KR20090132495A - Urethane-forming composition, polyol composition, and process for preparing urethane resin - Google Patents

Abstract

PURPOSE: An urethane-forming composition is provided to ensure long shelf life at a room tempareature, to realize short curing time, and to improve workability and moldability during a manufacturing process of urethane resin. CONSTITUTION: An urethane-forming composition comprises an isocyanate component containing at least one selected from the group consisting of an aliphatic and alicyclic isocyanate, their derivative and denaturant, and their mixture; a polyol component which is liquid at a room temperature; a reaction inhibitor; and an organometallic catalyst which is solid at a room temperature.

Description

A urethane forming composition, a polyol composition, and a manufacturing method of a urethane resin {URETHANE-FORMING COMPOSITION, POLYOL COMPOSITION, AND PROCESS FOR PREPARING URETHANE RESIN}

The present invention relates to a urethane resin, and more particularly, to a forming composition, a polyol composition, and a method for producing a urethane resin, which enable long pot life at room temperature and are excellent in curability.

Urethane resins are tough and have excellent physical properties such as abrasion resistance, oil resistance, and solvent resistance. Various types of foams, films, elastomers, powders, solutions, emulsions, and the like can be used in various forms such as flexible foams, rigid foams, elastomers, adhesives, paints, and binders. It is used for a purpose. This urethane resin is formed by reacting a polyol and a polyisocyanate in the presence of a catalyst and additives such as a blowing agent, a surfactant and a crosslinking agent.

When forming a urethane resin, when all raw materials are mixed and it is left as it is, the reaction of a mixed composition may advance and it may become unusable during the stay. Particularly, in the manufacture of heavy weight fabrics or air bags, the urethane-forming composition is used as a binder of a filler or a functional filler for a base cloth. It became a problem especially when retention of the mixed liquid of a raw material arises. From this background, in order to improve workability, what is called an extension of the pot life was calculated | required. In the prior art, in order to prolong this pot life, a method using a low activity catalyst or adding a high melting point metal catalyst in a solid form is known.

For example, Japanese Patent Laid-Open No. 2-242875 (Patent Document 1) discloses a thermosetting adhesive comprising a prepolymer containing both an isocyanate group and a polyether segment, at least one polyhydroxyl compound and a catalyst. A composition comprising a catalyst in solid form comprising at least one of salts of bismuth, cadmium, lead or zinc of carboxylic acids containing more than 12 carbon atoms and having a melting temperature higher than 100 ° C. A thermosetting adhesive composition is disclosed.

Further, Japanese Patent Application Laid-Open No. 2004-269733 (Patent Document 2) is made by blending a curing catalyst with a two-component solution of an isocyanate component as a polyol component and a curing agent as a main agent, and as the curing catalyst, a metal system having a melting point of 110 to 500 ° C. Disclosed is a two-component urethane composition comprising a thermosensitive curing catalyst blended to the main agent side at room temperature as a powder or a solid.

<Patent Document 1> Japanese Unexamined Patent Publication No. 2-242875

<Patent Document 2> Japanese Patent Application Laid-Open No. 2004-269733

However, in the technique disclosed in Patent Document 1, in order to achieve a desired urethanization reaction, melting of a solid powdery polyhydroxyl compound is premised. Therefore, the compound R (NCO group and OH group) of an isocyanate component and a polyol component is assumed. The local nonuniformity of the ratio of (b) was brought about, and it was not enough from a viewpoint of the moldability of the urethane resin, and the characteristic obtained. In addition, in the technique disclosed in Patent Document 2, the curing time in the curing conditions may be about several minutes. Even if the pot life is extended, the curing time is about 20 to 30 minutes or more at room temperature to about 40 ° C. It was not enough from the viewpoint of making both the extension of and the shortening of hardening time under the hardening conditions compatible.

Therefore, urethane formation is still excellent in the uniformity of the mixed composition, and realizes a long pot life time of at least 24 hours of the mixed composition of the polyol and polyisocyanate, and a short curing time of about several minutes to 25 minutes under curing conditions. It has been desired to provide a composition, a polyol composition, and a method for producing a urethane resin.

This invention is made | formed in view of the subject in the said prior art, and this invention is a urethane forming composition, a polyol composition, and a urethane resin which implement | achieves compatibility with the long pot life at normal temperature and the short hardening time under hardening conditions. An object of the present invention is to provide a method for producing the same.

MEANS TO SOLVE THE PROBLEM In the urethane forming composition comprised from a polyol component and an isocyanate component, it is the pot life time after fluidity | liquidity disappears after mixing, and the hardening time from a liquid state to a rubbery state under hardening temperature conditions. As a result of earnestly examining the pot life and curing time results obtained from various compositions, the organometallic catalyst of a room temperature solid is cured by using a polyol component of a room temperature liquid and an aliphatic or alicyclic polyisocyanate component. By adding a reaction inhibitor which disperses in solid form as a catalyst and further suppresses the curing reaction, surprisingly little yellowing in the urethane-forming composition without the use of a blocking agent is carried out for at least 24 hours at room temperature. Pot life, also minutes to 25 minutes under curing conditions By the short curing time of between about found possible to achieve, but early in the present invention.

That is, in the present invention, an isocyanate component including one or more selected from the group consisting of aliphatic and alicyclic isocyanates, and derivatives and modified substances thereof, a polyol component in a room temperature liquid phase, a reaction inhibitor, and a solid in the composition To prepare a urethane-forming composition in which an organometallic catalyst of a room temperature solid is blended. And this composition can harden | cure, for example by heating to 100-250 degreeC as hardening conditions.

As the isocyanate component, an aliphatic or alicyclic isocyanate which is not an aromatic isocyanate is used, and a polyol of a room temperature liquid rather than a room temperature solid is used as the polyol component, and is not a room temperature liquid in the presence of a reaction inhibitor that suppresses the curing reaction. By mixing an organometallic catalyst of a room temperature solid and presenting it in a solid form in the composition, a long pot life of 24 hours or more at room temperature with little yellowing and a short curing time of several minutes to 25 minutes under curing conditions are achieved. The urethane forming composition to be obtained is obtained. Thereby, it becomes possible to improve the workability and moldability in a urethane resin manufacturing process. In addition, since the blocking agent becomes unnecessary, the load is reduced in terms of the environment and safety in the manufacturing process of the urethane resin such as the residue of the blocking agent in the final molded product and the contamination caused by the scattering of the blocking agent during molding.

That is, according to the present invention, an isocyanate component including at least one selected from the group consisting of aliphatic and alicyclic isocyanates, and derivatives and modified substances thereof and mixtures thereof as the urethane-forming composition, a polyol component in a room temperature liquid phase, There is provided a urethane-forming composition in which a reaction inhibitor and an organometallic catalyst of a room temperature solid present in a solid form in the composition are combined. Moreover, according to this invention, the polyol composition for obtaining the said urethane forming composition, and the manufacturing method of resin using the said urethane forming composition are provided.

In the present invention, the polyol component may preferably include one or more or a mixture of polyester polyols and polycarbonate polyols. In the present invention, the organometallic catalyst is preferably an organotin compound. In the present invention, the reaction inhibitor may preferably be an acidic phosphate ester. In the present invention, the isocyanate component may include one or more or a mixture thereof, preferably selected from the group consisting of hexamethylene diisocyanate having an average number of functional groups of 2 to 5, derivatives and modified substances thereof.

In the present invention, the polyol component, the reaction inhibitor and the organometallic catalyst may be mixed at a temperature of 20 to 40 ° C. to prepare a polyol composition in which the organometallic catalyst is dispersed. In addition, in the present invention, the urethane-forming composition may be prepared by mixing the prepared polyol composition and the isocyanate component. In the present invention, the prepared urethane-forming composition may be cured by heating to a temperature of 100 to 250 ℃.

As described above, according to the present invention, a urethane-forming composition is obtained in which a long pot life of 24 hours or more at room temperature and a short curing time of about several minutes to about 25 minutes under curing conditions are achieved, whereby a urethane resin In the manufacturing process, the workability and the moldability can be improved.

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in specific embodiment, this invention is not limited to embodiment mentioned later.

Hereinafter, the urethane forming composition of this invention, the polyol composition for obtaining the said urethane forming composition, and the manufacturing method of the urethane resin using the said urethane forming composition are stated.

The urethane-forming composition of the present invention is mainly produced by blending an isocyanate component, a polyol component, a reaction inhibitor, and an organometallic catalyst.

The isocyanate component may include at least one of aliphatic isocyanates and alicyclic isocyanates, and derivatives and modified substances thereof or mixtures thereof. Examples of such isocyanates include aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate and lysine methyl ester diisocyanate, hydrogenated diphenylmethane diisocyanate and isophorone di. Alicyclic polyisocyanates, such as an isocyanate and hydrogenated trienedi isocyanate, are mentioned.

From the standpoint of achieving a long pot life and a short cure time, more preferably the isocyanate component may comprise HDI having an average number of functional groups of 2 to 5, and derivatives and modifications thereof. Such HDI derivatives or modified substances include urethane modified polyisocyanates obtained from HDI and 1,3-butanediol, allophanates obtained from HDI and isopropanol, allophanates obtained from HDI and 3-methyl-1,5-pentadiol (MPD) The isocyanurate group containing polyisocyanate etc. which are obtained by isocyanurate formation from modified polyisocyanate, HDI, and 1, 3- butanediol are mentioned. The NCO content of the isocyanate component is preferably in the range of 10 to 30% by mass, and more preferably in the range of 15 to 25% by mass.

The polyol component may include at least one or a mixture of polyols in a room temperature liquid phase, and more specifically, polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol in a room temperature liquid phase. In addition, in this invention, normal temperature means the temperature state in which the range of 20 degreeC is a tolerance of 15 degreeC, ie, the range of 5 degreeC-35 degreeC as 20 degreeC standard temperature similarly to the provision of Japanese Industrial Standard (JIS Z 8703). . In addition, in this invention, a liquid state means the state evaluated based on 2 "definition of a liquid phase" of Article 69 of the Regulation on the Regulation of Dangerous Goods, and made a test tube (30 mm in diameter; 120 mm in height; flat bottom cylindrical glass) ), The time from the tip of the moving surface of the test sample to a distance of 85 mm from the bottom of the test tube when the test sample is placed up to 55 mm high from the bottom of the test tube and the test tube is leveled. Within 90 seconds, the liquid phase is defined.

As said polyol, from the viewpoint of making a long pot life and a short hardening time compatible, it is preferable to use a polyester polyol and a polycarbonate polyol in a room temperature liquid. As the polyester polyol, a room temperature liquid polyester polyol obtained from 3-methyl-1,5-pentanediol (MPD) and adipic acid, a room temperature liquid polyester polyol obtained from trimethylolpropane (TMP), MPD and adipic acid, etc. Can be mentioned. Moreover, as said polycarbonate polyol, the normal temperature liquid polycarbonate diol etc. which are obtained from 1, 6- hexanediol, MPD, and diethyl carbonate (DEC) are mentioned.

Other examples include polyhydric carboxylic acids such as adipic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic anhydride, adipic acid, sebacic acid, fumaric acid, maleic anhydride, dodecaneic acid, azelaic acid, and the like. Polyester polyol obtained from polyhydric alcohols, such as ethylene glycol, propylene glycol, 1, 4- butanediol, 1, 6- hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, 3-methyl- 1, 5- pentanediol In addition, a liquid thing can also be employ | adopted at normal temperature.

From the viewpoint similar to the above, the number average molecular weight of the said polyol can be preferably in the range of 1000 to 5000, and more preferably in the range of 1500 to 3500. In addition, the average functional group number of the said polyol can be made into about 2-4 about the same viewpoint as mentioned above.

The blending ratio of the isocyanate component and the polyol component may be a blending ratio in which the urethane resin is smoothly formed. Usually, the molar ratio (NCO / OH, R value) of the isocyanate group (NCO group) to the hydroxyl group (OH group) is 0.2 to 1.5. It can mix with the compounding ratio which becomes a range, Preferably it is the range of 0.3-1.3, More preferably, it is the range of 0.9-1.1.

The reaction inhibitor may include at least one of phosphoric acid, phosphorous acid, acidic phosphate ester, and acidic phosphite ester or a mixture thereof, and in view of achieving a long pot life and a short curing time, preferably 1 to 18 carbon atoms. Acidic phosphate esters, and mixtures thereof. Examples of the acidic phosphate esters include ethyl phosphate, diethyl phosphate, isopropyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) acid phosphate, isodecyl acid phosphate, and lauryl An acid phosphate, a tridecyl acid phosphate, a stearyl acid phosphate, an isostearyl acid phosphate, an oleyl acid phosphate, a stearyl acid phosphate, etc. are mentioned.

The addition amount of the reaction inhibitor is preferably in the range of 50 to 1200 mass ppm (hereinafter simply referred to as ppm) with respect to the polyol component from the viewpoint of achieving both a long pot life and a short curing time, more preferably 80 to It may be in the range of 700 ppm, and more preferably in the range of 80 to 300 ppm.

The organometallic catalyst is an organometallic compound that exhibits a catalytic action of a curing reaction at predetermined curing temperature conditions. Examples of such organometallic compounds include Sn, Pb, Cd, Zn, Al, Zr, Bi, Mg, Room temperature solids among maleate compounds, oxide compounds, ester compounds, mercaptide compounds and chelate compounds containing metals such as Fe, Ti, Cu, Co, Ni, In, Ca, Y, Ce, Sr, Mo, and La And mixtures thereof may be employed.

It is preferable to use an organic tin compound of a room temperature solid as the organometallic catalyst, and as such a tin compound, dibutyltin distearate, dibutyltin maleate polymer, dibutyltin bis (alkyl maleate ester) salt, bis (di Butyl tin maleic acid alkyl ester) maleate, dibutyl tin s, o-mercaptocarboxylate polymer, dioctyl tin distearate, dioctyl tin maleate polymer, dioctyl tin bis (maleic acid alkyl ester) salt, Bis (dioctyl tin maleic acid alkyl ester) maleate, dioctyl tin s, o-mercaptocarboxylate polymer, dioctyl tin dioctoate, dioctyl tin oxide, and the like. Can be adopted.

From the viewpoint of achieving a long pot life and a short curing time under curing conditions of 100 ° C to 250 ° C, dialkyl such as dialkyl tin oxide compounds and dialkyl tin maleate compounds having 2 to 30 carbon atoms are more preferable. Tin compounds can be employed. As an organotin compound of the said room temperature solid, More preferably, a di-n-octyl tin maleate compound and a dioctyl tin oxide compound can be used.

In addition, the organometallic catalyst is preferably added to the composition in a powder state. From the viewpoint of increasing the dispersibility, the organometallic catalyst is more preferably pulverized and kneaded with a plasticizer or the like by a triaxial roll mill or the like, and added as a finely dispersed paste-like catalyst master in the plasticizer. In that case, the particle diameter of the organometallic catalyst is preferably 70 µm or less, and more preferably 50 µm or less. The addition amount of the organometallic catalyst is preferably in the range of 250 to 2000 ppm with respect to the polyol component, and more preferably in the range of 400 to 1500 ppm from the viewpoint of achieving both a long pot life and a short curing time. In addition, addition of the tertiary amine catalyst in addition to the organometallic catalyst is not prevented in order to produce the desired reactivity.

In addition, the urethane-forming composition of the present invention has properties of urethane resins such as surfactants, foam stabilizers, defoamers, flame retardants, plasticizers, pigments, dyes, stabilizers, bactericides, fillers and the like, depending on the form of the particular use or purpose. It may also include additives for improving.

The urethane-forming composition of the present invention preferably first prepares a polyol composition (hereinafter referred to as a premix) by combining a polyol component, a reaction inhibitor, an organometallic catalyst, and other additives, and the premix and isocyanate component prepared above. By mixing the above, the urethane-forming composition can be produced. The preparation of the premix is preferably performed by mixing the raw materials uniformly under a temperature condition not exceeding 40 ° C. so that the organometallic catalyst of a room temperature solid does not dissolve and is present in the composition, and more preferably at room temperature. desirable. Although the temperature conditions at the time of mixing a premix and an isocyanate component are not specifically limited, It is preferable to set it as the temperature of 60 degrees C or less from a viewpoint of the moldability of a urethane resin, etc.

In addition, the production method of the urethane-forming composition is a mixture of the entire raw material including the isocyanate component, the polyol component, the reaction inhibitor, the organometallic catalyst, and other additives at the same time in addition to the production method of mixing the premix and the isocyanate component prepared first It can also be adopted.

In the urethane-forming composition of the present invention, the pot life, which is defined as the time required from the liquid state to the loss of fluidity after mixing, can achieve at least 24 hours or more at room temperature, and at least 70 hours depending on the composition. You may. Therefore, even after long-term retention occurs after mixing, proper fluidity can be maintained to improve workability and formability in the manufacturing process.

The urethane-forming composition of the present invention can be cured within 0.7 to 25 minutes, more preferably within 3 minutes by heating to a predetermined curing temperature condition. Therefore, even if long term retention occurs after mixing, it is possible to quickly cure under curing conditions during molding while maintaining proper fluidity, thereby improving workability and formability in the manufacturing process. Moreover, as said hardening conditions, it can be set as the temperature conditions which an organometallic catalyst melt | dissolves in a composition and exhibits the catalysis of a desired hardening reaction. More specifically, it can be set as the temperature conditions of 100 to 250 degreeC under normal pressure.

In addition, in this invention, hardening time is defined as the time required until it becomes a rubbery state from a liquid phase by heating. The measurement of the curing time is performed by, for example, using a scanning vibrating needle curemeter (SVNC), putting the vibrating needle needle into the measurement sample composition, and forcibly vibrating the needle needle to continuously change the amplitude. It can carry out by measuring the time from the liquid state to a rubbery state in the SVNC (frequency or amplitude) curve obtained by measuring by.

The urethane forming composition of this invention forms a urethane resin by hardening reaction of an isocyanate component and a polyol component under hardening conditions. The urethane-forming composition of the present invention uses an aliphatic or alicyclic isocyanate which is not an aromatic isocyanate as an isocyanate component, and uses a polyol of a room temperature liquid rather than a room temperature solid as a polyol component to suppress a curing reaction. In the presence of an inhibitor, an organometallic catalyst of a room temperature solid, not a room temperature liquid, is blended and prepared to be present in solid form in the composition. As a result, a urethane-forming composition having almost no yellowing attaining a pot life of at least 24 hours or more at room temperature and a curing time of about several minutes to about 25 minutes under curing conditions is obtained. Moreover, depending on the composition conditions, the urethane-forming composition which achieves pot life time of 70 hours or more at normal temperature and hardening time within 3 minutes in hardening conditions can also be obtained.

Since the urethane forming composition of this invention can maintain fluidity for 1 day or more after manufacture, and can harden | cure rapidly by heating at the time of shaping | molding, this is the operation | work in the manufacturing process of a urethane resin It becomes possible to improve the formability and moldability. This urethane forming composition can be used as a pseudo one-component thermosetting type urethane forming material.

The urethane resin produced by the urethane-forming composition of the present invention can be provided in various forms such as foams, films, elastomers, powders, solutions, emulsions, and the like, depending on additives and methods applied to the urethane-forming compositions. It can be used for various applications such as foams, elastomers, adhesives, paints, and binders.

Hereinafter, although the urethane forming composition of this invention, the polyol composition for obtaining the said urethane forming composition, and the manufacturing method of the urethane resin using the said urethane forming composition are demonstrated more concretely using an Example, this invention is It is not limited to the specific embodiment.

<Example>

Experimental Example 1

(1) Preparation of Mixed Composition

Room temperature liquid polyesterpolyols obtained from 3-methyl-1,5-pentanediol (MPD) and adipic acid and having a number average molecular weight of 2000 and a nominal average number of functional groups 2 (referred to as polyesterpolyol A in Tables 1 and 2) And, hereinafter referred to simply as A) 636 parts by mass, trimethylolpropane (TMP), 3-methyl-1,5-pentadiol (MPD) and adipic acid, number average molecular weight 3000, nominal average Room temperature liquid polyester polyol having a functional number of 3 (hereinafter referred to as polyesterpolyol B in Tables 1 and 2, hereinafter referred to simply as B) 159 parts by mass, and reaction inhibitor JP-508 (acidic phosphate ester: mono ( A mixture of 2-ethylhexyl acid phosphate) and bis (2-ethylhexyl acid phosphate) were produced by Johoku Chemical Co., Ltd. (100 ppm) for the polyol component and NW-96 for the polyol component. By mixing the ppm, the premix mixing composition Got it. NW-96 is KS-1010A-1 (di-n-octyl tin maleate polymer: manufactured by Kyodo Yakuching Co., Ltd.) and PN-250 (adipic acid ester plasticizer). The dispersion processed product obtained by mix | blending (manufactured by ADEKA Co., Ltd.) at a mass ratio of 50:50, and kneading until the particle diameter of KS-1010A-1 reaches a maximum of 30 µm by a triaxial roll.

Urethane-modified polyisocyanates obtained from hexamethylene diisocyanate (HDI) and 1,3-butanediol and having an NCO content of 17.5 mass% and an average number of functional groups 2 (hereinafter referred to as isocyanate A in Tables 1 and 2, hereinafter simply referred to as isocyanate A) 205 parts by mass and the entire amount of the premix mixed composition were mixed to obtain a urethane-forming mixed composition. R value was 1.05. In addition, the temperature at the time of mixing | blending made urethane modified polyisocyanate 45 degreeC, and made the premix mixed composition 25 degreeC. In addition, the premix composition was kept at the temperature not exceeding 40 degreeC until it mix | blended.

(2) measuring pot life

50 g of the obtained urethane-formable mixed composition was taken in a 100 ml glass bottle, and the loss of fluidity was visually confirmed at 25 degreeC. It was 48 hours when the time from manufacture of the urethane forming mixed composition of Experimental Example 1 to loss of fluidity was measured. In addition, the fluidity was taken as a point at which the flow of the composition fell down and the flow of the composition did not occur immediately, and was determined to be lost.

(3) measurement of curing time

0.3 ml of the urethane-forming mixed composition obtained in a sample stage heated to 150 ° C. in advance by a scanning vibrating needle curing machine (manufactured by Scanning Vibrating Needle Curemeter (SVNC: RAPRA TECHNOLOGY LTD.) Was prepared) The excitation was performed at a frequency of 60 Hz to measure the change over time of the amplitude of the vibrating needle. From the obtained SVNC curve, the time required for the amplitude value to be lowered from the initial liquid state 9000 to the rubber state 2000 was found to be 2 minutes.

(4) comprehensive evaluation

Table 1 shows the results obtained by integrating the mixed composition of each experimental example including Experimental Example 1 and the curing time, pot life and overall evaluation of the obtained urethane-forming mixed composition. In the comprehensive evaluation, the curing time within 3 minutes and the pot life time of 24 hours or more were achieved under a temperature condition of 150 ° C. for the curing time and 25 ° C. for the pot life. The case where the hardening time of and the pot life time of 24 hours or more were achieved was made into (circle), and the case where hardening time within 25 minutes and the pot life time of 24 hours or more was achieved was (triangle | delta). In addition, when the hardening time exceeded 25 minutes irrespective of the pot life under the same conditions, and when only the pot life of less than 24 hours could be achieved irrespective of the hardening time, all were evaluated as x. In the said Experimental Example 1, since the hardening time of 2 minutes and the pot life of 48 hours were achieved, comprehensive evaluation determined with (circle). In addition, Experimental Example 1 is an embodiment of the present invention.

Experimental Example 2

(1) Preparation of Mixed Composition

A premix mixed composition having the same composition as in Experimental Example 1 was obtained except that JP-508, a reaction inhibitor, was set to 200 ppm, and 2000 ppm, NW-96, which was an organic tin compound catalyst. In the same manner as in Experiment 1, 205 parts by mass of isocyanate A and the entire amount of the premix composition were mixed to obtain a urethane-forming mixed composition.

(2) measuring pot life

In the same procedure as in Experimental Example 1, 50 g of the obtained urethane-forming mixed composition was taken in a 100 ml glass bottle, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C., which was 48 hours.

(3) measurement of curing time

In the same procedure as in Experimental Example 1, the time required for the amplitude to decrease from 9000 in the liquid state to 2000 in the rubber state was found to be 1.2 minutes.

(4) comprehensive evaluation

In Experimental Example 2, since the curing time of 1.2 minutes and the pot life of 48 hours were achieved, the comprehensive evaluation was determined as ◎. Similarly, the results of Experimental Example 2 are shown in Table 1. In addition, Experimental Example 2 is an embodiment of the present invention.

Experimental Examples 3 to 5

(1) Preparation of Mixed Composition

A premix mixed composition having the same composition as in Example 1 was obtained except that JP-508, a reaction inhibitor, was set to 200 ppm (Experimental Example 3), 500 ppm (Experimental Example 4), or 1000 ppm (Experimental Example 5). In the same manner as in Example 1, a total amount of 205 parts by mass of isocyanate A and the respective premix compositions were mixed to obtain a urethane-forming mixed composition for each experimental example.

(2) measuring pot life

In the same procedure as in Experimental Example 1, 50 g of the urethane-forming mixed composition of each Experimental Example was taken in 100 ml of glass bottles, respectively, and the time was measured until the loss of fluidity was visually observed at 25 ° C. It was time (experimental example 3) 72 hours (experimental example 4) and 48 hours (experimental example 5).

(3) measurement of curing time

About each experiment example, the time required for the amplitude to fall from the liquid state 9000 to the rubber state 2000 was calculated | required by the same procedure as Experimental example 1, respectively. It was 20 minutes (Experimental example 5).

(4) comprehensive evaluation

In Experimental Example 3, since curing time of 5 minutes and pot life of 56 hours were achieved, comprehensive evaluation was determined as (circle). Since the hardening time of 11 minutes and the pot life of 72 hours were achieved in Experimental Example 4, comprehensive evaluation was determined as (circle). In Experimental Example 5, since curing time of 20 minutes and pot life of 48 hours were achieved, comprehensive evaluation was determined as (triangle | delta). Similarly, the results of Experimental Examples 3 to 5 are shown in Table 1. In addition, Experimental Examples 3 to 5 are examples of the present invention.

In consideration of Experimental Example 1 and Experimental Examples 3 to 5, the curing time tended to increase at the same time as the addition amount of the reaction inhibitor. On the other hand, the pot life was extended to 500 ppm of the addition amount of the reaction inhibitor, but on the contrary, the pot life tended to be shortened. In addition, in comparison with Experimental Example 2 and Experimental Example 3, when the conditions of the reaction inhibitor were the same, when the addition amount of the organometallic catalyst was increased, the pot life tended to be slightly shortened, but the curing time was preferably shortened, and A tendency to obtain favorable results was seen.

Experimental Example 6

(1) Preparation of Mixed Composition

Instead of polyol A and polyol B as polyol components, a mass ratio of 1,6-hexanediol and 3-methyl-1,5-pentadiol (MPD) is obtained from a mixture of 1: 9 and diethylcarbonate (DEC). Obtained by a deethanol reaction, using a room temperature liquid polycarbonate diol having a number average molecular weight of 2000 and a nominal average number of functional groups of 2 (referred to as polycarbonate polyol C in Tables 1 and 2, hereinafter referred to simply as polyol C) In addition, a premix mixed composition having the same composition as in Experimental Example 2 was obtained. In the same manner as in Experimental Example 2, a total amount of 205 parts by mass of isocyanate A and the premix composition was mixed to obtain a urethane-forming mixed composition.

(2) results

In the same procedure as in Experimental Example 1, 50 g of the obtained urethane-forming mixed composition was taken in a 100 ml glass bottle, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C., and it was 36 hours. In the same procedure as in Experimental Example 1, the time required for the amplitude to become a rubber state from the liquid state was found to be 0.9 minutes.

(3) comprehensive evaluation

In Experimental Example 6, since the curing time of 0.9 minutes and the pot life of 36 hours were achieved, the comprehensive evaluation was determined to be ◎. The results of Experimental Example 6 are shown in Table 1. In addition, Experimental Example 6 is an embodiment of the present invention. Comparing Experimental Example 2 with Experimental Example 6, when the polycarbonate polyol was used, the pot life was slightly shorter than when the polyester polyol was used, but the curing time tended to be shorter.

Experimental Example 7

(1) Preparation of Mixed Composition

A premix mixed composition having the same composition as in Experimental Example 2 was obtained except that 649 parts by mass of polyol A and 162 parts by mass of polyol B were used as the polyol component. As isocyanate components, allophanate-modified polyisocyanates obtained from hexamethylene diisocyanate (HDI) and isopropanol, having an NCO content of 19.3 mass% and an average number of functional groups of 2 (referred to as isocyanate B in Tables 1 and 2, hereinafter simply 189 parts by mass of the isocyanate B) and the entire premix mixture composition were mixed to obtain a urethane-forming mixture composition. R value was 1.05. In addition, the temperature at the time of mix | blending made the allophanate modified polyisocyanate and the premix mixed composition together to 25 degreeC.

(2) results

In the same procedure as in Experimental Example 1, 50 g of the obtained urethane-forming mixed composition was taken in a 100 ml glass bottle, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C., and it was 36 hours. In the same procedure as in Experimental Example 1, the time required for the amplitude to become the rubber state from the liquid state was found to be 1.3 minutes.

(3) comprehensive evaluation

In Experimental Example 7, since the curing time of 1.3 minutes and the pot life of 36 hours were achieved, the comprehensive evaluation determined that it was (circle). The results of Experimental Example 7 are shown in Table 1. In addition, Experimental Example 7 is an Example of this invention. When Experimental Example 2 and Experimental Example 7 were compared, it was confirmed that when the isocyanate B was used, the pot life was shortened slightly compared with the case where the isocyanate A was used, but an equivalent curing time was achieved.

Experimental Example 8

(1) Preparation of Mixed Composition

As a polyol component, the premix mixed composition which has a composition similar to Experimental example 2 except having polyol A as 809 mass parts and not using polyol B was obtained. As isocyanate components, allophyte-modified polyisocyanates obtained from hexamethylene diisocyanate (HDI) and 3-methyl-1,5-pentanediol (MPD) having an NCO content of 19.2% by mass and an average number of functional groups of 4.8 (Table 1 and Table 1). It referred to as double isocyanate C, hereinafter referred to simply as isocyanate C), and the entire amount of the premix mixture composition was mixed to obtain a urethane-forming mixed composition. R value was 1.05. In addition, the temperature at the time of mix | blending made the allophanate modified polyisocyanate and premix mixed composition 25 degreeC.

(2) results

In the same procedure as in Experimental Example 1, 50 g of each of the obtained urethane-forming mixed compositions was taken in a 100 ml glass bottle, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C., and it was 40 hours. In the same procedure as in Experimental Example 1, the time required for the amplitude to become a rubber state from the liquid state was found to be 0.8 minutes.

(3) comprehensive evaluation

In Experimental Example 8, since the curing time of 0.8 minutes and the pot life of 40 hours were achieved, the comprehensive evaluation was determined as ◎. The results of Experimental Example 8 are shown in Table 1. In addition, Experimental Example 8 is an example of the present invention. Comparing Experimental Example 2 with Experimental Example 8, it was confirmed that when isocyanate C was used, the pot life was shortened slightly compared with the case where isocyanate A was used, but the curing time was shorter. Comparing Experimental Example 7 and Experimental Example 8, it was confirmed that when isocyanate C was used, the pot life was extended slightly and the curing time was further shortened as compared with the case where isocyanate B was used.

Experimental Example 9

(1) Preparation of Mixed Composition

As a polyol component, the premix mixed composition which has the composition similar to Experimental example 2 except having polyol A as 829 mass parts and not using polyol B was obtained. As an isocyanate component, a part of hexamethylene diisocyanate (HDI) is obtained by urethanization with 1,3-butanediol and then isocyanurate, a polyisocyanate having an NCO content of 21.8 mass% and an average number of functional groups of 3.5 (Table 1 and Table 2, referred to as isocyanate D, hereinafter referred to simply as isocyanate D), and 171 parts by mass of the premix mixed composition were mixed in total amount to obtain a urethane-forming mixed composition. R value was 1.05. In addition, the temperature at the time of mix | blending made the polyisocyanate and premix mixed composition 25 degreeC.

(2) results

In the same procedure as in Experimental Example 1, 50 g of each of the obtained urethane-forming mixed compositions was taken in a 100 ml glass bottle, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C., and it was 40 hours. In the same procedure as in Experimental Example 1, the time required for the amplitude to become a rubber state from the liquid state was found to be 0.7 minutes.

(3) comprehensive evaluation

In Experimental Example 9, since a curing time of 0.7 minutes and a pot life of 40 hours were achieved, the comprehensive evaluation was determined to be ◎. The results of Experiment 9 are shown in Table 1. In addition, Experimental Example 9 is an embodiment of the present invention. Comparing Experimental Example 2 with Experimental Example 9, when isocyanate D was used, it was confirmed that the pot life was slightly shorter than when using isocyanate A, but the curing time was shorter. Comparing Experimental Example 7 and Experimental Example 9, it was confirmed that when the isocyanate D was used, the pot life was extended slightly and the curing time was further shortened as compared with the case where the isocyanate B was used. Comparing Experimental Example 8 with Experimental Example 9, it was confirmed that when isocyanate D was used, the curing time was slightly shortened compared with the case where isocyanate C was used.

Experimental Example 10

(1) Preparation of Mixed Composition

As a reaction inhibitor, a premix mixed composition having the same composition as in Experimental Example 1 was obtained except that phosphoric acid (85%) was replaced with 50 ppm instead of JP-508. In the same manner as in Experimental Example 1, 205 parts by mass of isocyanate A and the entire amount of the premix composition were mixed to obtain a urethane-forming mixed composition.

(2) results

In the same procedure as in Experimental Example 1, 50 g of the obtained urethane-forming mixed composition was taken in a 100 ml glass bottle, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C., which was 48 hours. In the same procedure as in Experimental Example 1, the time required for the amplitude to become a rubber state from the liquid state was found to be 18 minutes.

(3) comprehensive evaluation

In Experimental Example 10, since it was 18 minutes of hardening time and 48 hours of pot life, comprehensive evaluation was determined as (triangle | delta). The results of Experimental Example 10 are shown in Table 1. In addition, Experimental Example 10 is an embodiment of the present invention. Comparing Experimental Example 1 with Experimental Example 10, when phosphoric acid was used instead of acidic phosphate ester as a reaction inhibitor, the curing time tended to be longer.

Experimental Example 11

(1) Preparation of Mixed Composition

As a organometallic catalyst, a premix mixed composition having the same composition as in Experimental Example 1 was obtained except that 500 ppm of DBTO (dibutyltin oxide) was used. In the same manner as in Experimental Example 1, 205 parts by mass of isocyanate A and the entire amount of the premix composition were mixed to obtain a urethane-forming mixed composition.

(2) results

In the same procedure as in Experimental Example 1, 50 g of the obtained urethane-forming mixed composition was taken in a 100 ml glass bottle, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C., which was 48 hours. In the same procedure as in Experimental Example 1, the time required for the amplitude to become a rubber state from the liquid state was found to be 6 minutes.

(3) comprehensive evaluation

In Experimental example 11, since it was the hardening time of 6 minutes and the pot life of 48 hours, comprehensive evaluation was determined as (circle). The results of Experimental Example 11 are shown in Table 2. Experimental Example 11 is an example of the present invention. Comparing Experimental Example 1 with Example 11, even when an organic tin compound of the same room temperature solid was used, the side using the di-n-octyl tin maleate polymer showed a tendency to shorten hardening time.

Experimental Example 12

(1) Preparation of Mixed Composition

As a reaction inhibitor, a premix mixed composition having the same composition as in Experimental Example 10 was obtained except that phosphoric acid (85%) was 100 ppm. In the same manner as in Experiment 10, 205 parts by mass of isocyanate A and the entire amount of the premix composition were mixed to obtain a urethane-forming mixed composition.

(2) results

In the same procedure as in Experimental Example 1, 50 g of the obtained urethane-forming mixed composition was taken in a 100 ml glass bottle, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C., which was 48 hours. In the same procedure as in Experimental Example 1, the time required for the amplitude to become a rubber state from the liquid state was found to be 23 minutes.

(3) comprehensive evaluation

In Experimental example 12, since it was the hardening time of 23 minutes and the pot life of 48 hours, comprehensive evaluation was determined as (triangle | delta). The results of Experimental Example 12 are shown in Table 2. In addition, Experimental Example 12 is an Example of this invention. Comparing Experimental Example 10 with Experimental Example 12, when the amount of phosphoric acid added increased, the curing time tended to be longer.

Experimental Examples 13 to 20

(1) Preparation of Mixed Composition

About each experiment example of Experimental Examples 13-20, the said premix composition which the polyol component, the reaction inhibitor, and the catalyst were mixed on the composition conditions shown in Table 2 was obtained. About each test example, the isocyanate component of the composition conditions shown in Table 2 and whole quantity of each premix composition were mixed, and the urethane formation mixing composition was obtained about each test example. Incidentally, in the table, isocyanate E is obtained by carbodiimide-forming a part of diphenylmethane diisocyanate and represents a modified polyisocyanate having an NCO content of 28.8% by mass and an average number of functional groups of 2.1 (hereinafter simply referred to as isocyanate E). . In addition, DB60 in the table shows TOYOCAT-DB60 (manufactured by Tosoh Corporation) as an amine catalyst. In the table, DOTDL represents dioctyl tin dilaurate which is an organic tin compound of room temperature liquid. In addition, (A) in a table | surface shows that after a catalyst addition, the premix composition is heated once at 80 degreeC, a solid catalyst is dissolved, and it cooled to 25 degreeC after that.

(2) results

In the same procedure as in Experimental Example 1, 50 g of the urethane-forming mixed composition of each Experimental Example was taken in 100 ml of glass bottles, respectively, and the time was measured until the disappearance of fluidity was visually observed at a temperature of 25 ° C. Indicating pot life was obtained. Moreover, about each experiment example, when the time required from the liquid state to a rubber state was calculated | required in the same procedure as Experimental example 1, the hardening time shown in Table 2 was obtained.

(3) comprehensive evaluation

From the curing time and pot life obtained in Experimental Examples 13 to 20, the overall evaluation was determined to be x for all the Experimental Examples. In addition, Experimental Examples 13-20 are comparative examples.

Experimental Example 13 was made under the same conditions as in Experimental Example 1, except that the reaction inhibitor and the catalyst were not used together. When the reaction inhibitor and the organometallic catalyst were not added, a long pot life of 72 hours was obtained, but the curing time was obtained. It took this 60 minutes and was not compatible with a sufficiently long pot life and a sufficiently short curing time.

Experimental Example 14 was subjected to the same conditions as Experimental Example 1, except that no catalyst was used. When no organometallic catalyst was added, a long pot life of 72 hours was obtained. Silver took more than 60 minutes and was not compatible with sufficiently long pot life and sufficiently short cure times.

Experimental Example 15 was carried out under the same conditions as in Experimental Example 1, except that no reaction inhibitor was used and dioctyltin dilaurate of a room temperature liquid was used instead of the organic tin compound of a room temperature solid. In the case of using the catalyst, a short curing time of 1.8 minutes was obtained, but before the heating, the catalyst was dissolved and uniformized in the premix composition, resulting in a very short pot life of 0.5 hours, thereby achieving a sufficiently long pot life and a sufficiently short curing time. It wasn't worth it.

Experimental Example 16 was used in the same conditions as Experimental Example 1, except that dioctyltin dilaurate in a room temperature liquid was used instead of the organic tin compound in a room temperature solid. Although a short curing time of minutes was obtained, the catalyst was dissolved and homogenized before heating, resulting in a very short pot life of 1 hour, which was not compatible with a sufficiently long pot life and a sufficiently short curing time. When Experimental Example 15 is compared with Experimental Example 16, since a reaction inhibitor is used, in Experimental Example 16, both the pot life and the curing time are long.

Experimental Example 17 was made under the same conditions as in Experimental Example 1 except that no reaction inhibitor was used. When no reaction inhibitor was added, a short curing time of 1.5 minutes was obtained, but a short pot life of 2 hours was sufficient. Long pot life and short enough curing times were not compatible.

Experimental Example 18 was the same conditions as Experimental Example 1 except that the premix composition was once heated to 80 ° C and then cooled to 25 ° C after the addition of the catalyst, but once the premix composition was heated to 40 ° C or more, It has been shown that a sufficiently long pot life cannot be achieved because the solid catalyst dissolves and does not precipitate upon cooling. In Experimental Example 18, a short curing time of 1.4 minutes was obtained, but the pot life was very short at 0.5 hours, so that a sufficiently long pot life and a sufficiently short curing time were not compatible.

Experimental Example 19 was made under the same conditions as Experimental Example 1, except that the composition and blending conditions of the polyol component were slightly changed using isocyanate E, which is an aromatic isocyanate, instead of isocyanate A, compared to aliphatic and alicyclic systems. In the case of using a highly reactive aromatic isocyanate, the curing time was shorter than that of Experimental Example 1, which was 1 minute, while the short pot life was 4 hours, which was not compatible with a sufficiently long pot life and a sufficiently short curing time. .

Experimental Example 20 was made under the same conditions as Experimental Example 1 except that TOYOCAT-DB60, which is an amine catalyst of a room temperature liquid, was used instead of an organic tin compound of a room temperature solid, but an amine catalyst other than an organic tin compound was used. Although 36 hours and a relatively long pot life were obtained, it was necessary to cure for 60 minutes or more because of low catalyst activity, so that a sufficiently long pot life and a sufficiently short cure time were not compatible.

As described above, according to the present invention, there is provided a urethane-forming composition, a polyol composition, and a method for producing a urethane resin, which realizes compatibility between a long pot life at normal temperature and a short cure time under curing conditions. Since the urethane-forming composition of the present invention can maintain fluidity for at least one day after production, and can be cured rapidly by heating during molding, the workability in the manufacturing process of the urethane resin is thereby achieved. And moldability can be improved.

The urethane-forming composition can be used as a pseudo one-component heat curable urethane-forming material, and the urethane resin produced by the urethane-forming composition may be foamed, film, or the like according to additives or methods applied to the urethane-forming composition. It can be provided in various forms such as elastic bodies, powders, solutions, emulsions, etc., and can be used for various applications such as flexible foams, rigid foams, elastomers, adhesives, paints, and binders. It is expected to improve moldability and workability.

Although embodiments and examples of the present invention have been described so far, embodiments and examples of the present invention are not limited to the above-described embodiments and examples, and other embodiments and examples, additions, changes, As long as a person skilled in the art can change, such as a deletion, it can be changed and it is included in the scope of the present invention as long as it exhibits the action and effect of this invention in either aspect.

Claims (13)

An isocyanate component comprising at least one selected from the group consisting of aliphatic and cycloaliphatic isocyanates and derivatives and modified substances thereof or mixtures thereof; Polyol component of normal temperature liquid, Reaction inhibitors, Organometallic catalyst of room temperature solid present in solid form in the composition Urethane forming composition blended. The urethane-forming composition according to claim 1, wherein the polyol component comprises at least one of polyesterpolyols and polycarbonate polyols or mixtures thereof. The urethane-forming composition according to claim 1 or 2, wherein the organometallic catalyst is an organotin compound. The urethane-forming composition according to any one of claims 1 to 3, wherein the reaction inhibitor is an acidic phosphate ester. The method according to any one of claims 1 to 4, wherein the isocyanate component comprises one or more selected from the group consisting of hexamethylene diisocyanate having an average number of functional groups of 2 to 5 and derivatives and modified substances thereof. The urethane forming composition. Polyol component of normal temperature liquid, Reaction inhibitors, Organometallic catalyst of room temperature solid present in solid form in the composition It is formulated to include, A polyol composition for forming a urethane resin by reacting with an isocyanate component comprising at least one selected from the group consisting of aliphatic and cycloaliphatic isocyanates and derivatives and modified substances thereof or mixtures thereof. The method of claim 6, wherein the polyol component comprises at least one of polyesterpolyols and polycarbonate polyols or mixtures thereof, The organometallic catalyst is an organic tin compound, The reaction inhibitor is an acidic phosphate ester, The isocyanate component is a polyol composition comprising one or more selected from the group consisting of hexamethylene diisocyanate having an average number of functional groups of 2 to 5 and derivatives and modified substances thereof. Of an isocyanate component, at least one polyol component in a room temperature liquid phase, a reaction inhibitor, and a room temperature solid present in a solid form in the composition, including at least one selected from the group consisting of aliphatic and cycloaliphatic isocyanates, and derivatives and modified compounds thereof Preparing a urethane-forming composition in which an organometallic catalyst is blended; Heating and curing the urethane-forming composition Method for producing a urethane resin comprising a. The method of claim 8, wherein the preparing comprises mixing the polyol component, the reaction inhibitor, and the organometallic catalyst at a temperature of 20 to 40 ° C., and preparing a polyol composition in which the organometallic catalyst is dispersed in the composition. Mixing the prepared polyol composition and the isocyanate component to produce the urethane-forming composition, The step of curing comprises the step of heating to a temperature of 100 to 250 ℃. 10. The process according to claim 8 or 9, wherein the polyol component comprises at least one of polyesterpolyols and polycarbonate polyols or mixtures thereof. The production method according to any one of claims 8 to 10, wherein the organometallic catalyst is an organotin compound. The production method according to any one of claims 8 to 11, wherein the reaction inhibitor is an acidic phosphate ester. The method according to any one of claims 8 to 12, wherein the isocyanate component comprises one or more selected from the group consisting of hexamethylene diisocyanate having an average number of functional groups of 2 to 5 and derivatives and modified substances thereof. Urethane-forming composition.