JPH03244623A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition improved in durability, especially weath ering resistance in a good working environment and workability by mixing a specified isocyanurate polyisocyanate with a nonpolar organic solvent as the essential components. CONSTITUTION:A resin composition essentially consisting of an isocyanurate polyisocyanate obtained from a 11-20C saturated hydrocarbon diisocyanate compound and a nonpolar organic solvent. A desirable diisocyanate compound is a 11-20C alkylene diisocyanate compound, especially 1,12-dodecamethylene diisocyanate. A desirable nonpolar organic solvent is one having an aniline point of 12-65 deg.C. The above composition can be put into practical use in the form of a combination of a resin composition, as a commercial product, for example, a curing agent for polyurethane resin, obtained by mixing the polyisocyanate with the nonpolar organic solvent in a mixing ratio in the range of about (10-90)/(90-10), with a polyol as a base of polyurethane resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful resin composition. More specifically, the present invention relates to a resin composition containing an isocyanurate type polyisocyanate obtained using a specific diisocyanate compound and a specific organic solvent.

The resin composition of the present invention has low toxicity, good workability and weather resistance, and can be used in a wide range of applications such as paints, adhesives, fibers, and molding materials, and can provide highly durable films. It is extremely useful in the industrial field.

[Conventional technology]

Until now, biuret-type or adduct-type non-yellowing polyisocyanates have been used industrially to obtain polyurethane resins with excellent mechanical properties such as abrasion resistance and chemical resistance. The polyisocyanate inevitably has poor solubility in non-polar organic solvents, and therefore it is necessary to use a so-called polar organic solvent such as ethyl acetate or methyl isobutyl ketone as a diluting solvent.

However, these polar organic solvents generally have a strong odor and high dissolving power, so they attack various materials such as plastic materials that have been widely used in recent years, and have become difficult to protect the working environment. This poses a serious problem in practical use, as it interferes with workability and workability.

In addition, in recent years, non-yellowing isocyanurate-type polyisocyanates derived from hexamethylene diisocyanate have begun to be used as curing agents.
Although they have better solubility than the above-mentioned billet type polyisocyanates and are soluble in, for example, non-polar aromatic hydrocarbon organic solvents such as toluene and xylene, these organic solvents also Because it has a strong odor and has a strong enough dissolving power to attack plastic materials, even conventional isocyanurate-type polyisocyanates have practical limitations. , you could say.

Furthermore, in order to overcome the drawbacks or deficiencies of the various conventional techniques listed above, the present inventors have already developed diols having 10 to 40 carbon atoms, particularly 12-hydroxystearic acid, as an essential component. polyester diol,
An isocyanurate ring obtained by reacting various diols such as and long-chain hydrocarbon ester diols with a saturated hydrocarbon diisocyanate compound having 2 to 8 carbon atoms in the presence of an incyanurate catalyst. We have proposed a resin composition comprising a polyisocyanate having the following properties and a nonpolar organic solvent. (Japanese Patent Publication No. 51968/1982, 209124/1982, and 257313/1989.) By the way, each of the above-mentioned resin compositions contains a polyisocyanate having an isocyanurate ring, Swazol 310
Carbonized aliphatic products with little odor and weak dissolving power, such as J (round petrochemical ■ product; aniline point = 16℃) and LAWS J (product of Shell, Netherlands; aniline point -44℃) It is a non-polar organic solvent including a hydrogen-based organic solvent, and it can certainly be said that the above-mentioned preservation of the working environment and securing of workability have been significantly improved.

However, each polyisocyanate disclosed in each of the above-mentioned patent applications has what is called a urethane bond in the molecule, which is unsuitable for dissolving in a non-polar organic solvent. Because they contain polar groups that have the ability to form intermolecular hydrogen bonds, hydrolyzable properties, and in some cases ester bonds that impair durability, they end up having poor performance. It is thought that the fact that there is still room for improvement in terms of this will become a new problem.

[Problem to be solved by the invention]

To this end, the present inventors have earnestly embarked on research in order to eliminate and solve the drawbacks or problems in the various conventional techniques as described above.

Therefore, the problem to be solved by the present invention is to provide a means for improving the working environment, workability, and durability, especially weather resistance.

In other words, the present invention uses non-polar organic solvents such as turpentine, which has low toxicity, and therefore helps to preserve the working environment.Moreover, it does not damage the material itself, and therefore, it also ensures workability. It is an object of the present invention to provide an extremely useful resin composition that can be used in a variety of applications, and can also maintain durability such as weather resistance.

[Means to solve the problem]

Therefore, the inventors of the present invention focused on the problems to be solved by the invention as described above, and as a result of repeated studies,
It comprises an isocyanurate ring-containing polyisocyanate obtained using a specific diisocyanate compound called a saturated hydrocarbon diisocyanate compound in which the saturated hydrocarbon chain portion serving as an isocyanate residue has 11 to 20 carbon atoms, and a specific poor solvent. The present invention was completed by discovering that the resin All-in-one sole has each of the above-mentioned excellent properties and is extremely useful.

That is, in the present invention, as an essential component, each of the saturated hydrocarbon chain portions as isocyanate residues has 11 carbon atoms.
It contains an isocyanurate-type polyisocyanate obtained using a saturated hydrocarbon diisocyanate compound of In addition, it is intended to provide highly useful resin & II compound acid.

Here, first of all, the above-mentioned saturated hydrocarbon diisocyanate compound having 11 to 20 carbon atoms refers to α, β-
An ethylenically unsaturated double bond is also an unsaturated bond (cyclic bond) that forms an aromatic ring, for example, a benzene nucleus.
Therefore, it does not have any single bond (−
Among the diisocyanate compounds, only the most representative ones are exemplified, including 1,12-dodecamethylene diisocyanate, 1,16-hexazocamethylene, Alkylene diisocyanate compounds such as diisocyanate or 1.18-octadecamethylene diisocyanate; or alicyclic diisocyanate compounds as shown by the following formula (1), and these may be used alone or in combination of two or more types.

By the way, saturated hydrocarbon diisocyanate compounds having 10 or less carbon atoms tend to be difficult to produce isocyanurate type polyisocyanates having sufficient solubility in non-polar organic solvents as described below. Saturated hydrocarbon diisocyanate compounds having a number of 21 or more are undesirable in any case because they unnecessarily reduce the content of the isocyanurate type polyisocyanate obtained using them.

In addition, among the diisocyanate compounds, alkylene diisocyanate, especially 1,12-dodecamethylene diisocyanate, has a low viscosity of the obtained isocyanurate type polyisocyanate, and therefore, the resin composition diluted with a non-polar organic solvent can be used. It can be said that it is a preferable compound because it can be put to practical use in a high concentration state.

The isocyanurate type polyisocyanate obtained using the diisocyanate compound can be easily prepared using a known and commonly used isocyanurate catalyst, and only typical isocyanurate catalysts are used. To name just a few, there are quaternary ammonium compounds as shown by the following general formula,
Specifically, N-2 as shown in the following formula (II-1)
-Hydroxypropyl-N,N,N-)limethylammonium p-rert-butylbenzoate, or formula (
N-2-hydroxypropyl-N,N,N-tributylammonium-2,2-dimethylpentanoate as shown by the formula [n-2) is particularly representative. It is desirable to use compounds shown in (2).

...(II-1) ...(II-2) If particularly desired, metal salts of carboxylic acids such as potassium propionate, or metal alcoholades such as sodium ethylate, etc. may be used as the catalyst. You can also do that.

The amount of the catalyst to be used is not particularly limited, but it is usually 10 to 10% of the diisocyanate compound.
A suitable range is 500 ppm, preferably 20 to 300 ppm.

Among the catalysts, the quaternary ammonium compound represented by the above-mentioned general formula (II) has sufficient catalytic activity by itself, so there is no need to use a co-catalyst. However, if desired, this does not preclude the use of various known and commonly used active hydrogen compounds such as alcohols and phenols as cocatalysts.

However, it goes without saying that the amount of such co-catalyst used should be kept to a minimum.

In addition, although the incyanurate reaction carried out in preparing the isocyanurate type polyisocyanate is usually carried out in the absence of a solvent, if particularly desired, a general-purpose solvent such as toluene or xylene may be used. Of course, this does not preclude the use of various so-called non-reactive organic solvents that do not inhibit the reaction.

The reaction temperature is usually within the range of 20 to 120'C, preferably within the range of 40 to 100'C.

The catalyst is deactivated by adding a so-called deactivating agent such as tI4 acid, monochloroacetic acid or benzoyl chloride to the crude reaction product (reaction mixture) obtained after completing the isocyanurate reaction. It's good too,
After that, it is of course possible to further perform an operation of filtering to remove insoluble substances from the system, if necessary.

Therefore, the conversion rate through such an isocyanuration reaction is suitably within the range of 20 to 701 ffili%, preferably within the range of 30 to 65% by weight,
It is recommended that it be implemented within this range.

By the way, an ungrooved conversion rate of 2 Offi weight % is not suitable for industrial use, and on the other hand, if it exceeds 70 weight %, the number of nuclei, that is, the molecular weight of the obtained isocyanurate type polyisocyanate will inevitably decrease. If it becomes too high, the solubility tends to deteriorate further, which is not preferable in either case.

Next, the above-mentioned non-polar organic solvent is preferably a hydrocarbon organic solvent, more preferably an aliphatic hydrocarbon organic solvent, or an aromatic hydrocarbon mainly composed of such an aliphatic hydrocarbon organic solvent. Examples include mixtures with hydrogen-based organic solvents.

In the present invention, in particular, the aniline point is 12
It is desirable to use a hydrocarbon organic solvent within the range of ~65°C, but to exemplify only typical non-polar hydrocarbon organic solvents, HAWS J (Shell product; aniline point =
15℃), Swazol 310J, Essonaphtha 6
” (Product from Exxon, USA; Aniline point = 43℃
), ``Rouse'', ``Essonaphtha 5'' (product of the same company; aniline point = 55℃) or ``Pegasol 3040J
(A product of Mobil Oil Co., USA; aniline point = 55'c).
40°C) or ethylcyclohexane (aniline point = 4
4° C.), so-called alicyclic hydrocarbon organic solvents.

Thus, the resin composition of the present invention can be produced by mixing the isocyanurate type polyisocyanate obtained as described above with the various non-polar organic solvents listed above as essential structural components. prepared.

That is, the resin composition of the present invention can be prepared by simply mixing the above-mentioned polyisocyanate and a non-polar organic solvent.
A resin composition obtained by mixing the resin composition in an arbitrary ratio in the range of ~90/90 to 10 is commercialized as it is, for example, as a curing agent for polyurethane resin, and is used as a curing agent for polyurethane resin. It can be put to practical use in combination.

Moreover, the resin composition of the present invention not only contains the above-mentioned polyisocyanate and non-polar organic solvent as constituent components, but also
It also includes compositions containing the base polyol (solution) of the polyurethane resin, as well as fillers, additives, and the like as constituent components.

Here, only particularly representative polyols as the main component used to obtain the above-mentioned polyurethane resin will be exemplified: - polyols having two or more hydroxyl groups in the molecule; Alkyd polyols, acrylic polyols, acrylated alkyd polyol necks, polyester polyols, or polybutadiene oligomers, which are soluble or have a certain degree of affinity or dispersibility in the above-mentioned non-polar organic solvents. It is something.

The thus obtained resin composition of the present invention has low toxicity, good workability and weather resistance, and can be used in a wide range of fields such as paints, adhesives, fibers, and molding materials, among others.

〔Example〕

Next, the present invention will be specifically explained using reference examples, examples, comparative examples, applied examples, and comparative applied examples. In the following, "%" means "% by weight" unless otherwise specified.

Reference Example 1 (Preparation example of isocyanurate type polyisocyanate) 1.756 g of 12-dodecamethylene diisocyanate
(3.0 mol) was charged into a reaction vessel and heated to 60°C,
Maintaining this temperature, add 25% of a 25% butyl cellosolve solution of N-2-hydroxypropyl-N,N,N-)liptylammonium-2,2-dimethylpentanoate to the solution.
．． 5 g was added in 3 portions, being careful not to generate heat.

During this time, the progress of the isocyanurate reaction was tracked by measuring the refractive index of the contents over time, and the refractive index changed from 1.4567 to 1 with some heat generation.
．． It was confirmed that it took 3 hours to rise to 4680.

When the refractive index reaches 1.4680, 2.5% of a 7% xylene solution of monochloroacetic acid, which is a quenching agent, is added.
5 g was added and cooled to room temperature to complete the isocyanurate reaction.

Next, in order to purify the polyisocyanate and obtain the target product, 7 of the reaction solution after isocyanurate is purified.
When 50 g was applied to a molecular distillation machine, 272 g (conversion rate = 36.3%) of the target polyisocyanate having an isocyanurate ring and a distillate (
475 g (recovery rate = 63.3%) of 1.12-dodecamethylene di-isocyanate was obtained as distillate).

Therefore, the process loss in the distillation process is only 3g.
(Loss rate -0.4%).

Example 1 150 g of the isocyanurate type polyisocyanate obtained in Reference Example 1 was dissolved in 50 g of "Essonaphtha-Hiro 6" to form a uniform resin composition with a nonvolatile content of 75%.

The resin composition obtained here was liquid and had an isocyanate content of 11.0%.

By the way, this resin composition is further made into "Esso naphtha\6".
I tried diluting it 20 times, but there was no turbidity or two-layer separation.
It did not occur. Incidentally, it was also confirmed that the tolerance of this resin composition was 2,000%.

Therefore, the content of the aliphatic hydrocarbon organic solvent in this resin & Il Precepts Acid Book "Esson Naphtha No. 6 J is about 75%, containing an aliphatic hydrocarbon organic solvent,
Moreover, it is known that it can dissolve well in non-polar organic solvents that have weak dissolving power.

Application example 1 First, the main ingredient is tert-butyl methacrylate.
Non-volatile content is 50%, hydroxyl value is 30, acid value is 3.5
And the non-volatile content is 75% obtained in Example 1 for the acrylic polyol whose diluent is "house".
A resin varnish was prepared by blending the following resin composition in equivalent amounts so that the isocyanate group (NGO)/hydroxyl group (OH) equivalent ratio was 1.0.

Next, this resin varnish was applied to a glass plate in a conventional manner, and a tough cured coating film was obtained.

Furthermore, when this clear varnish was applied onto a previously cured coating film of a long-oil modified alkyd resin enamel, no lifting was observed at all. Therefore, the resin composition of this example had an extremely good cured coating film. It is also known that it gives

Reference Example 2 An incyanurate reaction was carried out in the same manner as Reference Example 1, except that the same amount of 1-isocyanate-9-isocyanatemethyloctadecane was used instead of 1.12-dodecamethylene diisocyanate. However, the desired polyisocyanate was obtained with a conversion rate of 39%.

Example 2 The isocyanurate type polyisocyanate obtained in Reference Example 2 was diluted with "Essonaphtha Nα6" to obtain a uniform target resin composition with a non-volatile content of 75%.

The resin composition obtained here was liquid, had an isocyanate content of 8.0%, and had no turbidity or separation of two layers. Incidentally, the tolerance of this resin composition is 2.00
It was also confirmed that it was 0% or more.

Application Example 2 First, equivalent blending was carried out in the same manner as in Application Example 1, except that the resin composition obtained in Example 2 was used, and a coating test was conducted. A strong cured coating film was obtained. Obtained.

Separately, the clear varnish thus obtained was applied onto the previously cured coating film of the long-oil modified alkyd resin enamel, and no lifting was observed at all. Therefore, the resin composition of this example also had good results. It is known that it provides a cured coating film.

Comparative Example 1 504 g (3.0 mol) of hexamethylene diisocyanate and 0.4 g of a 25% butyl cellosolve solution of N-2-hydroxypropyl-N,N,N-tributylammonium-2,2-dimethylpentanoate. and the refractive index is changed from 1.4510 to 1.4.
The isocyanurate reaction was carried out in the same manner as in Reference Example 1, except that the isocyanurate reaction was allowed to proceed until the temperature reached 680, and then 0.5 g of a 7% xylene solution of monochloroacetic acid was added and the reaction was carried out. was terminated.

Thereafter, 500 g of the reaction solution obtained in this way was subjected to molecular distillation in the same manner as in Example 1, and 18 g of the isocyanurate ring-containing polyisocyanate for control was obtained.
1 g (conversion rate = 36.2%) and 371 g (recovery rate = 63.4%) of hexamethylene diisocyanate.

150 g of this control polyisocyanate was then treated with "
When 50 g of Essonaphtha Inhibitor 6 was added and mixed, the control resin m-acid obtained here became cloudy by the time the nonvolatile content had already reached 75%. As a result, it completely separated into two layers.

Therefore, it can be said that this control resin composition is extremely difficult to put into practical use.

Comparative Application Example 1 First, the control polyisocyanate obtained in Comparative Example 1 was prepared by using "Essonaphtha N" (which does not dissolve in L6J, so toluene, which has a large dissolving power, was used instead, and the nonvolatile content was 75%. A control resin composition was prepared by diluting the resin composition as follows.

Next, this control resin & Il oxidant "Acrydic A-801PJ': Acrylic polyol manufactured by Dainippon Ink & Chemicals Corporation; non-volatile content = 50%, hydroxyl value =
50, acid value=2.5, and a mixture of toluene and butyl acetate is used as the diluent solvent. ] was blended in an equivalent amount so that NC010H was 1.0 to prepare a control resin varnish.

Thereafter, when the clear varnish thus obtained was applied onto the previously cured coating film of the long-oil modified alkyd resin enamel, it was observed that significant lifting had occurred. Therefore, it is known that the control resin composition of this example causes significant coating film defects.

(Effects of the Invention) When the resin composition of the present invention is put to practical use as a curing agent component for obtaining polyurethane resin, it is far more conducive to the working environment than conventional isocyanurate-type polyisocyanates. , as well as securing a workable form (for example, in paint applications, it is possible to ensure that the material is not damaged during painting), and it is also possible to provide a cross-linked cured material with good durability, making it extremely useful. It is highly useful.

teenager Reason Man

Claims (1)

[Claims] 1. A resin composition containing an isocyanurate type polyisocyanate obtained using a saturated hydrocarbon diisocyanate compound having 11 to 20 carbon atoms and a nonpolar organic solvent. . 2. The resin composition according to claim 1, wherein the saturated hydrocarbon diisocyanate compound having 11 to 20 carbon atoms is an alkylene diisocyanate compound having 11 to 20 carbon atoms. 3. The resin composition according to claim 1, wherein the saturated hydrocarbon diisocyanate compound having 11 to 20 carbon atoms is 1,12-dodecamethylene diisocyanate. 4. The resin composition according to claim 1, wherein the non-polar organic solvent has an aniline point of 12 to 65°C.