JPH0214941B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated polyester resin composition. More specifically, the present invention relates to a fast-curing unsaturated polyester resin composition containing an amine compound that has excellent storage stability and little change in low-temperature curing characteristics over time. Generally, unsaturated polyester resin compositions containing aromatic tertiary amines such as dimethylaniline,
By using diacyl peroxide such as benzoyl peroxide as a curing agent, it cures extremely quickly even at low temperatures, so it is widely used as a low-temperature, rapid-curing unsaturated polyester resin composition. However, such amine compound-containing unsaturated polyester resin compositions have poor storage stability, and therefore are currently subject to restrictions on the conditions of use. The inventors of the present application have conducted various studies to improve these points, and as a result, they have developed an unsaturated polyester that is quick-curing at low temperatures, has virtually no change in curing characteristics over time, and has good storage stability. This led to the development of a resin composition. That is, the present invention consists of an unsaturated polyester (A), a polymerizable monomer (B), an amine compound (C), a tin compound (D), and a polymerization inhibitor (E), and the unsaturated polyester (A)
has an acid value of 12 or less, the amine compound (C) is at least one selected from the group consisting of compounds represented by the following general formula () or general formula (), and is polymerizable with the unsaturated polyester (A). The sum of monomers (B) is
100 parts by weight, the ratio of the amine compound (C) is 0.01 to 2.0 parts by weight, the tin compound (D) is 0.05 to 3.0 parts by weight, and the polymerization inhibitor (E) is 0.005 to 0.5 parts by weight. This invention relates to a saturated polyester resin composition. (Note) General formula () (However, in the formula, R ₁ is -H, -CH ₃ , -OCH ₃ or -
_OC2H5 , _R2 represents _{a C1-4} alkyl group, _{and R3 is (-C2H4O ) -n ( -C3H6O} ) _-oH (however _{, m} and n are integers from 0 to 5, respectively, and m+n=1 to 5
The (-C ₂ H ₄ O)- unit and the (-C ₃ H ₆ O)- unit may be randomly bonded. ). ) General formula () (However, in the formula, R ₄ is -H, -CH ₃ , -OCH ₃ or -
OC ₂ H ₅ , R ₅ and R ₆ are both (-
_{( - _ _ _ _}
C ₂ H ₄ O)-units and (-C ₃ H ₆ O)-units may be randomly bonded. ), and R ₅ and R ₆ may be the same or different. ) The unsaturated polyester (A) used in the present invention is
It is obtained from an acid component that is essentially an α,β-unsaturated dibasic acid and optionally an aromatic saturated dibasic acid or an aliphatic saturated dibasic acid, and an alcohol component such as a glycol or an epoxidized product. be. Of course,
A monobasic acid or a trivalent or higher polybasic acid may be used in place of a portion of the dibasic salt, and a monovalent or trivalent or higher valence alcohol may be used in place of a portion of the glycol or epoxy compound. . The acid value of the unsaturated polyester (A) must be 12 or less. When the acid value exceeds 12, the change in low temperature curing properties over time becomes large. Setting the acid value of the unsaturated polyester (A) to 12 or less can be achieved by selecting the ratio of the raw acid component and alcohol component. As the polymerizable monomer (B), those commonly used for unsaturated polyester resins, such as styrene, vinyltoluene, α-methylstyrene, diallyl phthalate, and methyl methacrylate, can be used. What is unsaturated polyester (A) and polymerizable monomer (B)?
This constitutes an unsaturated polyester resin, and the ratio of the two can be in the range of 10:90 to 90:10 by weight. The amine compound (C) is at least one type selected from the group consisting of compounds represented by the above general formula () or general formula (). Compounds represented by the general formula () include N-methyl-N-β-hydroxyethylaniline, N-ethyl-N-β-hydroxyethylaniline, N-butyl-N-β-hydroxyethylaniline, and N-ethyl -N-β-hydroxyethyl-m-toluidine, N-ethyl-
N-β-hydroxyethyl-p-toluidine, N
-Ethyl-N-β-hydroxypropylaniline, N-ethyl-N-β-hydroxypropylaniline, N-ethyl-N-β-hydroxypropyl-p-toluidine, N-ethyl-N-β-hydroxyethyl-p - Anisidine, etc. In addition, as a compound represented by the general formula (), N,N-di(β-hydroxyethyl)-
Aniline, N,N-di(β-hydroxyethyl)
-m-toluidine, N,N-di(β-hydroxyethyl)-p-toluidine, N,N-di(β-hydroxyethyl)-p-anisidine, N,N-di(β-hydroxyethyl)-p -phenetidine,
N,N-di(β-hydroxypropyl)-aniline, N,N-di(β-hydroxypropyl)-p
-toluidine, N,N-di(β-hydroxypropyl)-m-toluidine, N,N-di(β-hydroxypropyl)-p-anisidine, and the like. The amount of amine compound (C) used is based on the total of unsaturated polyester (A) and polymerizable monomer (B) being 100 parts by weight.
The ratio ranges from 0.01 to 2.0 parts by weight. If it is less than 0.01 part by weight, it will not cure quickly during curing, and
If a large amount exceeding 2.0 parts by weight is used, storage stability will deteriorate. Examples of tin compounds (D) include inorganic compounds such as hydroxides, carbonates, sulfates, and borates; organic acid salts such as naphthenates, octenoates, and aromatic carboxylates;
Examples include organic tin compounds such as dibutyltin oxide, and one or two of these can be used.
More than one species can be used. The amount of tin compound (D) used is
The total of (A) and polymerizable monomer (B) is 100 parts by weight.
The ratio ranges from 0.05 to 3.0 parts by weight. If it deviates from this range, the storage stability of the resulting unsaturated polyester resin composition will deteriorate. As the polymerization inhibitor (E), hydroquinone, p-
benzoquinone, tetrachlorobenzoquinone, t-
Examples include quinones such as butylhydroquinone; catechols such as pt-butylcatechol; and phenols such as 2,4-dinitrophenol; one or more of these may be used. . The amount of polymerization inhibitor (E) used is
The total of (A) and polymerizable monomer (B) is 100 parts by weight.
The ratio ranges from 0.005 to 0.5 parts by weight. If the amount is less than 0.005 part by weight, storage stability will be poor, and if the amount is more than 0.5 part by weight, it will be difficult to cure during curing. The unsaturated polyester resin composition of the present invention thus contains the unsaturated polyester (A) and the polymerizable monomer.
(B), an amine compound (C), a tin compound (D), and a polymerization inhibitor (E) in specific ratios, and these components work together inseparably to achieve the excellent effects of the present invention. It is something that demonstrates the. These components may be mixed in any order, and any mixing method and equipment commonly used in the industry of unsaturated polyester resins can be used. Further, the tin compound (D) and the polymerization inhibitor (E) may be added in whole or in part in the step of producing the unsaturated polyester (A) from the acid component and the alcohol component. The thus obtained unsaturated polyester resin composition of the present invention may contain fillers such as calcium carbonate, clay, tarta, silica sand, glass powder, etc.; coloring agents; Modifiers; stabilizers such as copper compounds and iron compounds can also be added and used. To cure the unsaturated polyester resin composition of the present invention, organic peroxide catalysts commonly used in the unsaturated polyester resin industry can be used. Among these, when diacyl organic peroxides such as benzoyl peroxide are used,
It exhibits excellent low-temperature, rapid curing properties and can exhibit the characteristics of the unsaturated polyester resin composition of the present invention. Further, the unsaturated polyester resin composition of the present invention exhibits excellent storage stability, and its low temperature curing properties show little change over time, even though it contains an amine compound. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Incidentally, parts and percentages in the examples represent parts by weight and percentages by weight unless otherwise specified. Reference Example 1 A ratio of 0.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, 0.5 mol of propylene glycol, and 0.6 mol of ethylene glycol was charged into a four-necked flask, and a dehydration condensation reaction was carried out at 200°C in a nitrogen stream as usual to determine the acid value. 11 unsaturated polyesters () were obtained. Reference Example 2 A 4-necked flask was charged with a ratio of 0.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, 0.5 mol of propylene glycol, and 0.65 mol of ethylene glycol, and 0.1 part of dibutyltin oxide per 100 parts of the raw material charged. A dehydration condensation reaction was carried out at 200° C. in a nitrogen stream in a conventional manner to obtain an unsaturated polyester (2) having an acid value of 5. Reference Example 3 A four-necked flask was charged with a ratio of 0.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, 0.5 mol of propylene glycol, and 0.7 mol of ethylene glycol, and 0.1 part of dibutyltin oxide per 100 parts of the raw material charged. A dehydration condensation reaction was carried out in a nitrogen stream at 200°C in a conventional manner to obtain an unsaturated polyester (2) having an acid value of 2.5. Reference Example 4 A ratio of 0.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, 0.5 mol of propylene glycol, and 0.55 mol of ethylene glycol was charged into a four-necked flask, and the acid value was determined by dehydration condensation reaction at 200°C in a nitrogen stream as usual. 30 unsaturated polyesters () were obtained. Reference Example 5 Unsaturated polyester obtained in Reference Examples 1 to 4 ()
Unsaturated polyester resin compositions (A) to (N) having the compositions shown in Table 1 were obtained using unsaturated polyester resin compositions (A) to (N), respectively.

【table】

[Table] Example 1 Unsaturated polyester resin composition obtained in Reference Example 5
Using (A) to (N), storage stability, low-temperature curing properties, and changes over time in low-temperature curing properties were investigated. Second result
Shown in the table. In addition, each characteristic was investigated as follows. (Storage stability) Put each unsaturated polyester resin composition into a test tube with an outer diameter of 12 mmφ and a height of 120 mm until the height of the upper space is 5 mm, cover with aluminum foil, and then seal with cellophane tape. Leave it in a constant temperature bath at 60℃ for 24 hours.
The test tube was inverted every hour and the number of days until bubbles stopped rising was measured. (Low temperature curing properties) Take 30g of each unsaturated polyester resin composition in a polypropylene cup, cool it in a 5℃ cold water bath, add 6% of BPO50% paste to the unsaturated polyester resin composition, and mix for 30 seconds. After that, the height is 100mm in a test tube with an outer diameter of 18mmφ and a height of 180mm.
Add the catalyst mixed resin composition until
After inserting the thermistor thermometer described in K6911,
The test tube was immersed in a 5°C cold water bath and the exothermic curve was taken, and the gelation time (hereinafter referred to as GT), minimum curing time (hereinafter referred to as MCT), and maximum exothermic temperature (hereinafter referred to as MET) were measured. ) was measured. The reactivity was also calculated. In addition, GT, MCT, and reactivity are as follows. GT: The time required for the exothermic curve to reach 10°C from immediately after adding the catalyst and mixing for 30 seconds (hereinafter referred to as the start of measurement) is expressed in minutes. MCT: The time required from the start of measurement to reach the maximum exothermic temperature (MET) in minutes. Reactivity: Expressed as MET (°C)/MCT (min) - GT (min). (Change in low-temperature curing properties over time) The low-temperature curing properties of each unsaturated polyester resin composition stored at room temperature were examined immediately after preparation of the resin composition, 10 days later, 40 days, or 50 days later.

【table】

[Table] As shown in Table 2, Examples 1 to 10 all had excellent storage stability and good low-temperature curing properties, with little change over time in the low-temperature curing properties. On the other hand, it is clear that Comparative Examples 1 and 3 have poor storage stability, and Comparative Examples 2 and 4 have low reactivity. Reference Example 6 Using the unsaturated polyesters () and () obtained in Reference Examples 1 and 3, unsaturated polyester resin compositions (O) to (Z) having the compositions shown in Table 3 were obtained, respectively.

【table】

[Table] Example 2 Using the unsaturated polyester resin compositions (O) to (Z) obtained in Reference Example 6, the storage stability, low-temperature curing properties, and aging changes in low-temperature curing properties were measured in the same manner as in Example 1. I looked into it. The results are shown in Table 4.

【table】

【table】

Claims (1)

[Claims] 1. Unsaturated polyester (A), polymerizable monomer (B), amine compound (C), tin compound (D), and polymerization inhibitor (E)
, the unsaturated polyester (A) has an acid value of 12 or less, and the amine compound (C) is at least one selected from the group consisting of compounds represented by the following general formula () or general formula (), The total of unsaturated polyester (A) and polymerizable monomer (B) is 100 parts by weight, and amine compound (C) is 0.01 to 2.0 parts by weight, tin compound
(D) is 0.05 to 3.0 parts by weight and polymerization inhibitor (E) is 0.005
An unsaturated polyester resin composition characterized in that the proportion is ~0.5 parts by weight. (Note) General formula () (However, in the formula, R ₁ is -H, -CH ₃ , -OCH ₃ or -
_OC2H5 , _R2 represents _{a C1-4} alkyl group, _{and R3 is (-C2H4O ) -n ( -C3H6O} ) _-oH (however _{, m} and n are integers from 0 to 5, respectively, and m+n=1 to 5
The (-C ₂ H ₄ O)- unit and the (-C ₃ H ₆ O)- unit may be randomly bonded. ). ) General formula () (However, in the formula, R ₄ is -H, -CH ₃ , -OCH ₃ or -
OC ₂ H ₅ , R ₅ and R ₆ are both (-
_{( - _ _ _ _}
C ₂ H ₄ O)-units and (-C ₃ H ₆ O)-units may be randomly bonded. ), and R ₅ and R ₆ may be the same or different. )