JPH0749574B2 - Adhesive made of polyurethane composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive comprising a polyurethane composition using a diisocyanate compound produced by a specific production method.

[0002]

2. Description of the Related Art Polyurethane is used for adhesives as a composition in which other components are appropriately mixed or reacted with other compounds due to its excellent properties.

For example, (a) Japanese Patent Publication Nos. 64-11233 and 64-1231
No. 8, JP 61-47775, JP 61-2.
No. 09282, No. 63-196678, and other adhesives for laminating films, JP-B-62-
Printing ink binders described in JP-A-3188, JP-A-59-147066, JP-A-61-166769, JP-A-62-220568 and JP-A-63-165472.

(B) JP-A-60-51766, JP-A-6-51766
No. 0-51713, Japanese Patent Publication No. 63-66846, and the like, which comprises a urethane (meth) acrylate resin curable with an ultraviolet ray or an electron beam reacted with a hydroxy group-containing (meth) acrylate, Curable adhesives for fibers, large cathode ray tubes, magnetic materials, etc.

(C) Japanese Patent Laid-Open Nos. 61-177241, 61-179733, 61-281136, 61-225271 and 61-22527.
No. 2, JP 61-225273, and JP 61-22.
No. 3078, No. 63-132922, and other polyurethane adhesive sheets and laminates.

(D) Reactivity consisting of the isocyanate prepolymer composition described in JP-A-61-136570, JP-A-61-145268, JP-A-61-183121, and JP-B-60-58269. adhesive.

(E) JP-A-61-296075, JP-A-62-53337, 61-278582, 6
A polyisocyanate compound obtained by buretization and / or isocyanurate formation described in JP-A 1-233022, or an isocyanate adduct obtained by reacting with a low molecular weight diol or triol was used. A primer composition for a urethane resin composition.

(F) JP-A-61-228015, JP-A-1-146978, JP-A-1-146979
An adhesive composition mainly composed of a urethane-modified epoxy resin as described in JP-A No. 1-146980.

(G) JP-B-1-20270, JP-A-60-141711, 60-233120, 60-243163, 61-98720
Water-dispersed polyurethane adhesive composition described in JP-A No. 1993-242242, etc.

(H) JP-B-64-7633, JP-A-62-30176, JP-A-63-179987, JP-A-1-108286, and JP-A-2-84482.
Examples thereof include adhesive compositions such as plastic films described in JP-A No. 1994-242.

These urethane adhesives generally use a polyisocyanate compound and a polyol such as a polyether polyol, a polyester polyol or a low molecular weight polyhydric alcohol and, if necessary, an active hydrogen. The compound is added as a chain extender and synthesized by a polyaddition reaction.

Among them, the polyisocyanate compound is
Except for those with a special structure, most of them are industrially produced by directly isocyanate-forming polyamine with phosgene. That is, at least one of the starting materials is produced by using toxic phosgene in any of the production steps.

[0013]

In the above-mentioned various adhesive fields, the weather resistance of polyurethane, which is one of the main components,
Corrosion resistance and heat resistance are important physical properties, and the emergence of polyurethanes having improved physical properties has been awaited.

As mentioned above, if at least one of the starting materials is made by using a toxic phosgene during any of the manufacturing processes, the use of it to produce polyurethane is necessarily in the product. Chlorine compounds remain mixed in.

When polyurethane containing chlorine compounds is used, weather resistance and corrosion resistance are particularly affected among the above physical properties.

Usually, in a diisocyanate compound produced by directly isocyanate-forming a polyamine with phosgene, unreacted phosgene at a concentration of several hundred ppm, chlorformate which is a by-product of the reaction, or reaction. Various chlorine compounds such as mono- and dicarbamoyl chloride compounds which are intermediates are mixed.

Moreover, this chlorine compound cannot be removed by an economical method.

The content of the diisocyanate compound produced by using dialkyl carbonate and diamine produced by using phosgene is lower than that of the diisocyanate compound produced directly by the phosgene method.
Even so, various chlorine compounds are mixed in at a concentration of several tens of ppm.

Therefore, the influence on weather resistance and corrosion resistance is considerably reduced, but it is not completely improved. As a result of diligent studies, the present inventors have found that an adhesive made of a polyurethane composition produced using a diisocyanate compound produced without using phosgene anywhere in the production process of the starting material has weather resistance. They have found that they are extremely superior in terms of corrosion resistance and heat resistance, and have reached the present invention.

[0020]

That is, the present invention relates to "a diisocyanate compound prepared from a dialkyl carbonate and a diamine which are prepared substantially without phosgene in the process. An adhesive composed of the prepared polyurethane composition ".

The diisocyanate compound used in the present invention is a urethane compound synthesized by reacting a dialkyl carbonate represented by dimethyl carbonate produced without using phosgene with a diamine. It is produced by thermally decomposing and converting it into an isocyanate.

As used herein, the phrase "does not use phosgene ..." means that phosgene is not used even in the step of producing one of the starting materials, dialkyl carbonate.

Incidentally, a process using phosgene in the step of producing a dialkyl carbonate (Japanese Patent Publication No. 62-8).
53500, JP-A-60-197639 and JP-A-6.
No. 1-118349, etc.), of course, but this is not included in the scope of the present invention.

On the other hand, the isocyanate used in the present invention
Since the phosgene is produced by a method that does not use phosgene at all in the process, it does not substantially contain a chlorine compound derived from phosgene, and as a result, the adverse effect on the physical properties of the chlorine compound is extremely small. The object of the present invention is achieved.

As mentioned above, the dialkyl carbonate is
It used to be manufactured using phosgene as a raw material, but today it is also manufactured using carbon monoxide as a raw material.
Also, new industrialization technology is being established.

It is essential for the present invention to use phosgene-free dialkyl carbonate in order to keep chlorine out.

A method for producing a dialkyl carbonate without using phosgene is disclosed in JP-A-63-57522,
JP-A-63-72650, JP-A-63-7265
No. 1, JP-A-01-287062, JP-B-6
0-58739, Japanese Patent Publication No. 56-8020,
Japanese Patent Publication No. 60-23662, Japanese Patent Publication No. 61-8816
JP-B, JP-B-61-43338, JP-B-63-
38018, JP 62-8113, JP 61-26977, JP 60-94943, JP 60-11443 and JP 60.
No. 181051 is disclosed.

As another method for producing a dialkyl carbonate without using phosgene, first, an alkylene carbonate is synthesized using alkylene oxide and carbon dioxide as starting materials, and this is used. Further, it is a method of obtaining dimethyl carbonate by reacting with methanol.

A method for synthesizing an alkylene carbonate using alkylene oxide and carbon dioxide as starting materials is described, for example, in JP-B-48-27314 and JP-A-51-51.
No. 13720, No. 51-19722, No. 51-19723, and No. 51-11876.
No. 3, JP-A-59-128382, and the like.

Further, alkylene carbonate and alcohol
Examples of the method for synthesizing a dialkyl carbonate from a resin include JP-B-60-22697 and JP-B-60-22.
698, JP-B-61-4381, JP-B-5
6-40708, Japanese Patent Publication 61-16267, Japanese Patent Publication 60-27658, Japanese Patent Publication 59-28.
No. 542 and Japanese Patent Application No. 1-178347.
It is disclosed in Japanese Patent Application No. 1-178348.

Of course, the dialkyl carbonates obtained by these methods are also applicable to the present invention. Hereinafter, specific production methods for producing dialkyl carbonates without using phosgene are described. Kaihei 01-28
The method disclosed in Japanese Patent No. 7062 will be described as a representative.

The starting material of this method is carbon monoxide, alcohol and oxygen, which are reacted in the presence of a catalyst under atmospheric pressure or pressure.

The catalyst used is a divalent copper salt, and specifically, copper acetate, copper pivalate, copper benzoate and other carboxylic acid copper salts, copper hydrobromide, copper carbonate and phenols. Examples thereof include weak acid copper salts such as copper salts and halides such as cupric chloride and cupric bromide.

The amount of these divalent copper salts used is 1 alcohol.
1-3000 millimoles per liter, preferably
It is 10 to 1000 millimoles.

An alkaline earth metal halide is also used in combination with the above catalyst.

Specific examples of the alkaline earth metal are beryllium, magnesium, calcium and barium, and their chlorides, iodides, acetates and the like are used.

The amount of the alkaline earth metal compound used is preferably 1/10 mol times to 10 mol times the divalent copper salt,
In the catalyst system, it is preferable to use the atomic ratio of halogen to copper (halogen / copper) in the range of more than 1/2 and less than 2.

The catalyst to be used is not limited to the above divalent copper salt, but may be a platinum group compound such as ruthenium, palladium or rhodium.

These are used in the form of halides, acetates and nitrates.

However, when a chloride is used as a catalyst, the chlorine concentration in the obtained dialkyl carbonate is slightly higher.

However, since it is removed at each stage, it hardly exists in the diisocyanate compound.

When these platinum group compounds are used in combination, the amount is not more than equimolar, preferably not more than 1/10 mol with respect to the divalent copper salt.

Alcohol, one of the starting materials for this process
As the alcohol, aliphatic alcohol such as methanol and ethanol, and aromatic alcohol can be used.

Of these various alcohols, methanol is the most preferable.

The dialkyl carbonate obtained when methanol is used is dimethyl carbonate. The starting materials for this method other than alcohol are carbon monoxide and oxygen, but these do not require particularly high purity and are diluted with a gas inert to the reaction such as nitrogen, argon, carbon dioxide. May be used.

The reaction is carried out at 1 to 100 atm. When diluting the reaction system with an inert gas, the partial pressure of carbon monoxide is 0.1 to 10 atm and the partial pressure of oxygen is 0.1 to 10 atm. It is good to use atmospheric pressure. The reaction temperature is preferably in the range of 20 to 250 ° C.

The chlorine content in the dialkyl carbonate produced as described above is a chlorine compound (copper halide, etc.).
Even when produced as a catalyst, it is at most 15 ppm,
When the diisocyanate compound is produced by the reaction with a diamine described below, the chlorine content in the diisocyanate compound also becomes a smaller value.

It is known that the chlorine content in the dialkyl carbonate produced using phosgene is 150 to 600 ppm.

Therefore, when a diisocyanate compound is produced by reacting a dialkyl carbonate having such a chlorine content with a diamine, the chlorine content in the obtained diisocyanate compound is 15 to 60 pp.
m, that is, 10 of chlorine in the dialkyl carbonate
% Is carried over into the diisocyanate compound. In addition, as a method for producing a dialkyl carbonate without using phosgene in the process, it is not a commercialized method, but there are the following prior arts. For example,
Japanese Patent Publication No. 56-8020 and Japanese Patent Publication No. 61-8816.

The starting materials for all of these are carbon monoxide, alcohol and oxygen, but the combination of the catalysts used is the technique described in the above-mentioned four Japanese Patent Laid-Open Publications and Japanese Patent Application Nos. Somewhat different.

Of course, it is possible to produce an adhesive comprising the polyurethane composition of the present invention by using the dialkyl carbonate produced by these methods.

Next, a method for producing a diisocyanate compound from a dialkyl carbonate and a diamine will be described.

Recently disclosed (Japanese Patent Laid-Open No. 64-8595)
6) is introduced as a production technique for converting a diamine into an isocyanate with dimethyl carbonate. One of the techniques described therein is a diisocyanate compound used in the adhesive of the present invention. It can be used as a manufacturing method.

The technique disclosed in Japanese Patent Laid-Open No. 64-85956 will be described in more detail as follows. That is, in the presence of an alkali catalyst, a diamine and dimethyl carbonate are reacted to synthesize a corresponding urethane compound in a first-step reaction, and then the urethane compound is treated with manganese, molybdenum, or tungsten in a high-boiling solvent.
In the presence of one or more compound catalysts selected from the group of zinc,
It is a method for producing a diisocyanate compound which can be used in the present invention, by two steps of a second step of thermally decomposing under a reduced pressure of 700 Torr to obtain a corresponding diisocyanate compound compound.

It is necessary to use dimethyl carbonate produced without using phosgene, and dimethyl carbonate produced from carbon monoxide and methanol as raw materials is inexpensive and is a preferable starting material. It is a raw material.

Amine compounds are classified into aliphatic amine compounds and aromatic amine compounds based on their chemical reactivity. The aliphatic amine compound has a fast reaction with an alkali catalyst and is preferably used in this method.

Aliphatic amines are classified into alicyclic amine compounds having an alicyclic skeleton in the molecule and chain aliphatic amines having a chain skeleton.

As the amine compound that can be used in this method, the following amines can be given as examples. As alicyclic amine, isophorone diamine, 1,
3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, hydrogenated diaminodiphenylmethane, hydrogenated toluylenediamine, hydrogenated naphthalenediamine, etc. There is.

Isophoronediamine includes amino group --NH.
₂ and the aminomethyl group —CH ₂ NH ₂ are in the cis position and the trans position in the cyclohexane ring, but both isomers are used as raw materials, and as in commercially available isophoronediamine, the cis form is used. It does not matter even if it is a mixture of trans forms.

A diamine having an amino group bonded to a saturated carbon and having an aromatic ring in the skeleton is preferably used as a raw material, and xylylenediamine and the like can be mentioned as an example.

As the chain aliphatic amine, ethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, tetramethylenediamine, 1, 1
2-diaminododecane and the like can be mentioned.

Aromatic amines are inferior in space-time yield or yield in the first-step reaction as compared with aliphatic amines, but they can also be urethanized and used as raw materials in this method.

Examples include diaminodiphenylmethane, toluylenediamine, phenylene-1,3-diamine, phenylene-1,4-diamine and naphthalenediamine.

All amines may have stable groups such as ether bond, sulfone group, carbonyl group and halogen group in the skeleton.

The basic substance used as a catalyst in the first-step reaction is an alkali metal or alkaline earth metal alcoholate, such as lithium, sodium, potassium, calcium, barium methylate or ethylate. The
Tertiary butyrate etc. can be mentioned as the example.

The amount of the alkali catalyst used is determined according to the activity of the catalyst so that the reaction is completed in a practical time.
In the case of sodium methylate, 0.001 to 0.001 in the reaction crude liquid
The reaction proceeds with the addition of 5% by weight, preferably 0.1 to 3% by weight.

It is practically possible to select the reaction temperature in the range from 0 ° C. to the boiling point of the reaction crude liquid, but the reaction is slow at low temperature and the boiling of the by-produced methanol becomes intense at high temperature. Therefore, it is preferable to select in the range of 30 ° C to 80 ° C.

When the raw material is a solid or when it is desired to prevent the urethane compound from being precipitated, a solvent may be used. For example, a raw material and a product such as methanol, ethanol, tetrahydrofuran, dioxane, benzene and toluene may be used. A solvent that is inert to can be used.

When the basic catalyst is heated together with the urethane compound, the urethane compound is further changed to a high-boiling substance other than the target, so that the basic catalyst is neutralized after the first-step reaction.

The urethane compound is purified and taken out to the required purity from the neutralized reaction crude liquid by a general purification method such as distillation, crystallization, washing with water and reprecipitation.

As the urethane compound, the following urethane can be obtained corresponding to the diamine used as the raw material. Three
-Methoxycarbonylaminomethyl-3,5,5-trimethyl-1-methoxycarbonylaminocyclohexane, 1,3-bis (methoxycarbonylamino) cyclohexane, 1,4-bis (methoxycarbonylamino)
Cyclohexane, 1,3-bis (methoxycarbonylaminomethyl) cyclohexane, 1,4-bis (methoxycarbonylaminomethyl) cyclohexane, bis (methoxycarbonylaminocyclohexyl) methane, methylbis (methoxycarbonylamino) cyclohexane, bis (methoxycarbonylamino) ) Decalin, bis (methoxycarbonylaminomethyl) benzene, bis (methoxycarbonylamino) ethane, bis (methoxycarbonylamino) hexane, 2,2,4-trimethyl bis (methoxycarbonylamino) hexane, 2,4,4-trimethyl Bis (methoxycarbonylamino) hexane,
1,4-bis (methoxycarbonylamino) butane,
1,12-bis (methoxycarbonylamino) dodecane, bis (methoxycarbonylaminophenyl) methane, bis (methoxycarbonylamino) toluene, 1,
3-bis (methoxycarbonylamino) benzene, 1,
4-bis (methoxycarbonylamino) benzene, bis (methoxycarbonylamino) naphthalene and the like can be mentioned.

These compounds can be converted into isocyanate compounds in good yield by thermal decomposition which is a second-step reaction.

The urethane compound is thermally decomposed in an inert solvent under reduced pressure in the presence of a metal element such as manganese, molybdenum, tungsten, or zinc, or an inorganic compound or an organic compound, thereby desorbing alcohol. Happened,
A diisocyanate compound corresponding to the skeleton of the raw material urethane is produced.

For example, isophorone diisocyanate,
Cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, hydrogenated diphenylmethane diisocyanate -, Hydrogenated toluylene diisocyanate, hydrogenated naphthalene diisocyanate, xylylene diisocyanate, ethylene diisocyanate
, Hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4
-Trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, dodecane-1,12-diisocyanate, diphenylmethane diisocyanate, toluylene diisocyanate, phenylene-1,3-diisocyanate G, phenylene-1,4-diisocyanate
And an isocyanate compound such as naphthalene diisocyanate are produced.

The compound used as the catalyst is disclosed in JP-A-64-85956, that is, metal manganese, manganese oxide (MnO, or M).
n ₂ O ₃ ) manganese chloride, manganese sulfate, manganese phosphate, manganese borate, manganese carbonate, manganese acetate, manganese naphthenate, manganese (2) acetylacetona
, Manganese (3) acetylacetonate, metallic molybdenum, molybdenum trioxide, molybdenum acetylacetonate (MoO ₂ (acac) ₂ ) molybdenum dioxide, metallic tungsten, tungsten hexacarbonyl, tungstic anhydride, tungstic acid, etc. Not only that, but most other catalysts can be used as long as they are used as a catalyst for thermal decomposition of urethane compounds.

These can be used in the form of hydrated salt or anhydrous.

Zinc halides, manganese chloride, manganese sulfate, manganese acetate, and manganese naphthenate are particularly suitable because they are industrially easily available, inexpensive, and highly active. In particular, manganese acetate is preferable because it has sufficient activity at a low concentration in the reaction crude liquid.

The amount of the catalyst used is usually most preferably in the range of 0.0005% by weight to 5% by weight in the solvent.

When the reaction temperature is lower than 150 ° C., the isocyanate compound is slowly generated, which is not practical.
If it is higher, it is difficult to carry out industrially, which is disadvantageous. The solvent needs to be inactive with respect to the isocyanate compound and the urethane compound, and can be used by selecting from an aliphatic compound, an aromatic compound, an alkylated aromatic compound, an ether compound and the like. Even if it contains an inactive group such as a halogen group, it can be used as a solvent.

A solvent whose boiling point is not close to that of the isocyanate compound is preferable because it can be easily purified and separated. A solvent having a boiling point lower than that of the produced isocyanate compound is distilled out together with the isocyanate compound, which is disadvantageous because the process is complicated in practice, and a solvent having a higher boiling point than the produced isocyanate compound is preferable.

The reaction is an isocyanate produced from the reaction system.
It is carried out under reduced pressure at which the compound is distilled. As a result, the concentration of the isocyanate compound in the system is kept low, side reactions are suppressed, and a high reaction yield is achieved.

This effect is particularly effective when carried out under the boiling of the solvent. From this point, the reaction pressure is preferably carried out at the reaction temperature and at the degree of reduced pressure at which the solvent boils.

If the degree of reduced pressure is too high, it becomes difficult to recover the alcohol produced as a by-product, and it is disadvantageous in terms of equipment and utility. Therefore, it is usually 1 Torr or more and 700 Torr or less.

Preferred solvents are o-ta-phenyl,
m-ta-phenyl, p-ta-phenyl, mixed diphenylbenzene, partially hydrogenated triphenyl, dibenzylbenzene, dibenzyltoluene, biphenyl, phenylcyclohexane, bicyclohexyl, phenylether, benzylether, diphenylmethane, xylene. , Trimethylbenzene, ethylbenzene, dodecylbenzene, chlorobenzene, dichlorobenzene, hexadecane, tetradecane, octadecane, eicosane, and tetramethylene sulfone.

A continuous reaction in which a solvent containing a catalyst is boiled under reduced pressure and a urethane compound is charged therein is advantageous.

The alcohol by-product and the isocyanate compound produced in the reaction can be satisfactorily purified by introducing them from the reactor to the condenser as gas and condensing only the isocyanate compound.

The resulting diisocyanate compound can be further purified, if necessary. As mentioned above, the production technique examples of the diisocyanate compound which can be used in the present invention have been described, but not limited to this method, dimethyl carbonate and diamine produced substantially without using phosgene in the process. The diisocyanate compound produced from and can be used in the present invention.

For example, a technique for obtaining urethane from dimethyl carbonate and an amine compound by using a Lewis acid catalyst is disclosed (Japanese Patent Publication No. 51-33095), but it can be used in the first step reaction.

Also for the second-stage reaction, a technique of performing thermal decomposition in the gas phase (Japanese Patent Laid-Open Nos. 59-205352 and 5205/1985).
9-205353) and different liquid phase technologies (Japanese Patent Publication No. 57-
45736), SnO ₂ , CuO as a catalyst to obtain isophorone diisocyanate from isophorone dicarbamine ester.
There is no problem even if a diisocyanate compound obtained by using a technique for synthesizing a compound (JP-A-62-238255) is used. The diisocyanate compound thus obtained is used in the adhesive of the present invention by a polyaddition reaction using a polyol such as a polyether polyol, a polyester polyol, and a polycarbonate diol. The resulting polyurethane can be synthesized. For example, JP-A-1-135872 and JP-A-1-172.
No. 416, JP-A-1-242613, JP-A-60-195115, JP-A-62-7714, etc., coating agents for optical fibers, JP-A-60-36577. Publication (USP 50938
9), JP-A-62-116620 (USP 77).
9838) and other radiation-curable adhesives,
JP-A-62-746969, JP-A-62-6886
No. 1, JP-A 1-161073, JP-A 61
-87765, JP-A 61-145201, JP-A 62-174277, and JP-A 63-4.
3967, JP-A-64-85262, etc., cathodic deposition type electrodeposition adhesives, JP-A-60.
-250069, JP 61-89274, JP 62-164738, JP 2-61.
No. 9 (USP 549209), JP-A-2-487.
No. 8 (DE 3803628) and other polyurethane adhesives, JP-A-54-48777 (DE 2732622), JP-A-54-48896 (DE 2732775), JP-A-56-5096.
Publication 9 (DE 2938855), Japanese Examined Patent Publication No. 58-4
068 (DE 2346818), JP-A-59-
Japanese Patent No. 4658 (DE 3221558), Japanese Patent Publication No. 1-
One-component type baked urethane adhesives described in JP 50265 (DE 3030544) and the like, JP-A-58
-1185553 (DE 3151853), JP-A-59-95259, JP-A-61-176625.
JP-A-55-143978 (DE 31
51855), JP-A-58-118575 (DE)
3151855), JP-A-57-78460 (DE 3033864), JP-A-60-181114.
Japanese Laid-Open Patent Publication No. 61-28518, Japanese Patent Publication No. 61-33
852, Japanese Patent Publication No. 59-2865, and Japanese Patent Laid-Open No. 47-
5837 (DE 2043493), JP-A-5050
-419929 (DE2325824), JP-A-6-6
0-255861, JP 61-283669, JP 62-30160, JP 62-2.
Two-component acrylic urethane or polyester urethane adhesive obtained by using a polyisocyanate compound described in JP-A-77472, etc., JP-A-53-121
773 (DE 2712931), JP-A-54-
84584 (DE 2751805), JP-A-5
No. 4-44670 (DE 2729704), Japanese Examined Patent Publication No. 60-41062 (DE 2929224),
JP-B-64-5627 (DE 303055
8), JP-A-56-49761 (DE 2929)
150), JP-A-60-47079 (DE 33).
22718), JP-A-60-53511 (DE)
3328131), JP-A-57-63324 (D
E 3030539), Japanese Patent Publication No. 56-51190 (DE 2105777), Japanese Patent Publication No. 61-31744 (DE 2735497), and other urethane powder adhesives obtained using a block isocyanate curing agent. Agent, JP-A-62-146965 (U
S808762 / A), JP-A-60-13858 (DE 3322723), JP-A-62-16986.
4 and JP-A-62-246972, there are primer adhesives and rust preventive adhesives using urethane prepolymers.

The diisocyanate compound thus obtained, polyetherpolyol and polyesterpolyol.
A polyurethane resin composition that can be used in the adhesive of the present invention can be synthesized by a polyaddition reaction using a polyol such as polycarbonate or polycarbonate.

Among the urethane adhesives shown in the prior art, a method for producing a polyurethane resin composition will be described in more detail.

The kind of organic diisocyanate compound that can be used is not particularly limited as long as it is other than the one directly produced from phosgene and diamine.

However, the effect is particularly large in the case of an alicyclic diisocyanate compound which is originally characterized by yellowing resistance.

Among them, one kind or two or more kinds can be used.

At this time, if necessary, a chain extender may be allowed to coexist in the above mixture. As the chain extender, there are low molecular weight compounds having active hydrogen, and specific examples thereof include the following.

Ethylene glycol, propylene glycol
1,4-butylene glycol, 2-methylpropanediol, neopentyl glycol, pentanediole
1,6-hexanediol, ethylenediamine, propylenediamine, hydrazine, isophoronediamine,
Metaphenylenediamine, 4,4'-diaminodiphenylmethane, diaminodiphenylsulfone, 3,3'-
Dichloro-4,4'-diaminodiphenylmethane and the like can be mentioned.

In the present invention, as a method for producing polyurethane, the above-mentioned various polyols are reacted with an excess of an organic diisocyanate compound to produce a prepolymer having a terminal isocyanate group, and then a diamine. Any method such as a prepolymer method in which a chain extender such as a diamine or a diamine is reacted to form a polyurethane, or a one-shot method in which all components are simultaneously added to form a polyurethane can be used.

Further, these reactions can be carried out without solvent or in a solvent.

It is preferable to use an inert solvent.

Specific examples include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, dimethylformamide, and tetrahydrofuran.

Further, a urethane-forming catalyst may be used in the urethane-forming reaction.

Examples thereof include organic tin compounds such as tin octylate and dibutyltin dilaurate, and tertiary amines such as N.methylmorpholine and triethylamine.

When the polyurethane produced as described above is produced, the yellowing resistance is particularly excellent.

[0104]

The adhesive comprising the polyurethane resin composition of the present invention has improved physical properties such as weather resistance, corrosion resistance and heat resistance.

The effects of the present invention will be more specifically described below with reference to synthesis examples, examples and application examples, but these synthesis examples, examples and application examples do not limit the present invention.

[Synthesis Example-1] [Dimethyl Carbide Produced Without Using Phosgene in the Process]
Synthesis of Bonnet-Synthesis of Dimethyl Carbonate Using Carbon Monoxide and Methanol as Raw Materials] Synthesis of dimethyl carbonate using an autoclave coated with Teflon and having an internal volume of 5 liters. The reaction was carried out.

7.5 millimolar palladium chloride as a catalyst
1 / l, cuprous acetate 187.5 mmol / l and magnesium chloride 187.5 mmol / l 526 ml of methanol solution were used, nitrogen gas 47.5 vol%, argon / oxygen (oxygen concentration 3
3.0 vol%) 22.5 vol% mixed gas 12.
Inflow at 0 kg / cm ² and 130 in the autoclave.
The temperature was raised to ° C and the reaction was carried out for 1 hour.

The reaction crude liquid was distilled to obtain dimethyl carbonate. The above synthetic reaction was repeated 20 times to give 23
4 g of dimethyl carbonate was obtained.

The chlorine content in the obtained dimethyl carbonate was about 11 ppm.

An ion chromatograph (IC-500) was used for measuring the chlorine content. [Synthesis Example-2] The synthesis reaction was repeated 20 times in the same manner as in Synthesis Example-1 except that sodium chloride was used instead of magnesium chloride to obtain about 352 g of dimethyl carbonate.

However, the reaction in this case proceeded with the catalyst suspended in the liquid.

The chlorine content in the obtained dimethyl carbonate was about 8 ppm.

[Synthesis Example-3] 211 g of dimethyl carbonate synthesized in Synthesis Example-1
Was charged in a round bottom flask equipped with a stirrer, and the temperature was raised to 70 ° C. under a nitrogen stream while stirring.

Next, 5.22 g of 28% methanol solution of sodium methylate and 50 g of isophoronediamine were charged into the flask by two charging pumps at a uniform charging rate over 70 minutes.

During this time, the reaction temperature was maintained at 70 ° C.

Further, after the completion of the charging, the reaction crude liquid obtained by aging at the same temperature for 3 hours and then neutralizing with phosphoric acid was analyzed by gas chromatography. As a result, a urethane compound corresponding to isophoronediamine, that is, 3 -Methoxycarbonylaminomethyl-3,5,5-trimethyl-1-
It was confirmed that methoxycarbonylaminocyclohexane (abbreviated as isophorone dicarbonate, abbreviated IPDC) was produced at a yield of 99% based on isophoronediamine and a yield of 99% based on consumed dimethyl carbonate.

The above-mentioned crude reaction liquid was deboiled to a low boiling point and further washed with water to obtain IPDC, which was used as a raw material in Synthesis Example-5.

[Synthesis Example-4] Similar to Synthesis Example-3 except that the dimethyl carbonate obtained in Synthesis Example-2 was used in place of the dimethyl carbonate obtained in Synthesis Example-1. The synthetic reaction was carried out to obtain isophorone dicarbamate in almost the same yield.

The above reaction crude liquid was deboiled to a low boiling point and further washed with water to obtain IPDC, which was used as a raw material in Synthesis Example-6.

[Synthesis Example-5] 3-methoxycarbonylaminomethyl-3,5,5 obtained in Synthesis Example-3 using a glass reboiler having a capacity of 200 ml equipped with a 10-stage older tower. −
Trimethyl-1-methoxycarbonylaminosiloxane (abbreviation: isophorone dicarbonate, abbreviation IPD)
C) was continuously decomposed.

As the solvent, m-ta-phenyl was used.

First, 117 ml of m-
Ta-phenyl and anhydrous manganese acetate corresponding to 10 ppm of m-ta-phenyl were charged, and the mixture was heated under reduced pressure of 10 Torr until a boiling state was reached.

Then, 59.0% by weight of IPDC was added to the reactor,
120 g of a mixed liquid of 41.0% by weight of m-ta-phenyl
It was prepared at the speed of Hr.

Isophorone diisocyanate (abbreviation: IPDI) as a product was withdrawn from the top of the distillation column, and operation was carried out at a bottoms withdrawing speed such that the liquid level in the reactor was constant. Pour hot water at 60 ℃ into the condenser,
The IPDI component was condensed and the methanol was released as a gas. During operation, the concentration of anhydrous manganese acetate in the reactor was 10p
125ppm corresponding to the amount of bottoms so that it is kept at pm
Anhydrous manganese acetate solution was charged into the reaction solution.

When the temperature in the column, the weight of each of the distillate and the bottoms and the composition were stabilized, 18.2 g of the distillate was distilled out in 1 hour.
77.2% by weight of PDI, monoisocyanate (abbreviation:
IPMI) 22.7% by weight, m-ta-phenyl 0.05
% By weight.

The reactor temperature was 245 ° C.

The IPDC conversion was 99% by weight, and the IPDC high boiler conversion was 6% by weight. Yield is charged IP
Based on DC, IPDI was 74% and IPMI was 19%. The chlorine content in the obtained IPDI was 0.2 ppm.

[Synthesis Example-6] Anhydrous manganese acetate was dissolved in methanol to a concentration of 1% by weight.

This solution was diluted 80-fold with IPDI and
The catalyst solution was 25 ppm.

The liquid was uniform and had a low viscosity.

Using the above catalyst solution, the urethane compound was charged in 5 stages from the bottom of the distillation column, and the operation was performed in the same manner as in Synthesis Example 5 except that the catalyst charge stage was changed from the bottom to 13 stages.

When the internal temperature, the respective weights of the distillate and the bottoms, and the composition became stable, the distillate was distilled in 1 hour.
It was 8.1% by weight, IPMI 1.8% by weight, and m-ta-phenyl 0.05% by weight.

The IPDC conversion rate was 99% by weight, and the IPDC high boiler conversion rate was 2% by weight. Yield is charged IP
Based on DC, IPDI was 95.5% and IPMI was 1.5%. The obtained IPDI fraction was further purified by batch distillation to a purity of 99.7% and used as a raw material in the following test examples.

The chlorine content in the obtained IPDI was 0.1.
It was ppm.

[Example-1] In a reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube, 44.4 g of IPDI obtained in [Synthesis example-6] and polycaprolactone dio- with a number average molecular weight of 2000 were obtained. Le (trade name PCL-22 manufactured by Daicel Chemical Industries, Ltd.
0) 200 g and 46.2 mg (1.12 × 10 ⁻⁴ equivalent to the isocyanate group) of dibutyltin dilaurate, which is an example of Lewis acid, were charged and the temperature of the reaction system was adjusted while stirring in a nitrogen atmosphere. The temperature was set to 80 ° C. and the urethane reaction was continued for 3 hours to obtain a urethane prepolymer having an NCO content of 3.3% by weight.

After the temperature of the reactor was lowered to 40 ° C., 199 g of xylene and 161 g of methyl isobutyl ketone (MIBK) were added to this urethane prepolymer to make a uniform solution. Isophoronediamine (IPD) 16.5 g, di-isobutylamine 0.8 g, MIBK 38.0 g, isopropanol 1 were added to the obtained urethane prepolymer solution.
A solution of 99 g was added, and a chain extension reaction with diamine was performed.

The reaction temperature was set to 50 ° C. and the reaction was continued for 3 hours to obtain the desired polyurethane resin solution.

The resulting polyurethane resin solution had a solid content of 30.8% by weight, a viscosity of 4300 cP / 25 ° C., and a residual NC
O was less than 0.05% by weight.

Example 2 Instead of polycaprolactone diol having a number average molecular weight of 2000, polytetramethylene glycol having a number average molecular weight of 2000 (trade name PTG20 manufactured by Hodogaya Chemical Co., Ltd.) was used.
A polyurethane resin solution was synthesized by the same apparatus and method as in [Example-1] except that 200 g of 00) was used.

The obtained polyurethane resin solution had a solid content of 31.5% by weight, a viscosity of 3900 cP / 25 ° C., and a residual NC.
O was less than 0.04% by weight.

[Comparative Example-1] The same apparatus and the same apparatus as in [Example-1] except that the IPDI obtained by using phosgene was used in place of the IPDI obtained in [Synthesis Example-6]. A polyurethane resin solution was synthesized by various methods.

The obtained polyurethane resin solution had a solid content of 30.6% by weight, a viscosity of 4060 cP / 25 ° C., and a residual NC.
O was less than 0.01% by weight.

[Comparative Example-2] The same apparatus and the same apparatus as in [Example-1] except that IPDI which was considered to be produced by using phosgene was used in place of IPDI obtained in [Synthesis Example-6]. A polyurethane resin solution was synthesized by various methods.

The obtained polyurethane resin solution had a solid content of 31.2% by weight, a viscosity of 2160 cP / 25 ° C., and a residual NC.
O was less than 0.01% by weight.

Example-3 A reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube was used to prepare a tetrahydrofuran-propylene oxide copolymer having a number average molecular weight of 2000 (Hodogaya Chemical Co., Ltd. P
PTG2000) 1968 g, IPDI 444 g obtained in [Synthesis example-6], dibutyltin dilaurate 0.1 g, and paramethylbenzoic acid 0.5 g were charged.
The reaction was carried out at 70 ° C for 5 hours to obtain a urethane prepolymer.

The temperature was further lowered to 50 ° C., and 1.3 g of t-butylhydroquinone, 255 g of 2-hydroxyethyl acrylate and 0.3 g of dibutyltin dilaurate.
Was added and reacted for 5 hours to obtain a urethane acrylate resin.

70 g of the above resin was mixed with 20 g of trimethylolpropane triacrylate and 5 g of benzyl dimethyl ketone.
g and 5 g of benzophenone were blended to obtain an ultraviolet curable adhesive resin composition.

[Comparative Example-3] The same apparatus and the same apparatus as in [Example-3] except that IPDI which was considered to be produced by using phosgene was used in place of IPDI obtained in [Synthesis Example-6]. The ultraviolet curable adhesive resin composition was obtained by various methods.

Example 4 In a reactor equipped with a thermometer, a stirrer, a nitrogen introducing tube and a cooling tube, 60 g of xylene and 0.2 g of benzoyl peroxide were added, and the temperature was raised to 120 ° C.

To this, 15.6 g of styrene, 30.0 g of methyl methacrylate, 19.2 of n-butyl acrylate.
g, γ-methacryloxypropyltrimethoxysilane 3
A mixed solution of 7.3 g and azobisisobutyronitrile 0.1 g was added dropwise at 120 to 130 ° C. over 2 hours.

After continuing the reaction at the same temperature for another 3 hours, the reaction temperature was lowered to 70 ° C., and 52 g of polypropylene glycol having a number average molecular weight of 400 (Sanyox PP-400 manufactured by Sanyo Kasei Co., Ltd.) was prepared. -6] IPDI (28.9 g) and dibutyltin dilaurate (0.02 g) were added and the mixture was reacted at the same temperature for 4 hours, and then endoethylenepiperazine (2.0 g) and dibutyltin diacetate (2.0 g) were added. In addition, a urethane prepolymer resin solution containing an isocyanate group was obtained.

[Comparative Example-4] The same apparatus and the same apparatus as in [Example-4] except that IPDI which was considered to be produced by using phosgene was used in place of the IPDI obtained in [Synthesis Example-6]. A urethane prepolymer resin solution was obtained by various methods.

Example-5 Polytetramethylene glycol having a number average molecular weight of 1000 (PTG1000 manufactured by Hodogaya Chemical Co., Ltd.), 1,4-
Butanediol and polycaprolactone triol having a number average molecular weight of 540 (trade name PLACCEL305 manufactured by Daicel Chemical Industries, Ltd.) were mixed at a ratio of 35:55:10 parts by weight, and dibutyltin dilaurate was added to the mixture.
0.05 wt% was added.

On the other hand, IPDI obtained in [Synthesis example-6]
Was used to synthesize an isocyanato group-containing urea derivative having an NCO content of 31.5% by weight, which was obtained by the method described in JP-B-58-40536.

The above two components were used at NCO / OH = 1.0 (molar ratio), degassed under vacuum, then heated to about 40 ° C. and cast on a polycarbonate resin film. To do.

After curing and drying at about 120 ° C. for 25 minutes, an adhesive film having a thickness of about 0.5 mm was obtained. [Comparative Example-5]
An adhesive film was obtained by the same apparatus and the same method as in [Example-5] except that IPDI which was considered to be produced by using phosgene was used in place of the IPDI obtained in [Synthesis example-6].

[Application Example-1] The polyurethane resin solutions 100 obtained in [Example-1], [Example-2], [Comparative Example-1] and [Comparative Example-2].
50 parts by weight of titanium oxide (Type CR-90 manufactured by Ishihara Sangyo Co., Ltd.), 70 parts by weight of MIBK / toluene / IPA mixed solution (30:30:40 parts by weight ratio), DISPARON 1860 (Kusumoto Kasei) Leveling agent manufactured by Co., Ltd.) 0.75 parts by weight, Disparlon 1984-5
0 (Kusumoto Kasei Co., Ltd. Wetting and dispersing agent) 0.75 parts by weight and Disparon OX-77 (Kusumoto Kasei Co., Ltd.)
Defoaming agent) 0.75 parts by weight of a mixture was added to a ball diameter of 3 mm.
Approximately 1 with a vibration type disperser together with 150 parts by weight of glass media
After time-dispersing, a white printing ink was prepared.

The obtained printing ink was applied to OPP film and PET film in No. It was coated with 40 bar coater and dried for 1 week at room temperature and humidity of 60 to 70%.

The results of evaluation of the adhesiveness, oil resistance, heat resistance and humidity resistance of the prepared printed matter are shown in Table 1. The adhesive made of the polyurethane resin composition of the present invention shows excellent weather resistance and heat resistance. The physical properties are further improved.

[Application Example-2] The ultraviolet-curable adhesive resin compositions obtained in [Example-3] and [Comparative Example-3] were added to a vinyl chloride sheet with No. 20 bars
An OPP sheet coated with a coater and previously coated with a chlorinated polypropylene resin was applied.

This adhesive sheet has an output of 1 kW and an output density of 4
It was cured at a conveyor speed of 10 meters / minute using a 0 W / cm high pressure mercury lamp with a converging type reflection plate (manufactured by Iwasaki Electric Co., Ltd.). The results of evaluation of the adhesiveness, weather resistance and heat resistance of the adhesive sheet obtained by the above method are shown in Table 2. The adhesive comprising the polyurethane resin composition of the present invention shows weather resistance, heat resistance, etc. The physical properties of are improved.

[Application Example-3] The urethane prepolymer resin solution obtained in [Example-4] and [Comparative Example-4] was applied to an aluminum plate having a clean surface with No.
It was coated with 20 bar coater, a polyester non-woven sheet was stuck thereon, and cured under the conditions of 20 ° C. and humidity of 70% to obtain a moisture-curable laminate.

As a result of evaluating the adhesiveness, weather resistance and heat resistance of the laminate obtained by the above method, the adhesive comprising the polyurethane resin composition of the present invention has physical properties such as weather resistance, corrosion resistance and heat resistance. It is an improved one.

[Application Example-4] The adhesive sheets obtained in [Example-5] and [Comparative Example-5].
5kg / cm
While applying a pressure of ² , heat treatment was carried out at 80 ° C. for 30 minutes to obtain a polycarbonate / aluminum laminate.

The results of evaluation of the adhesiveness, weather resistance and heat resistance of the laminate obtained by the above method are shown in Table 4. The adhesive made of the polyurethane resin composition of the present invention shows the weather resistance and heat resistance. And other physical properties are improved. Table 1-Results of Application Example 1 Polyurethane Example 1 Example 2 Comparative Example 1 Comparative Example 2 Resin solution 100 100 100 100 100 A 50 50 50 50 50 B 70 70 70 70 70 C 0.75 0.75 0.75 0.75 D 0.75 0.75 0.75 0.75 E 0.75 0.75 0.75 0.75 Base material OPP PET OPP PET OPP PET OPP PET Adhesion test △ ○ △ ○ △ ○ △ ○ Oil resistance test △ ○ △ △ △ △ × △ Heat resistance test △ △ × △ × △ × × Accelerated weathering test △ △ × △ × △ × × Explanations of abbreviations in Table 1, test methods, judgment criteria, etc. A: Type CR-90 B: Thinner C: Desperon 1860 D: Desparon 1984-50 E: Despa -Ron OX-77 OPP: Stretched polypropylene film PET: Polyester film Adhesion test: 90 degree peeling test with cellophane tape ○ -No peeling, △ -Partial peeling, × -Complete peeling Oil resistance test: 80 ° C hot water After soaking for 2 hours, adhesion test Heat resistance test: 120 ° C., adhesion test after 60 hours Accelerated weathering test: Du-panel weatherometer (manufactured by Suga Test Instruments Co., Ltd.), 200 hours (condensation / exposure = 2 hours /
10 hours cycle) Adhesion test after exposure.

Table 2 Results of Application Example 2 UV curable resin used Example 3 Comparative Example 3 Adhesive strength kgf / 15 mm 78 76 Hot water resistance test% 88 65 Heat resistance test% 82 76 Accelerated weathering test 75 73 Table 3 Application example 3 Results Used urethane prepolymer Example 4 Comparative example 4 Adhesive strength kgf / 15mm 68 68 Hot water resistance test% 45 42 Heat resistance test% 62 67 Accelerated weathering test% 85 78 Table 4 Results of application example 4 Adhesive sheet used Example 5 Comparative Example 5 Shear strength kgf / 15 mm 150 145 Oil resistance test% 86 84 Heat resistance test% 78 76 Accelerated weathering test% 78 67 Description of test method in Table 2, Table 3 and Table 4 Heat resistant water test: Hot water at 80 ° C Adhesive strength retention rate after dipping for 48 hours in heat resistance test: Adhesive strength retention rate after 120 hours at 120 ° C. Accelerated weathering test: Du-panel weatherometer ( 200 hours with Suga Test Instruments Co., Ltd. (condensation / exposure = 2 hours / 1)
0 hour cycle) Adhesive strength retention rate after exposure (hereinafter referred to as margin)

Claims (7)

[Claims] 1. An adhesive comprising a polyurethane composition prepared with a diisocyanate compound prepared from a dialkyl carbonate and a diamine prepared substantially without phosgene in the process. 2. A dialkyl carbonate is dimethyl carbonate.
The adhesive according to claim 1, which is a bone. 3. The adhesive according to claim 1, wherein the dialkyl carbonate is dimethyl carbonate produced from carbon monoxide and methanol. 4. A propylene carbonate in which a dialkyl carbonate is produced from propylene oxide and carbon dioxide.
The adhesive according to claim 1, which is a dimethyl carbonate obtained by further reacting the carbonate with methanol. 5. The adhesive according to claim 1, wherein the dialkyl carbonate is obtained by using a nitrite ester as a starting material which becomes an alkoxy source. 6. The adhesive according to claim 1, wherein the diisocyanate compound is obtained by thermal decomposition of a urethane compound. 7. The adhesive according to claim 1, wherein the diamine is isophoronediamine.