JPS60210614A - Unsaturated polyester resin composition comprising cure accelerator - Google Patents

Abstract

PURPOSE:The titled resin composition which, even when stored for a long time, undergoes an extremely small change in a room temperature gelation time with the lapse of time, prepared by adding a specified cure accelerator to an unsaturated polyester resin. CONSTITUTION:A cure accelerator is obtained by mixing 100pts.wt. cobalt soap (A) selected from cobalt octylate and cobalt naphthenate with 1-100pts.wt. hexamethylenetetramine (B), 0.1-20pts.wt. compound (C) selected from among lactic acid, cobalt lactate, and cobalt acetate, about 50-2,000pts.wt., per 100pts.wt. total of components A, B, and C, high-boiling solvent (D) (having an atmospheric b.p. >=100 deg.C, e.g., xylene) and a hydrocarbon solvent (E) having an atmospheric b.p. of 60-90 deg.C and being azeotropically distillable with water (e.g., n-hexane), heating the obtained mixture to remove water as an azeotrope with solvent E, and distilling off the remaining solvent E. 0.005-10pts.wt. (in terms of Co metal), said cure accelerator is added to 100pts.wt. unsaturated polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an unsaturated polyester resin composition containing a curing accelerator. For more details,
The present invention relates to a two-component unsaturated polyester resin composition whose gelation time at room temperature shows very little change over time even during long-term storage.

A two-component unsaturated polyester resin composition that contains a curing accelerator in advance before use requires only adjusting the amount of catalyst in order to adjust the gelling time to the desired length 1c. Since there is no risk of explosion or ignition which tends to occur when a curing accelerator and a curing accelerator are added to an unsaturated polyester resin at the same time, it is currently produced and consumed industrially in large quantities. However, using cobalt metal soaps such as cobalt octylate, cobalt naphthenate, cobalt oleate, and cobalt stearate, which are commonly used as curing accelerators for two-component unsaturated polyester resin compositions, The two-component unsaturated polyester resin composition has the disadvantage that the gelation time during use increases with the storage period even at the same use temperature and the same amount of catalyst.

If such a two-component unsaturated polyester resin composition is stored for an even longer period of time, the gelation time will become even longer, and practical curing properties will be lost.

In such cases, the current practice is to adjust the desired gelation time by adding a new curing accelerator or increasing the amount of catalyst, but this is preferable from both cost and workability points of view. It's not a thing.

The present inventors have conducted intensive research to improve the drawback of conventional two-component unsaturated polyester resin compositions, in which the gelation time changes with the passage of the storage period. Developed a curing accelerator for unsaturated polyester resins that, when blended with unsaturated polyester resins, provides a two-component unsaturated polyester resin composition with extremely small changes in gelation time over long periods of storage. This led to the completion of the present invention.

That is, the unsaturated polyester resin composition of the present invention contains cobalt soap (2) selected from the group consisting of cobalt octylate and cobalt naphthenate (hereinafter simply referred to as cobalt soap (5)), hexamethylenetetramine (B
), a compound (C) selected from the group consisting of lactic acid, cobalt lactate, and cobalt acetate (hereinafter simply referred to as compound (C)), a solvent with a boiling point of 100°C or higher at normal pressure (
D) (hereinafter referred to as a high boiling point solvent (D)) and a hydrocarbon solvent (1) whose boiling point is 60 to 90°C at normal pressure and is azeotropic with water (hereinafter referred to as a low boiling point solvent (E)) (B) 1 to 10 parts by weight per 100 parts by weight of (A)
0 parts by weight and +CI in a ratio in the range of 0.1 to 20 parts by weight (hereinafter simply referred to as mixture +M).

) and distilled off (■) after removing water by azeotroping with El to make it substantially water-free.
It is called accelerator (I). ) in a specific amount.

Cobalt soap (Allot) used in the present invention
, cobalt octylate, or cobalt naphthenate may be used alone, or both may be used in combination.

Commercially available hexamethylenetetramine (Bl) can be used as is.

As the compound (C1), lactic acid, cobalt lactate, or cobalt acetate may be used alone, or two or more types may be used in combination.

These are used in a ratio of 1 to 100 parts by weight of hexamethylenetetramine (B) and 0.1 to 20 parts by weight of compound (C) per 1100 parts by weight of cobalt soap (A1).

The high boiling point solvent D) has a boiling point of 100°C at normal pressure.
The above solvents can be used. Examples of such substances include hydrocarbons such as toluene, xylene, n-octane, 6-mineral turbene (a product of Mitsubishi Oil Corporation), and ``mineral spirit''; Hydrolic or polyhydric alcohols; ethers such as butyl ether and dioxane; esters such as dimethyl phthalate and dibutyl phthalate; glycol ethers such as methoxyethanol and ethoxyethanol, or mixtures thereof; The high boiling point solvent (■) is the sum of cobalt soap (2), hexamethylenetetramine (B) and the compound TCI.
It is preferred to use proportionate amounts ranging from 50 to 2000 parts by weight, with 0 parts by weight.

In proportions less than 50 parts by weight, cobalt soap, hexamethylenetetramine or the compound (0
is not preferable because it may not be completely dissolved in the high boiling point solvent and may precipitate. On the other hand, if the amount exceeds 2,000 parts by weight, the concentration of the active ingredient in the resulting accelerator will decrease, making it difficult to add this accelerator to an unsaturated polyester resin to form an unsaturated polyester resin composition. A large amount of accelerator must be added, but in this case, a large amount of high boiling point solvent (■) will be included in the unsaturated polyester resin composition, and the cured product when the unsaturated polyester resin is cured. Physical properties deteriorate, which is not preferable.

To prepare accelerator (I) according to the present invention, a mixture + Ml is prepared from cobalt soap, hexamethylenetetramine (Bl), compound (C1, high boiling point solvent (Di) and low boiling point solvent (El). may be mixed in any order.For example, cobalt stone ken^, hexamethylenetetramine a3), compound (C),
A high boiling point solvent (DJ) and a low boiling point solvent (El may be mixed simultaneously to form a mixture (Ml).Also, cobalt soap powder,
Hexamethylenetetramine CB+, compound (q), high boiling point solvent (one or more arbitrarily selected from DJ) and low boiling point solvent (El are mixed and heated to form low boiling point solvent (E)
While refluxing, cobalt soap, hexamethylenetetramine (B), compound (q) and/or the remainder of the high boiling point solvent can be added to form a mixture (M).The order and method of mixing these can be The present invention is not limited by this.

The mixture thus prepared (from Ml, former low boiling point solvent) is heated under reflux to become substantially water-free by removing water by azeotroping the low boiling point solvent [F] and water. Refluxing for 0.5 to 5 hours is usually sufficient.

By azeotropically distilling this low-boiling point solvent with water to remove water and make it substantially water-free, the accelerator becomes a homogeneous solution that does not separate and is stable even during long-term storage. It can be made into a solution.

Water is removed from the mixture fM+ to make it substantially water-free, and then the low boiling point solvent is distilled off to obtain the promoter (Il). The method of distilling off these low boiling point solvents (El) does not affect the present invention.

The accelerator (Il) thus obtained is stable without separating even after several months of storage.Accelerator fI can be effectively used as a curing accelerator for two-component unsaturated polyester resin compositions. However, if necessary, it can be diluted with an organic solvent or a polymerizable monomer copolymerizable with the unsaturated polyester resin. Examples of such organic solvents include hydrocarbons such as toluene, xylene, and n-octane; alcohols such as methanol and ethanol; glycosols such as ethylene glycol, propylene glycol, and diethylene glycol; and methoxyethanol and ethoxyethanol. Examples include glycol ethers and glycerin. Moreover, as the polymerizable monomer copolymerizable with the unsaturated polyester resin, the polymerizable monomers constituting the unsaturated polyester resin described below can be mentioned as they are.

The unsaturated polyester resin (1) used in the present invention is composed of an unsaturated polyester and a polymerizable monomer. Unsaturated polyesters include hepatic acid, phthalic anhydride, isophthalic acid, adipic acid, 3-methyl-4-cyclohexene in addition to β-unsaturated dibasic acids such as fumaric acid, maleic anhydride, and itaconic acid. The acid component is one to which a saturated dibasic acid such as -1,2-dicarboxylic acid is added, and ethylene glycol, propylene glycol, L3-
Acid value 6 obtained by dehydration condensation reaction of polyhydric alcohols such as butanediol and glycerin as alcohol components.
0 or less and a molecular weight of 500 to 10,000 can be used. Examples of polymerizable monomers include styrene,
Examples include halogenated styrene, vinyltolunin, methyl methacrylate, diallyl phthalate, etc., and one or more of these can be used in a ratio of 20 to 300 parts by weight per 10 parts by weight of unsaturated polyester. .

The unsaturated polyester resin composition of the present invention has an accelerator (I
) and unsaturated polyester resin (Co., Ltd.), and contains an accelerator (Il as cobalt metal content in a ratio of 0.005 to 1.0 parts by weight as cobalt metal content) to 100 parts by weight of unsaturated polyester resin ([). If the amount of cobalt metal is less than o or oos parts by weight, the effect will not be sufficient, and conversely, if the amount is more than 1.0 parts by weight, the amount added will increase. No accompanying increase in effect was observed, and both are unfavorable.

The unsaturated polyester resin composition using the accelerator (I) obtained based on the production method of the present invention is stable without separating even during long-term storage, and has extremely low gelation time. It is small in size, and the gelation time can be adjusted to a desired length simply by adding an organic peroxide as a catalyst during curing, and has excellent industrial workability.

Additives such as fillers such as calcium carbonate and clay, coloring pigments, mold release agents, and thixotropic agents may be added to the unsaturated polyester resin composition of the present invention, if necessary. The present invention is not limited by the use of .

Furthermore, an amine accelerator known in the art such as dimethylaniline, diethylaniline, dimethyl p-toluidine, etc. can be used in combination with the unsaturated polyester resin composition of the present invention. The present invention does not depend on whether or not the agent is used.

To cure the unsaturated polyester resin composition according to the present invention, organic peroxide curing agents commonly used in the art, such as methyl ethyl ketone peroxide and cumene hydroperoxide, can be effectively used.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is of course not limited to these Examples. In addition, in the examples, "part" means part by weight, and "%" means % by weight.

Example 1 A reactor equipped with a partial condenser was charged with 33.8 Ii of cobalt octylate, 0.4 g of cobalt lactate, 60.81 g of xylene, and 19 BII of 71-hexane, and heated with stirring at 6 to 75° C. Water was removed azeotropically without refluxing the hexane. After refluxing for 1 hour, 5.09 g of hexamethylenetetramine was added, and the mixture was heated for another 1 hour at 70~
Water was removed under reflux azeotropy at 75°C, resulting in a substantially water-free state. The amount of water removed was 1.51. Subsequently, by distilling off n-hexane, the accelerator (hereinafter referred to as
It is called accelerator (1). ) was obtained. The cobalt metal content of promoter (1) was 5.8%.

When accelerator (1) was stored at room temperature in a sealable container, no separation was observed even after 6 months.

Example 2 In a reactor similar to that in Example 1, 28.61 cobalt naphthenate (copal octylate) 16. sg, cobalt lactate 0.5g, cobalt acetate o, sIi.

Hexamethylenetetramine s, og, "Mineral Turpene" (Mitsubishi Oil Company product) 46.311 and benzene 26
4 Ii was charged and heated at 80 to 100°C to azeotrope the mixture under reflux of benzene to remove water and make it substantially water-free. The water removed by refluxing azeotrope for 1.5 hours was 1.5 g.

Subsequently, benzene was distilled off to obtain a promoter (hereinafter referred to as promoter (2)). The cobalt metal content of promoter (2) was 5.796.

Example 3 Into the same reactor as in Example 1, 91.0 g of cobalt octylate solution (cobalt octylate 46.996) was charged, and cobalt lactate i, og, hexane Add 8.0 g of methylenetetramine and 264 g of benzene and stir
Water was removed by heating to 0-98°C and azeotropically distilling with benzene. 1.61 of water was removed in 1.5 hours of reflux azeotrope. After further heating and stirring at 80 to 90°C for 1 hour, benzene was distilled off to remove the accelerator (hereinafter referred to as accelerator).
3). ) was obtained. The cobalt metal content of promoter (3) was 8.0%.

Example 4 Cobalt acetate 1.01 hexamethylenetetramine 8° OII was added to 91 g of a xylene solution containing 42.0% by weight of cobalt naphthenate and 26.0% by weight of cobalt octylate.
198 g of beef sun was added to and n- and mixed. This mixture was charged into a reactor similar to that in Example 11,
Water was removed by heating to 65-75°C to azeotrope with n-hexane.

1.71 of water was removed in 2 hours. Furthermore, a promoter (hereinafter referred to as promoter (4)) was obtained by distilling off n-hexane. The cobalt metal content contained in promoter (4) was 8.0%.

Example 5 In a reactor similar to that in Example 1, a dispersion of hexamethylenetetramine in bovine siren (hexamethylenetetramine 1
5.9%) 37. 'l Prepare lactic acid o, s
y, cobalt naphthenate 61.8Fk and benzene 26
49 was added and heated under stirring to azeotrope the mixture with benzene to remove water for 2 hours. Subsequently, benzene was distilled off to obtain an accelerator (hereinafter referred to as accelerator (5)). The cobalt metal content of promoter (5) was 6.096.

Example 6 A dispersion of cobalt acetate (cobalt acetate 1.75%) 86.4.9 (cobalt acetate 1.75%) was charged into a reactor similar to that in Example 1, and further cobalt octylate 50 was added. .1,9. Hexamethylenetetramine 13.5II and n-hexane 297g were added and heated with stirring, and water was removed by azeotroping with n-hexane. Subsequently, n-hexane was distilled off. A promoter (hereinafter referred to as promoter (6)) was obtained.Promoter (
6) The cobalt metal content contained in I was 6.0%.

Example 7 Maleic anhydride, phthalic anhydride, and propylene glycol in a molar ratio of 0.5: 0.5: 1.0, respectively.
A dehydration condensation reaction was carried out at 20° C. under a nitrogen stream to obtain an unsaturated polyester with an acid value of 35. 0.01 part of hydroquinone and 40 parts of styrene were added to 60 parts of this unsaturated polyester and mutually dissolved to form an unsaturated polyester resin (hereinafter referred to as resin (1)).

An unsaturated polyester resin composition was prepared by adding 1110.5 parts of accelerator to +11100 parts of resin. This unsaturated polyester resin composition was put into a can, tightly capped, and
The samples were stored at 40°C and 40°C, respectively, and changes in gelation time over time were examined. Measurements were carried out immediately after the preparation of the unsaturated polyester resin composition and at various times after 5, 10, 20, 40, and 60 days, and 100 parts of the unsaturated polyester resin composition was compared with methyl ethyl ketone based on the method described in JIS K6901. One part of a solution of peroxide in 5596 dimethyl phthalate was added, and the gelation time at room temperature was measured.

The results when stored at 20°C are shown in Table 1, and the results when stored at 4°C are shown in Table 2. In both cases, the change in gelation time over time was small.

Comparative Example 1 Changes in gelation time over time were carried out in the same manner as in Example 7, except that only 0.5 part of a cobalt octylate solution with a metal content of 896 was added to 100 parts of the resin (1) obtained in Example 7. was measured. Table 1 shows the results when stored at 20°C.
Table 2 shows the results when stored at 40°C. The changes in gelation time over time were large in all cases.

Table 1 (Storage at 20°C) Example 8 1 part of the accelerator (2) obtained in Example 2 and 3 parts of the accelerator obtained in Example 3 for 11,100 parts of the resin obtained in Example 7, respectively. ) to prepare two unsaturated polyester resin compositions.The two unsaturated polyester resin compositions were stored at 40°C and the gelation time was adjusted as in Example 7. The changes over time were investigated. The results were as shown in Table 3, No. ζ, and the changes over time were small.

Table 3 Example 9 Maleic anhydride, phthalic anhydride, ethylene glycol and 1,3-butanediol in a ratio of 0.4:0.6, respectively.
: 0.6 : 0.45, and in the same manner as in Example 7, an unsaturated polyester having an acid value of 33 was obtained. This unsaturated polyester resin (hereinafter referred to as resin (2
). ).

To 21,100 parts of the resin, 1 part of Aerosil #200 (finely powdered silicon oxide) was added as a thixotropic agent, and after thorough kneading with a homomixer, 1 part of the accelerator (4) obtained in Example 4 was added. A thixotropic unsaturated polyester resin composition was prepared. Using this thixotropic unsaturated polyester resin composition, 40% was prepared in the same manner as in Example 7.
Changes in gelation time over time during storage at °C were measured. As shown in Table 4, the gelation time did not change over time.

Comparative Example 2 Example 9 except that only 1 part of a cobalt octylate solution with a metal content of 896 was added to the resin (21,100 parts, 1 part of Aerosil #200 was added as a thixotropic agent, and thoroughly kneaded with a homomixer). Changes in gelation time over time during storage at 40° C. were investigated in the same manner as in the case of Inoro.The results showed large changes over time as shown in Table 4.

Table 4 Example 10 Resin (accelerator (5) for each 21100 parts 0
．． 5 parts and an accelerator (610.5 parts) were added to obtain two types of unsaturated polyester resin compositions. These two types of unsaturated polyester resin compositions were used and stored at 40°C in the same manner as in Example 7. The changes over time in the gelation time were investigated.The results are shown in Table 5.The changes over time in the gelation time were slight.

Table 5

Claims (1)

[Claims] 1. A cobalt soap selected from the group consisting of cobalt octylate and cobalt naphthenate, hexamethylenetetramine (B), lactic acid, a compound selected from the group consisting of cobalt lactate and cobalt acetate (Q, boiling point at normal pressure is 100°C or higher, and 6ζ is a hydrocarbon solvent whose boiling point at normal pressure is 60 to 90°C and is azeotropic with water, and (A) 100 parts by weight per day.
After heating the mixture (M) in a ratio of ~100 parts by weight and IQ 0.1 to 20 parts by weight and azeotroping with ■ to make it substantially water-free except for water. It consists of (I) a curing accelerator for unsaturated polyester resin obtained by distilling off (I) and an unsaturated polyester resin, and (I) is o, oos as a cobalt metal content per 100 parts by weight of (II). An unsaturated polyester resin composition characterized in that the proportion ranges from 1.0 to 1.0 parts by weight.