JPH0412744B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to unsaturated polyester resin compositions. More specifically, it is an unsaturated polyester resin in which an unsaturated polyester and a polymerizable vinyl monomer are safely mixed without gelation, and the gelation time is prevented from changing over time even if it contains a polymerization accelerator. It provides: Usually, unsaturated polyester resin is a polymerizable unsaturated polyester obtained by a dehydration condensation reaction between an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride, a mixture of a saturated dicarboxylic acid or a saturated dicarboxylic anhydride, and a polyhydric alcohol. It is obtained by mutually dissolving a vinyl monomer and a polymerization inhibitor selected from polyphenols. This unsaturated polyester resin (hereinafter referred to as "resin A") is used as a base resin, and this "resin A"
An unsaturated polyester resin (hereinafter referred to as "resin B") is prepared by adding a polymerization inhibitor for gelling time adjustment, a polymerizable vinyl monomer or polymerization accelerator for viscosity adjustment, etc. to the unsaturated polyester resin (hereinafter referred to as "resin B"), which is used for molding. ) is mixed. If necessary, additives such as air blocking agents, inorganic fillers, ultraviolet absorbers, etc. may be mixed, but these are mainly used in "Resin A".
It is added in the process of manufacturing "Resin B" by blending a polymerization accelerator and the like. Cured products of such unsaturated polyester resins have excellent mechanical strength, chemical resistance, heat resistance, etc. Utilizing these properties, unsaturated polyester resins can be used for casting, painting, or decorative laminates. As a material for boats, ships, bathtubs, water tanks, septic tanks, chemical storage tanks, etc. It is effectively used in a wide range of fields. By the way, in preparing the above-mentioned "Resin A", polymerization inhibitors such as polyhydric phenols or quinones have traditionally been added. One reason is that the unsaturated polyester and the polymerizable This is to prevent gelation when mixed under heating to facilitate mutual dissolution with vinyl monomer, and to prevent gelation during long-term storage of "Resin A". It is to be. Then, this "Resin A" is mixed with a polymerizable vinyl monomer for viscosity adjustment and a polymerization accelerator to form "Resin B", and a radical polymerization initiator is added to the resulting "Resin B". A cured product is obtained by carrying out a curing reaction at room temperature or under heating. On this occasion,
In order to obtain "Resin B" with the desired gelation time in consideration of the molding operation time, it is necessary to adjust the amount of radical polymerization initiator and polymerization accelerator while considering the ambient temperature, or to inhibit polymerization. Methods such as adding agents have been used. However, when "Resin B" prepared in this way, that is, an unsaturated polyester resin containing a polymerization accelerator, is cured at room temperature, even if the same amount of radical polymerization initiator is used at the same ambient temperature, A significant drawback is that the gelation time of "Resin B" changes with the storage period. This type of change in gelation time over time poses various troublesome problems in terms of quality control during the production of unsaturated polyester resins and in terms of curing and molding workability, and its prevention is strongly desired. By the way. Various methods have already been proposed to prevent this gelation time from changing over time; for example,
No. 7135 discloses a method of adding monohydric or dihydric alcohols having 3 or less carbon atoms to an unsaturated polyester resin containing a polymerization accelerator, and JP-A-51-37148 discloses Methods of adding mono-, bis- or tris-hydroxyalkylamines are disclosed. The present inventors investigated these known methods in detail and found that the period from preparing the above-mentioned "resin A" to blending "resin B", that is, the storage period in the state of "resin A" It was discovered that there was a difference in the effectiveness of "Resin B" in preventing changes in gelation time over time. That is, when the storage period of "Resin A" is long, the above-mentioned known additives exhibit the effect of preventing the gelation time of "Resin B" from changing over time, but when the storage period is short, It is not effective, and practical problems still cannot be solved in terms of quality control during the production of unsaturated polyester resins and curing and molding workability. The present inventors have conducted intensive studies to solve the above-mentioned problems in the conventional technology, and have determined that the present inventors can solve the above-mentioned problems in the prior art, and have determined that the present inventors can solve the problems in the prior art, regardless of the length of the storage time of the "resin A" and regardless of the elapse of the storage time of the "resin B". The inventors have discovered that "Resin B" with a stable gel value time can be obtained without any oxidation, and have thus arrived at the present invention. That is, the present invention adds an arylantimony compound represented by the general formula () in an amount ranging from 0.0005 to 0.5 parts by weight to 100 parts by weight of a mixture of an unsaturated polyester and a polymerizable vinyl monomer,
The mixture is heated to 60 to 120°C and dissolved into the resulting unsaturated polyester resin (1), a polymerization promoter (2) consisting of an organic acid cobalt salt or a combination thereof and an amine, and an unsaturated polyester resin (2).
A polymerization accelerator-containing unsaturated polyester resin composition comprising 0.005 to 0.1 part by weight per 100 parts by weight of the following combined polymerization inhibitor (C), wherein the polymerization inhibitor (C) is trimethylhydroquinone. A mixture of D and a compound selected from the group consisting of hydroquinone, parabenzoquinone, toluhydroquinone and tertiarybutylcatechol, wherein D is 50 to 80% by weight, preferably
The combined mixture accounts for 60-75% by weight. formula (In the formula, R is a hydrogen atom or a methyl group) In the thus obtained unsaturated polyester resin composition containing a polymerization accelerator of the present invention, the unsaturated polyester and the polymerizable vinyl monomer are heated Even though they are mixed at the same time, they are stably dissolved in each other without gelation, and the obtained unsaturated polyester resin composition containing a polymerization accelerator exhibits stable curing regardless of the length of storage time. It shows performance. The unsaturated polyester used in the composition of the present invention refers to a mixture of an unsaturated dicarboxylic acid or its anhydride and a saturated dicarboxylic acid or its anhydride as the acid component, and a polyhydric alcohol as the alcohol component. It is a well-known polycondensate obtained by dehydration condensation reaction by a method known per se. Here, examples of the unsaturated dicarboxylic acid or its anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride,
Examples of the saturated dicarboxylic acid or its anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hettic acid, tetrahydrophthalic anhydride, adipic acid, and sebacic acid. I can do it.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, and neopentyl glycol. Examples of the polymerizable vinyl monomer to be mixed with this saturated polyester include styrene, chlorostyrene, vinyltoluene, (meth)acrylic acid, and derivatives thereof. In preparing the unsaturated polyester resin by the method of the present invention, the unsaturated polyester is in the range of 80 to 30 parts by weight, and the polymerizable vinyl monomer is in the range of 20 to 70 parts by weight, respectively. used. The arylantimony compounds represented by the general formula [] used in the present invention include triphenylstibine (C ₆ H ₅ ) ₃ Sb, tri(2-tolylfniel) stibine (2-CH ₃ C ₆ H ₄ ) ₃ Sb, Tori (3
-tolylphenyl) stibine (3-
Examples include CH ₃ C ₆ H ₄ ) ₃ Sb, which may be used alone or in combination of two or more compounds. This aryl antimony compound is
It is blended in an amount ranging from 0.0005 to 0.5 parts by weight, preferably from 0.005 to 0.1 parts by weight, based on 100 parts by weight of the mixture of unsaturated polyester and polymerizable vinyl monomer. In the present invention, the above-mentioned arylantimony compound contains a small amount of a known phenolic or quinone polymerization inhibitor, such as hydroquinone, di-
tert-butylhydroquinone, parabenzoquinone,
It may be used in combination with toluhydroquinone or an organic acid copper salt, such as copper naphthenate or copper octylate, and is particularly effective in combination with an organic acid copper salt. The amount of organic acid copper to be used is 0.0005 to 0.05 parts by weight based on metal weight, preferably 0.0005 to 0.05 parts by weight based on 100 parts by weight of the mixture of unsaturated polyester and polymerizable vinyl monomer.
It may be appropriately selected within the range of 0.0005 to 0.005 parts by weight. The amount of the polymerization inhibitor used is 0.005 parts by weight or less per 100 parts by weight of the unsaturated polyester resin. The unsaturated polyester resin thus obtained may contain organic acid cobalt salts, such as cobalt naphthenate and cobalt octylate, alone or as desired, together with aromatic amines, such as dimethylaniline, as a polymerization accelerator. Diethylaniline and phenyldiethanolamine are blended in combination, and the predetermined combination of polymerization inhibitors C is further blended. The polymerization accelerator-containing unsaturated polyester resin composition of the present invention may be prepared immediately after preparing the unsaturated polyester resin A, or the polymerization accelerator may be added to the stored unsaturated polyester resin A at a desired time. There is no substantial difference in curing performance depending on which formulation is used.
Furthermore, there is no substantial difference in curing performance even with the passage of storage days after the composition of the present invention is formulated. In either case, the composition of the invention is cured using known radical polymerization initiators. For the unsaturated polyester resin of the present invention,
If necessary, additives such as inorganic fillers such as calcium carbonate and clay, coloring pigments, mold release agents, thixotropic agents, and air blocking agents may be added, but the scope of the present invention may be affected by the use of these additives. It is not something that will be done. The present invention will be explained below with reference to Examples and Comparative Examples. Example 1 Preparation synthesis example of unsaturated polyester resin A reactor equipped with a stirrer, a thermometer, a nitrogen gas introduction pipe, and a partial refluxer with a thermometer attached to the top of the column was
888 g of phthalic anhydride, 392 g of maleic anhydride, and 836 g of propylene glycol were charged, heated to 210°C while flowing nitrogen gas, and subjected to a condensation reaction according to a conventional one-stage method to obtain an unsaturated product with an acid value of 25. Polyester was obtained. 1,920 g of this unsaturated polyester was cooled to 180°C, 0.89 g of triphenylstibine was added in advance, and dissolved in 1,030 g of styrene kept at 25°C. -”
Obtained 2948g. Synthesis Example 861 g of phthalic anhydride, 380 g of maleic anhydride, 836 g of propylene glycol, and 240 g of ethylene glycol were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a partial reflux device with a thermometer attached to the top of the column.
A condensation reaction was carried out according to a conventional one-step method while heating the mixture to 215° C. while flowing nitrogen gas to obtain an unsaturated polyester having an acid value of 23. 1840g of this unsaturated polyester was cooled to 180℃, and 0.57g of triphenylstibine and
0.11 g of copper naphthenate (copper content 5%) was dissolved in 995 g of styrene that had been added in advance.
2830 g of an unsaturated polyester resin containing 35% styrene ("Resin A-") were obtained. Comparative Synthesis Example 1 The formulation and operation were exactly the same as in Synthesis Example () except that 0.89g of triphenylstibine in Synthesis Example (1) was replaced with 0.19g of hydroquinone.
% of styrene-containing unsaturated polyester resin (Resin A
-1'') was obtained. Comparative Synthesis Example 2 A 35% styrene-containing unsaturated polyester was prepared using the same formulation and operation as in Synthesis Example (), except that 0.89g of triphenylstibine in Synthesis Example () was replaced with 0.19g of toluhydroquinone. A resin ("Resin A-2") was obtained. Comparative Synthesis Example 3 All the formulations and operations were carried out in the same manner as in Synthesis Example (), except that 0.57 g of triphenylstibine and 0.11 g of copper naphthenate in Synthesis Example () were replaced with 0.19 g of hydroquinone. % of styrene-containing unsaturated polyester resin (“Resin A-
3") was obtained. Example 2 "Resin A-1" obtained in Synthesis Example () was placed in a tin container, covered with a lid, and stored in a thermostatic chamber kept at 20°C. Desired amounts of this resin were taken out the day after synthesis, 14 days later, and 28 days later, respectively, to prepare polymerization accelerator-containing unsaturated polyester resins, which were used as samples for measuring changes in gelation time over time. An unsaturated polyester resin containing a polymerization accelerator was prepared according to the following recipe, placed in a glass container, sealed tightly, and stored in a constant temperature room at 20°C. "Resin A-" 400g Styrene 33g Trimethylhydroquinone 0.057g Toluhydroquinone 0.029g Dimethylaniline 0.22g Cobalt naphthenate (Co content 6%) 1.73g The sample prepared the day after synthesis was "Sample A--1",
Samples prepared after 14 days were given sample names such as "Sample A--14." Table 1 shows the gelation time of these polymerization accelerator-containing unsaturated polyester resin samples over time. In addition, the gelation time is
It was determined in accordance with JIS K6901 by adding 0.5 g of a 55% solution of methyl ethyl ketone peroxide (trade name "Permec N", manufactured by NOF Corporation) to 50 g of a sample, and measuring the time until gelation occurred. As is clear from Table 1, the unsaturated polyester resin containing a polymerization accelerator of the present invention has substantially no change in gelation time over time, has extremely stable curability, and is compounded with a polymerization accelerator. It can be seen that the gelation time of the unsaturated polyester resin before gelation changes only slightly over time. Comparative Example 1 Trimethylhydroquinone in Example 1
The same blending and operations as in Example 1 were carried out except that 0.086 g of tertiary butylcatechol was used in place of 0.057 g and 0.029 g of toluhydroquinone. The sample prepared the day after preparation was labeled as “Sample A-
1-1'', and the following names were given in the same manner. Table 1 also shows the measurement results of the gelation time of the unsaturated polyester resin sample containing a polymerization accelerator over time.

[Table] Example 3 and Comparative Example 2 Styrene was added to "Resin A-" obtained in Synthesis Example () to obtain an unsaturated polyester resin containing 40% styrene. Cobalt naphthenate (Co content 6%) and dimethylaniline were added to this unsaturated polyester resin at 0.5 PHR and 0.5 PHR, respectively.
It was added and dissolved at a rate of 0.05 PHR. After adding a specified amount of the compound listed in Table 2 and dissolving it, place it in a glass container, seal it tightly, and store it in a constant temperature room at 20°C. After a specified period of time, gelation time is measured and gelation occurs. The changes over time were tracked. The results are shown in Table 2. For comparison, the results obtained without using trimethylhydroquinone are also listed in Table 2 as Comparative Example 2.

[Table] Comparative Example 3 Styrene was added to each of "Resin A-1" to "Resin A-3" obtained in Comparative Synthesis Examples (1) to (3), and 40
% of styrene-containing unsaturated polyester resin was obtained. To this unsaturated polyester resin, cobalt naphthenate (Co content 6%) 0.5PHR, dimethylaniline 0.05PHR, trimethylhydroquinone
0.0133PHR and toluhydroquinone
0.0067 PHR was added and dissolved. These polymerization accelerator-containing unsaturated polyester resins were placed in a glass container, sealed tightly, and stored in a constant temperature room at 20°C.
Changes in gelation time over time were tracked. The results are shown in Table 3. In the table, "Sample 1" corresponds to "Resin A-1", and the same applies hereinafter.

【table】

Claims (1)

[Claims] 1. An arylantimony compound represented by the general formula () is added in an amount ranging from 0.0005 to 0.5 parts by weight to 100 parts by weight of a mixture of an unsaturated polyester and a polymerizable vinyl monomer. , the mixture at 60-120℃
0.005 to 0.005 to 100 parts by weight of the unsaturated polyester resin (I), a polymerization accelerator (B) made of an organic acid cobalt salt or a combination of this and an amine, and an unsaturated polyester resin (I) obtained by heating and dissolving each other.
An unsaturated polyester resin composition containing a polymerization accelerator, which contains 0.1 part by weight of the following combination of polymerization inhibitors. formula (In the formula, R is a hydrogen atom or a methyl group.) Polymerization inhibitor C: A mixture of trimethylhydroquinone and a compound selected from the group consisting of hydroquinone, parabenzoquinone, toluhydroquinone, and tertiarybutylcatechol. , Ni accounts for 50 to 80% by weight. 2. The polymerization accelerator-containing unsaturated polyester resin composition according to claim 1, which uses an unsaturated polyester resin obtained by combining an aryl antimony compound with an organic acid copper.