is discharged from the desolventizing tower through a crude product transfer line and continuously transferred to a tar remover. The crude product is then detarring in a detarring device to produce an intermediate product. The content ratios of MCB, H6XDI, CIC in the intermediate materials are shown in table 1.

Next, the intermediate matters were continuously fed into the rectifying column at a feed rate of 175 parts by mass/hr. The rectifying column was packed with a packing material having a theoretical plate number of 20. The light components are then removed from the top of the column in a rectification column from which the 1,3-H6XDI composition product is withdrawn.

The rectification conditions in the rectification column are shown below.

Bottom temperature: 140-155 DEG C

Overhead temperature: 95-125 DEG C

Overhead pressure: 0-500Pa

Overhead reflux ratio: 8-40:1

Residence time: 1-5 hr

Thus, a 1,3-H6XDI composition was produced. The 1,3-H6XDI and CIC contents in the 1,3-H6XDI composition are shown in Table 1.

Comparative example 1

The experiment of comparative example 1 was conducted under the same conditions as in example 7 except that the amount of chlorobenzene in the washing unit was 0, as shown in Table 1, to obtain 1,3-H6XDI compositions of comparative example 1.

Comparative example 2

1 part by mass of the 1,3-H6XDI composition obtained in example 1 was mixed with 0.6 part by mass of the 1,3-H6XDI composition obtained in comparative example 3 to obtain a 1,3-H6XDI composition of comparative example 2.

Comparative example 3

Preparation of H6XDI as comparative example 3 using the procedure of example 9 of patent CN 105263618

TABLE 1 conditions and results for examples 1-7 and comparative examples 1-3

4. Elastomer (TPU)

Into a four-necked flask equipped with a stirrer, a thermometer, a reflux tube and a nitrogen supply line, 230.8 parts by mass of each of the 1,3-H6XDI compositions (polyisocyanate component) of examples 1 to 7 and comparative examples 1, 2 and 3 and 1000 parts by mass of an adipic acid-based polyester polyol (TAKELAC U-2024, an active hydrogen group-containing component) having a number average molecular weight of 2000 were charged, and the reaction was carried out at 80℃under a nitrogen atmosphere until the NCO group content became 4.7% by mass, to prepare an isocyanate group-terminated prepolymer.

Further, 3.9 parts by mass of a heat stabilizer (Ciba Specialty Chemicals, IRGANOX 245) and 0.07 parts by mass of a solution obtained by diluting tin octoate (inoKai reagent) as a catalyst to 4% by mass with diisononyl adipate (cinnoate reagent) were added to the isocyanate-terminated prepolymer, and the mixture was stirred and mixed with stirring at 600rpm using a mechanical stirrer (IKA, RW 20). Next, 61.4 parts by mass of 1, 4-butanediol (enokie reagent) which had been previously adjusted to 80 ℃ as a chain extender was added to the isocyanate-terminated prepolymer. Further, the mixed solution of the isocyanate-terminated prepolymer and the chain extender was sufficiently stirred for about 2 minutes until the whole was uniform.

Then, the mixed solution was poured into a stainless steel plate having been previously adjusted to a temperature of 150℃and reacted at 150℃for 1 hour, followed by a reaction at 100℃for 23 hours, to thereby produce an elastomer.

Then, the elastomer was removed from the tray, and cured at room temperature of 23℃under constant temperature and humidity conditions of 55% relative humidity for 7 days.

(evaluation of elastomer)

The color difference in the xenon lamp irradiation test of the obtained elastomer (TPU) was measured, and the results thereof are shown in table 2.

5. Optical material (Plastic lens)

The flask was charged with 0.01 part by mass of dibutyltin dichloride, 0.07 part by mass of an internal mold release agent (ZELECUN, acid phosphate, manufactured by Stepan Co., ltd.), 0.05 part by mass of an ultraviolet absorber (Biosorb 583, manufactured by Sakai chemical industry Co., ltd.), and 37.5 parts by mass of each of 1,3-H6XDI compositions of examples 1 to 7 and comparative examples 1,2 and 3. Then, they were stirred at 25℃for 1 hour to dissolve them, to prepare a polyisocyanate component.

Then, 33.6 parts by mass of 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane (polythiol component) was charged into the polyisocyanate component and mixed to prepare a polymerizable composition.

The polymerizable composition was defoamed at 600Pa for 1 hour, and then filtered through a 3-. Mu.mPTFE filter. Then, the molten glass was injected into a mold formed of a glass mold and a belt. The mold was put into an oven, gradually heated from 30℃to 120℃and polymerized for 22 hours. After the polymerization, the mold was taken out of the oven, and the mold was released from the oven to produce an optical material.

(evaluation of optical Material)

The y.i. value of the obtained plastic lens was measured. The results are shown in Table 2.

6. Two-component coating material

(TMP adduct of agent A1:1, 3-H6 XDI)

The 1,3-H6XDI compositions 477.2 parts by mass of each of examples 1 to 7 and comparative examples 1, 2 and 3 were mixed with 36.7 parts by mass of trimethylolpropane, and reacted at 70℃for 6 hours under a nitrogen atmosphere. The unreacted 1,3-H6XDI was distilled off using a thin film distillation apparatus from the reaction solution, whereby a 1,3-H6XDI modified composition was produced. The H6XDI modified composition contains a urethane group as a reaction product of 1,3-H6XDI and trimethylolpropane.

To this 1,3-H6XDI modified composition, ethyl acetate was added so that the solid content was 75% by mass, to prepare a polyisocyanate component (agent A1).

(agent A2: isocyanurate modified product comprising 1,3-H6 XDI)

To 100 parts by mass of each 1,3-H6XDI composition of examples 1 to 7 and comparative examples 1, 2 and 3, 2 parts by mass of 1, 3-butanediol was added, and the temperature was raised to 75℃under a nitrogen atmosphere to carry out a urethanization reaction for 2 hours. The equivalent ratio (NCO/OH) of the isocyanate groups of 1,3-H6XDI to the hydroxyl groups of 1, 3-butanediol was 24. Next, 0.1 part by weight of a solution of tetrabutylammonium hydroxide (37% methanol solution) was blended as an isocyanurate catalyst at the same temperature, and after 4 hours from the start of the reaction, the isocyanurate reaction was terminated. The obtained reaction solution was passed through a thin film distillation apparatus (temperature: 150 ℃ C., vacuum: 50 Pa) to remove unreacted 1,3-H6XDI (distillation yield: 60 mass%) to thereby produce a 1,3-H6XDI modified product composition. The 1,3-H6XDI modified composition contains isocyanurate groups as a trimer of 1,3-H6 XDI. To this 1,3-H6XDI modified composition, ethyl acetate was added so that the solid content was 75% by mass, to prepare a polyisocyanate component (agent A2).

(agent B)

40 parts by mass of a fluorine polyol (ZEFFLE GK-570, manufactured by DAIKIN INDUSTRIES, LTD., hydroxyl value (solid content: 64mgKOH/g, solvent: butyl acetate), 52.5 parts by mass of titanium oxide (CR 93 manufactured by Shiniter Co., ltd.), 33.8 parts by mass of butyl acetate, and 110 parts by mass of glass beads having a diameter of 2mm were stirred with a paint shaker (paint shaker) for 2 hours. Then, the glass beads were removed from the mixture by filtration. Then, a solvent was added so that the solid content concentration was 58 mass%, and a component (agent B) containing an active hydrogen group was produced. The content of titanium oxide in the active hydrogen group-containing component was 45 mass%.

(evaluation of coating)

The obtained polyisocyanate component (agent A) and the component (agent B) containing an active hydrogen group were mixed so that the equivalent ratio of isocyanate groups to hydroxyl groups (NCO/OH) became 1.0, to prepare a mixed solution. Next, butyl acetate was added to the mixed solution so that the NV value (coating film component mass) became 60%. Then, the mixture was applied to the surface of a polyethylene terephthalate (hereinafter referred to as PET) substrate, and heat-cured at 120 ℃ for 2 minutes. Next, the PET substrate coated with the mixed solution was cured at 60 ℃ for 2 days. Thus, a coating layer having a thickness of about 15 μm was formed on the PET substrate.

The weather resistance of the coating (color difference Δb of the coating in the wet heat test (= |b2-b1|) was measured, and the results are shown in table 2.

TABLE 2

Industrial applicability

The bis (isocyanatomethyl) cyclohexane composition and the polymerizable composition of the present invention can be suitably used as various industrial materials such as polyurethane materials. The resin of the present invention can be suitably used as various industrial products such as coating materials (paints, adhesives), elastomers, foams, and optical materials, for example.

Claims

1. A bis (isocyanatomethyl) cyclohexane composition comprising bis (isocyanatomethyl) cyclohexane and 0.5 to 600ppm chloromethyl isocyanatomethyl cyclohexane represented by the following structural formula (1):

the bis (isocyanatomethyl) cyclohexane composition is prepared by a process comprising the steps of:

an isocyanating step of isocyanating cyclohexyldimethylamine or its hydrochloride with phosgene to produce bis (isocyanatomethyl) cyclohexane, and producing chloromethylisocyanatomethyl cyclohexane represented by the structural formula (1) to prepare a reaction product containing bis (isocyanatomethyl) cyclohexane and chloromethylisocyanatomethyl cyclohexane;

A separation step of purifying the reaction substance to prepare a bis (isocyanatomethyl) cyclohexane composition having a chloromethylisocyanatomethyl cyclohexane content of 0.5 to 600ppm,

wherein the total content of iron and nickel in the cyclohexyldimethylamine or salt thereof is less than 100ppm.

2. The bis (isocyanatomethyl) cyclohexane composition according to claim 1, wherein said composition comprises bis (isocyanatomethyl) cyclohexane and 0.5 to 300ppm chloromethylisocyanatomethyl cyclohexane represented by structural formula (1).

3. A bis (isocyanatomethyl) cyclohexane modified composition which is a modified bis (isocyanatomethyl) cyclohexane composition according to claim 1 or 2, and which contains at least 1 of the following functional groups (a) to (i),

(a) An isocyanurate group,

(b) A uretdione group, which is a group,

(c) A biuret group,

(d) A urethane group,

(e) A ureido group, a hydroxyl group,

(f) An iminooxadiazinedione group, which is,

(g) An allophanate group, a radical of an allophanate,

(h) A uretonimine group, a group of which is shown in the specification,

(i) Carbodiimide groups.

4. A resin which is a reaction product of the bis (isocyanatomethyl) cyclohexane ingredient in the bis (isocyanatomethyl) cyclohexane composition according to claim 1 or 2 or the bis (isocyanatomethyl) cyclohexane modifier ingredient in the bis (isocyanatomethyl) cyclohexane modifier composition according to claim 3, with an active hydrogen group-containing ingredient.

5. The resin according to claim 4, which is an optical material.

6. The resin of claim 4 which is an optical lens.

7. The resin according to claim 4, wherein the active hydrogen group-containing component is a polyhydric alcohol having two or more hydroxyl groups, a polythiol having two or more mercapto groups, and/or a polyamine having two or more amino groups.

8. A process for preparing the bis (isocyanatomethyl) cyclohexane composition of claim 1 or 2, said process comprising the steps of:

9. The method for preparing a bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a chloromethyl isocyanatomethyl cyclohexane content in the bis (isocyanatomethyl) cyclohexane composition is 0.5 to 300ppm.

10. The method for producing a bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a solution concentration of the cyclohexyldimethylamine solution or the hydrochloride thereof is 3.0 mass% or more.

11. The method for producing a bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a solution concentration of the cyclohexyldimethylamine solution or the hydrochloride thereof is 5.0 mass% or more.

12. The method for producing a bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a solution concentration of the cyclohexyldimethylamine solution or the hydrochloride thereof is 30 mass% or less.

13. The method for producing a bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a solution concentration of the cyclohexyldimethylamine solution or the hydrochloride thereof is 20 mass% or less.

14. The method for producing a bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a molar ratio of phosgene to cyclohexyldimethylamine or hydrochloride thereof is 4 or more.

15. The method for producing the bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a molar ratio of the phosgene to cyclohexyldimethylamine or hydrochloride thereof is 5 or less.

16. The method for producing the bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a molar ratio of the phosgene to cyclohexyldimethylamine or hydrochloride thereof is 40 or less.

17. The method for producing the bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a molar ratio of the phosgene to cyclohexyldimethylamine or hydrochloride thereof is 30 or less.

18. The method for producing the bis (isocyanatomethyl) cyclohexane composition according to claim 8, wherein a molar ratio of the phosgene to cyclohexyldimethylamine or hydrochloride thereof is 20 or less.

19. An elastomer which is a reaction product of the bis (isocyanatomethyl) cyclohexane ingredient in the bis (isocyanatomethyl) cyclohexane composition according to claim 1 or 2 or the bis (isocyanatomethyl) cyclohexane modifier ingredient in the bis (isocyanatomethyl) cyclohexane modifier composition according to claim 3 with an active hydrogen group-containing ingredient.

20. The elastomer of claim 19, wherein the active hydrogen group-containing component is a high molecular weight polyol and one or both selected from a low molecular weight polyol having a molecular weight of 60 to 400 and/or a low molecular weight polyamine having a molecular weight of 60 to 400, and the high molecular weight polyol has a number average molecular weight of 401 to 10000.

21. A two-component curable resin raw material comprising the bis (isocyanatomethyl) cyclohexane composition according to claim 1 or 2 and/or the bis (isocyanatomethyl) cyclohexane modified composition according to claim 3, and an active hydrogen group-containing component.

22. The two-component curable resin raw material according to claim 21, wherein the two-component curable resin raw material is a coating raw material.