JPS62215619A - Resin composition - Google Patents

Abstract

PURPOSE:A resin resin composition especially suitable as a coating compound for line coating, having improved workability and weather resistance, comprising an isocyanurate ring-containing polyisocyanate, a polar organic solvent and an aromatic hydrocarbon organic solvent. CONSTITUTION:An isocyanurate ring-containing polyisocyanurate obtained by reacting a diisocyanate compound selected from 2-8C alkylene diisocyanate (e.g. 1,4-tetramethylene diisocyanate, etc.), 6-8C cycloalkylene diisocyanate (e.g. 1,3-diisocyanatocyclohexane, etc.) and 7-8C aralkylene diisocyanate (e.g. 1,3-xylylene diisocyanate, etc.) with 10-40C diol (e.g., 1,10-decanediol, N-2- hydroxypropylammonium p-tertiary butylbenzoate, etc.) in the presence of an isocyanurating catalyst (e.g. N,N,N-trimethyl, etc.) is blended with a polar organic solvent (e.g. ethyl acetate, etc.) and/or an aromatic hydrocarbon organic solvent (e.g. toluene, etc.) to give the aimed resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful resin composition. More specifically, it consists of a specific polyisocyanate having isocyanurate ffl and a polar organic solvent and/or an aromatic hydrocarbon organic solvent. This is a resin composition that is extremely useful in the industrial field such as welding agents and molding materials.In the paint field, it is particularly useful for road vehicles such as cars and trucks, motorcycles, industrial machinery, etc. machine,
The present invention provides a resin composition that is extremely useful in the field of top coatings for building materials, various industrial parts and structures such as bridges, and in particular, in the field of line coatings.

[Conventional technology]

A curing agent for polyurethane resin with excellent mechanical properties such as abrasion resistance and chemical resistance.

Traditional polyisocyanates such as alkylene diisocyanates, cycloalkylene diisocyanates, and peelet types derived from aralkylene diisocyanates, known as non-yellowing diisocyanates, are polyisocyanates derived from aromatic diisocyanates such as tolylene diisocyanate. Although it is known to have superior weather resistance compared to other materials, recently there is a need for an even higher level of weather resistance.

It can be said that the performance of conventional polyisocyanates is no longer sufficient.

[Problem that the invention seeks to solve]

Therefore, in addition to mechanical properties such as abrasion resistance and basic properties such as chemical resistance, there is a strong desire for the emergence of polyisocyanates that have even higher weather resistance. At the same time, it is suitable for line painting using general-purpose organic solvents.

The emergence of polyurethane resin paints with good workability is highly desired.

To this end, the inventors of the present invention, in view of the above-mentioned actual situation,
As a result of intensive research aimed at providing a preisocyanate with particularly excellent workability and weather resistance, the present invention has been completed.

[Means for solving problems]

That is, 1 the present invention has 2 to 8 carbon atoms as an essential component.
A diisocyanate compound selected from the group consisting of alkylene - cycloalkylene having 6 to 8 carbon atoms and aralkylene diisocyanate having 7 to 8 carbon atoms, and a diol having 10 to 40 carbon atoms as an isocyanurate catalyst. The purpose of the present invention is to provide a resin composition comprising a preisocyanate having an isocyanurate ring obtained by reaction in the presence of a polar organic solvent and/or an aromatic hydrocarbon organic solvent. The aim is to solve the problems with conventional polyisocyanates.

Examples of the alkylene diisocyanate having 2 to 8 carbon atoms, which is one of the essential components of the composition of the present invention, include 1.4-tetramethylene diisocyanate, 1.6
-hexamethylene diisocyanate, etc., but it is of course possible to use these in combination.

Examples of cycloalkylene diisocyanates having 6 to 8 carbon atoms include 1.3-4-diisocyanate cyclohexane, 1.3- or 1.4-bis(isocyanatomethyl)-cyclohexane, and the like. However, it is of course possible to use these in combination.

Furthermore, examples of the aralkylene diisocyanate having 7 or 8 carbon atoms include 1.3- or 1.4-xylylene diisocyanate, but of course a combination of these can also be used.

In the present invention, a particularly desirable diisocyanate compound is an alkylene diisocyanate or a cycloalkylene diisocyanate, and a diisocyanate compound having 9 or more carbon atoms is preferably used.

However, since it undesirably lowers the isocyanate content of the diisocyanate, it is unfavorable in terms of the 111 resin design and is unavoidable from an economical disadvantage in practical use.

However, if a diisocyanate compound having 9 or more carbon atoms is used in combination with the diisocyanate specified by the present invention, it may be included in the diisocyanate compound of the present invention, but for the above-mentioned reasons, the proportion of the combined use should be 50 or less, and It is preferable to keep it to 30% or less.

It is desirable to keep the usage ratio of rukylene diisocyanate to 30% or less. - Examples of diisocyanate compounds having 9 or more carbon atoms that can be used in combination include:
2.2.4- or 2.4.4-)limethylhexamethylene diisocyanate, isopropylidene-bis(4-cyclohexylisocyanate))6 or 3-isocyanatomethyl-3,5,5-)limethyl Examples include cyclohexyl isocyanate.

The diol used as one of the constituent elements of the present invention is usually a diol having 10 to 40 carbon atoms, which reduces the isocyanate content of the polyisocyanate having an isocyanurate ring used in the light. This is not desirable because it causes Furthermore.

The diol having 10 to 40 carbon atoms in the present invention is usually 1.

Man771nosoa*Iwk+//a口〒弗Reso 摓摓桑呑杂胺二醇，并且可以具备烃碱等栅样。 It is a diol, which may have a substituent such as a hydrocarbon. Examples of such diols of the present invention include 1.10-decanediol.

1.12-dodecanediol, 2-hydroxypalmityl alcohol, 2-hydroxystearyl alcohol,
Examples include hydrogenated dimers of 12-hydroxystearyl alcohol and oleyl alcohol, 2,2-bis(4-hydroxycyclohexyl)furopane (commonly known as hydrogenated bisphenol A), and mixtures thereof.

The use of different monohydric alcohols, such as long-chain alcohols with similar chain lengths, reduces the functionality of the polyisocyanate having isocyanurate rings of the present invention and impairs the performance of the urethane resin. , undesirable.

On the other hand, the use of trihydric or higher-functional alcohols is also undesirable because it increases the functionality of the polyisocyanate too much, increases the viscosity, and makes it more likely to become dull.

However, the mixing or combined use of a small amount of monoalcohol, triol, etc. with respect to the diol of the present invention is permissible as long as the properties of the polyisocyanate of the present invention are not significantly impaired.

When producing the polyisocyanate having an isocyanurate ring of the present invention, the diol of the present invention is preferably used in an amount of 1 to 40%, more preferably 2 to 30%, based on the total amount of diisocyanate.

The isocyanuration catalyst that can be used in the present invention is:
Compounds containing atoms (groups) with low electron density and strong cationic properties are suitable; examples include 1, for example, N, N, N-
) trimethyl, N-2-hydroxypropylammonium para-tertiary butyl penzoate [:I:], sodium ethylate, sodium pro-), etc. In particular, catalysts of the formula are easy to purify. Therefore, it is suitable for producing polyisocyanate.

Note that the catalyst is usually prepared in a diluted solution with an organic solvent,
10-1000 pp for diisocyanate compounds
It is advisable to use amounts in the range of m, preferably from 20 to 500 ppm.

The isocyanurate reaction carried out when obtaining the polyisocyanate having an isocyanurate ring of the present invention is carried out in 1
Usually, the reaction is carried out at a temperature range of 30 to 120°C, preferably 40 to 100°C, and the conversion rate of the reaction is 20 to 70% by weight based on the total amount of the diisocyanate compound and diol of the present invention. , preferably within a range of 30 to 65% by weight. At a 70% conversion rate,
The molecular weight of the polyisocyanate produced becomes too high,
This is not preferable because it reduces solubility.

After the reaction has been completed, the reaction mixture is deactivated with a compound such as phosphoric acid, monochloroacetic acid, dodecylbenzenesulfonic acid, etc., and then subjected to a method such as single molecule distillation to remove unreacted diisocyanate compounds. Polyisocyanates can be obtained.

Among the organic solvents that are the other essential component of the composition of the present invention, first, as polar organic solvents, ester solvents such as ethyl acetate, butyl acetate, or isoamyl acetate;
Typical examples include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; and ether ester solvents such as cellotul diacetate and cellosolzoacetate butyrate.

Next, typical aromatic hydrocarbon organic solvents include toluene, xylene, ethylbenzene, and styrene.

51 I Taishun button F# 伽H numbness summer each &+ban treasure pressure 1z7”
It is prepared by mixing the isocyanurate ring-containing polyicanate obtained by excretion, and these polar organic solvents and /i or aromatic hydrocarbon organic solvent as essential components. Ru.

At that time, the above-mentioned polyisocyanate and a polar organic solvent and/or an aromatic hydrocarbon organic solvent are mixed in a proportion of 10 to 9
A resin composition obtained by simply mixing at any ratio in the range of 0/90 to 10 (parts by weight) can be commercialized as it is, for example, as a curing agent for urethane resin. However, it can also be put to practical use in combination with a polyol, which is the main ingredient of polyurethane resin.

The resin composition of the present invention not only contains the above-mentioned IJ isocyanate and a polar organic solvent and/or an aromatic hydrocarbon organic solvent as its constituent components, but also contains 4 liol (solution) as a main ingredient of the urethane resin.

Furthermore, it also includes compositions containing fillers, additives, etc. as constituent components.

The main polyol of the above polyurethane resin is:

It refers to polyols having two or more hydroxyl groups in one molecule, such as alkyd polyols, acrylic I-liols, acrylated alkyds? Riolu, polyester 4
Including those that are commonly used in the past, such as Riolu,
Furthermore, fluorine-based compounds that are soluble in polar organic solvents and/or aromatic hydrocarbon organic solvents as mentioned above? Riolu is a typical example.

The resin composition of the present invention thus obtained can be used as a paint,
It is extremely useful as an adhesive and a molding material, and is especially practical as a paint for line painting.

In addition, the present invention provides a composition which is made of the above-mentioned I-line cyanate and a polar organic solvent and/or an aromatic hydrocarbon organic solvent, and which is put into practical use in the form in which a organic solvent is added thereto. It also includes.

Furthermore, as a special case, a resin composition in which the 4-liso-dissolved product of the present invention is prepared and mixed and used immediately before being put to practical use is also included in the resin composition of the present invention. .

In this case, the content of the non-polar organic solvent contained in the resin composition of the present invention should be kept to 40% by weight or less of the total organic solvent, more preferably to 35N or less, so as to impair the effects of the present invention as much as possible. It is necessary for a long time.

Incidentally, a representative example of the above-mentioned non-polar organic solvent is "・~us" (product of Shell Chemical Co., Ltd.; aniline point = 15
°C), "Swazol 310J (product of Maruichi Oil Co., Ltd.; aniline point = 16℃), "Esson Naphtha Flat 6" (product of Exxon Chemical Co., Ltd.; aniline point: 43℃), "Rouse" (product of Shell Chemical Co., Ltd.; aniline point = 44 °C), “Esso naphtha A
5 J (Exxon Chemical Co. product; aniline point = 55°C)
or aniline point = 55°C), petroleum hydrocarbon organic solvents such as methylcyclohexane (aniline point = 40°C) and ethylcyclohexane (
44℃).

〔Example〕

Next, the present invention will be specifically explained using Examples and Comparative Examples.

Hexamethylene diisocyanate (product of Bayer AG, trade name: Desmodur H) 3500JF and 12-hydroxystearyl alcohol (manufactured by Henkel, product name: Roxanol) were placed in a glass four-bottle flask with a capacity of 5 mm under a nitrogen gas atmosphere.

716.311 (purity 80%) was charged.

Next, the flask was placed in an oil bath and the temperature was raised to 65° C. while stirring, so that the contents of the flask became a homogeneous liquid. Subsequently, the temperature was maintained at the same temperature for 2 hours, and then the temperature was raised to 55°C.

Add 3.4 g of a 20% butyl cellosolve solution of thyl-N-2-hydroxyzorobylammonium paratertiary butyl penzoate [I] in portions, and then heat at 60°C.
After reacting for 3 hours at a temperature of
The isocyanuration catalyst was deactivated by adding 3.41% xylene solution.

The isocyanurate reaction was completed.

After cooling the reaction mixture to room temperature, the 10001 was subjected to molecular distillation, and the distillation residue was I diisocyanate 549.1' having an isocyanurate ring (conversion rate 55.0%).
) and hexamethylene diisocyanate 45 as a distillate.
0. Of! (Recovery rate: 45.0%) was obtained.

The obtained polyisocyanurate ring-containing polyisocyanurate ring*-
) 1 Dilute to 75% concentration with a mixed solvent of toluene/cellosolve acetate = 1/1 (parts by weight ratio) to obtain a transparent polyisocyanate solution (objective resin composition of the present invention) 73
2.2# was obtained.

The polyisocyanate solution thus obtained had a nonvolatile content of 75.1 cm, a Gardner color number of 1 or less, and a Gardner viscosity of D.
-E, the incyanate content was 11.2%, and the molecular weight was 953.

Next, "Acridic A-801°P" [Inu Nippon Ink Chemical Industry Co., Ltd.] was added to this polyisocyanate solution.
Acrylic Liol manufactured by Ajinomoto Co., Ltd.; non-volatile content as standard property values listed in the catalog = 50±1%.

Solvent = doluol/butyl acetate, viscosity; RT, acid value =
3 or less, hydroxyl value = 50 ± 2], NC010H = i, o
(equivalent ratio), and further added "Tie CR-93J [rutile type titanium oxide manufactured by Ishihara Sangyo Co., Ltd.]" so that the grooves were 40% to prepare white enamel. Then, this was painted on a dull steel plate (treated with Ndellite ÷144).

A cured coating film was obtained by drying at 80° C. for 20 minutes.

The initial gloss of this cured coating was 90 (yellowness = 2.1), but it was 3.00 on the Sunshine Web-Ometer.
The gloss after irradiation for 0 hours was 83 (3.4), so
The gloss retention rate of this cured coating is extremely excellent at 92 inches.

On the other hand, "Beccosol J-524" C alkyd polyol manufactured by Dainippon Ink and Chemicals Co., Ltd.; nonvolatile content = 60
±1%, solvent = xylene solvent water xylene content = 44
%, oil = coconut oil, oil content = 32%.

Viscosity=2. ~z31 color number = 1 or less, acid value = 7 or less] and the above polyisocyanate solution, the cured white enamel coating obtained by repeating the same operation had an initial gloss of 95 (yellowness = 1.9),
The gloss after 1,500 hours of irradiation by Sunshine Web-Ometer was 82 (2.7), and the gloss retention rate was 8.
It was 6chi.

Comparative Examples 1 and 2 As the polyisocyanate, "Desmoji-L NJ (manufactured by Bayer, biuret type polyisocyanate of hexamethylene diisocyanate; isocyanate group content = 16.5 ± 0.5%, solvent = xylene/cello The same operations as in Examples 1 and 2 were repeated, except that the initial gloss ran n / area b J #
mx q e ) ty
nnn This song nZ26J Koten+m4^
The gloss was 49 (4.9), and the gloss retention rate was extremely poor at 53.
In the case of cured coatings obtained for.

The initial gloss is 95 (1.9), the gloss after 1,500 hours of irradiation is 62 (2.8), and the gloss retention rate is 65.
%Met.

Comparative Examples 3 and 4 As the polyisocyanate, “Burnock DN-950
J (Agct type polyisocyanate of hexamethylene diisocyanate, manufactured by Dainippon Ink & Chemicals Co., Ltd.; non-volatile content = 75 ± 1%, incyanate group content = 12.
The same operations as in Examples 1 and 2 were repeated except that the solvent was ethyl acetate]. Then, the initial gloss is 89 (yellowness = 1.9)
The gloss after 3,000 hours was 55 (4.4), and the gloss retention rate was poor at 62%. The gloss after irradiation for 1.500 hours was 69, and the gloss retention rate was 72%.

Example 3 As a diisocyanate compound, hexamethylene diisocyanate 350ON was replaced with hexamethylene diisocyanate 2100.9.1.3-bis(incyanate methyl)-cyclohexane (Takeda Pharmaceutical Products, trade name Tagane 600) 14001. , Example 1 except that the same isocyanuration catalyst 13.9.9 as in Example 1 is used.
The isocyanurate reaction was carried out in exactly the same manner as above to obtain a reaction mixture 4215N in which the catalyst had expired.

10011i in the obtained reaction mixture was subjected to molecular distillation, and as a distillation residue, 541.71 polyisocyanate (conversion rate 54.2) and distillate 457.8 (recovery rate 45.8) were obtained. Obtained.

Next, the obtained polyisocyanate was diluted to a concentration of 75% with a mixed solvent of total toluene/cellosolve acetate (total toluene/cellosolve acetate) = 1/1 (parts by weight ratio) to give a transparent preisocyanate solution (objective resin composition of the present invention) 722. 3g was obtained.

The polyisocyanate solution thus obtained.

Non-volatile content 75.1%, Gardner color number 1 or less, Gardner viscosity g-F, isocyanate content 10.7 inches,
And the molecular weight was 929.

Thereafter, the same operations as in Example 1 were repeated, and the accelerated weather resistance test results for the cured coating film obtained using Acridic A-801PJ showed that the initial gloss was 89 (yellowness = 2.0). The gloss after irradiation for 3,000 hours was 72 (3.7), and the gloss retention rate was excellent at 81%.

Example 4 Using the same reactor as in Example 1, 1,3-bis(incyanatemethyl)-cyclohexane 3500.112-
Using hydroxystearyl alcohol 245II, the catalyst solution of Example 1 6.6. Using li', the reaction mixture was treated in the same manner as in Example 1 except that the isocyanurate reaction was carried out at 70°C to obtain a reaction mixture 375ON in which the catalyst had expired.

10011I in the obtained reaction mixture was subjected to molecular distillation, and the distillation residue was a polyisocyanate having an isocyanurate ring) 491.7 # (conversion rate 49.2%)
and 1,3-bis(isocyanatomethyl) as distillate
-Cyclohexane 506.711 (recovery rate 50.8%)
I got it.

Socyanate solution (objective resin composition of the present invention) 656I
I got it.

Thus obtained. If the lysocyanate solution had a non-volatile content of 75.0%, a Gardner viscosity of LM, a lysocyanate content of 12.8%, and a molecular weight of 727.

Thereafter, the same operations as in Example 1 were repeated, and the results of the accelerated weather resistance test for the cured coating film obtained using Acridic A-801PJ showed that the initial gloss was 89 (yellowness = 2. 1), the gloss after 3,000 hours of irradiation was 61 (same as 4).
．． 1), and the gloss retention rate was 69%.

Claims (1)

[Claims] A diisocyanate compound selected from the group consisting of alkylene having 2 to 8 carbon atoms, cycloalkylene having 6 to 8 carbon atoms, and aralkylene diisocyanate having 7 to 8 carbon atoms; and a diol having 10 to 40 carbon atoms. A resin composition comprising, as essential components, a polyisocyanate having an isocyanurate ring obtained by reacting the polyisocyanate in the presence of an isocyanurate-forming catalyst, and a polar organic solvent and/or an aromatic hydrocarbon organic solvent.