KR900006526B1 - Unsaturated polyester curable resin composition - Google Patents

Abstract

Compsn. comprises both block copolymer segment contg. polyester part and liq. rubber type cpd. and unsatd. polyester segment. The liq. rubber type cpd. is polybutadiene type cpd. The polyester part is formed by conde sing orgainc dicarboxylic acid anhydride and 1,2- epoxide alternately to the carboxyl gp. or hydroxyl gp. in the liq. rubber type cpd. The unsatd. polyester resin compsn. can be used for sheet moulding cpd. or block moulding cpd. and also comprises polymeric monomer, filler, hardening catalyst, releasing agent and reinforcing fiber.

Description

Unsaturated Polyester Curable Resin Composition

The present invention relates to an unsaturated polyester curable resin composition. Unsaturated polyester curable resin compositions are widely used in the wet mold method such as the so-called matched die method, the RIM method of the resin injection method, and the like, representing SMC (plate forming material), BMC (block forming material) and the like.

By the way, it is known that thermosetting unsaturated polyester resin has a large mold shrinkage at the time of molding hardening, and other thermoplastics are added to this unsaturated polyester resin for further improvement of physical properties, for example, impact resistance, for improving the dimensional accuracy of the molded product. Adding a high molecular compound is widely performed. However, in the composition of the degree to which both are simply mixed, the surface of the molded article is remarkably poor, and the degree of shrinkage reduction and impact resistance improvement is also very bad. Moreover, in general, such compositions are poor in moldability because they do not have sufficient commercial or dispersion stability. Therefore, there is a strong demand for the emergence of an unsaturated polyester curable resin composition which has sufficient commercial or dispersion stability, good molding workability, and which can give the molded article excellent physical properties such as surface properties, low shrinkage, impact resistance, and the like.

The present invention relates to an unsaturated polyester curable resin composition according to this request.

In the polymer compound molecule added to the thermosetting unsaturated polyester resin, a carbonic acid group is present in the molecule, and the carbonic acid group and the terminal free carbonic acid group of the thermosetting unsaturated polyester resin are bonded through an alkaline earth metal oxide such as magnesium oxide or a hydroxide thereof. have. In this case, a partial effect is recognized if the polymer compound to be added is a copolymer of beta or acrylic acid and methyl methacrylate, vinyl acetate or styrene. However, the composition by this kind of means is still far from implementing the above-described physical property improvement on the molded article.

On the other hand, it is also conceivable to use a diene-based polymer as a polymer compound to be added for the purpose of improving the impact resistance of the molded article, and to use it as a conventional means as described above. This occurs and other physical properties are also poor, and there is no effect of having a carboxyl group present in the diene polymer. The diene-based polymer itself having a carboxyl group is dissolved in a styrene monomer, which is a monomer component used in an unsaturated polyester curable resin composition, but when it is coexisted with, for example, α, β-ethylenically unsaturated polyester, it is separated into a layer quickly. do. The diene-based polymer having a carboxyl group is so compatible with the thermosetting unsaturated polyester resin that even if it adds such as magnesium oxide to them there is a significant amount of part separated before both the salt-bonding, which is eventually such a composition It is presumed that the cause of failure to improve the physical properties of the molded product obtained in

Therefore, a composition containing a block copolymer of a styrene-based polymer has been proposed to improve the compatibility or dispersibility with respect to a thermosetting unsaturated polyester resin (Japanese Patent Laid-Open No. 53-74592, Japanese Patent Laid-Open No. 60-60). 99158), which is to some extent to improve the compatibility or dispersibility, but in addition to the low shrinkage of the moldings obtained from this composition, in particular impact resistance, because the use of a block copolymer of a styrene-based polymer that is essentially tough Significantly behind.

The present invention solves the conventional problems such as papermaking, to provide a new unsaturated polyester curable resin composition that satisfies the above request.

Thus, the present inventors have diligently studied from the above point of view, and found that a composition containing a block copolymer which shares a polyester portion and a liquid rubber compound portion as a segment in a thermosetting unsaturated polyester resin is found to be most suitable. It was completed. That is, this invention relates to the unsaturated polyester curable resin composition characterized by containing both a block copolymer and unsaturated polyester which share a polyester part and a liquid rubber type compound part as a segment which comprises it.

In the present invention, the block copolymer is a starting material of a liquid rubber compound having one or two or more active hydrogen groups such as hydroxyl groups or carboxyl groups in a molecule, and an organic dicarboxylic anhydride and 1,2-epoxide in the presence of a catalyst. Alternately reacting to form a condensation of a polyester ring through an active hydrogen group of the liquid rubber compound or a liquid rubber compound having one or two or more hydroxyl groups in the molecule as a starting material and ε-aliphatic lactone in the presence of a catalyst The ring-opening polymerization can be obtained by stabilizing industrially by forming a polyester ring through the hydroxyl group of the liquid rubber compound, but it is also possible to connect the polyester ring to the liquid rubber compound directly or indirectly using a crosslinking agent.

The important point of the block copolymer of the present invention is to share a polyester part and a liquid rubber compound part as segments constituting the block copolymer, and the present invention specifically limits a method for producing a block copolymer or other structures. no. For example, the active hydrogen group present in the liquid rubber compound may be in the ring or at the terminal of the compound, may be directly connected to the ring, or may be indirectly connected through any atom. In addition, the liquid rubber compound constituting the segment does not cause stereoisomerism or structural isomerism due to differences in polymerization methods such as radical polymerization, ion polymerization, and living polymerization.

The monomer diene compound constituting the liquid rubber compound is butadiene, isoprene, chloroprene, 1,3-pentadiene, and the like, and examples of the liquid rubber compound that can be advantageously used in the present invention include α, ω-1,2-polybutadiene glycol. (Nisso PB-G series), α, ω-1,2-polybutadiene dicarboxylic acid (Nisso PB-C series), α, ω-1,2-polybutadiene terminal maleic acid half ester (Nisso PB-GM series, or more Three points are made by Nippon Kogyo Co., Ltd.), terminal carboxyl-modified 1,4-polybutadiene (Hycar CTB series, manufactured by Sanji Kogyo Co., Ltd. or BF Goodrich Co., Ltd.), terminal hydroxyl-modified 1,4-polybutadiene (Poly-bd R- 45M or R-45HT, manufactured by Iko Chemical Co., Ltd., or Ako Chemical Co., Ltd.), and those partially or completely hydrogenated, for example, hydrogenated α, ω-1,2-polybutadiene glycol ( Nisso PB-GI series), hydrogenated α, ω-1,2-polybutadiene dicarboxylic acid (Nisso PB-CI series, two or more points And Nitrogen Co., Ltd.), but also those obtained by adding alkylene oxide to the carboxyl group of the carboxy-modified liquid rubber compound, and hydroxy alkyl ester, and the epoxy group of the epoxy-modified liquid rubber compound to water, alcohol or monovalent organic acid. It is also possible to disclose that the reaction is carried out to ring-open an epoxy group.

On the other hand, regarding the formation of the polyester ring in the liquid rubber-based compound, in the above production example in which the organic dicarboxylic acid anhydride and the 1,2-epoxide are reacted, examples of the organic dicarboxylic acid anhydride include succinic anhydride, maleic anhydride, alkenyl amber anhydride, and the like. Aromatic dicarboxylic acid anhydrides such as aliphatic dicarboxylic acid anhydride, phthalic anhydride, naphthalene dicarboxylic acid anhydride, cycloaliphatic dicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride, alicyclic dicarboxylic acid anhydrides such as end methylene cyclohexene dicarboxylic acid anhydride have. Moreover, in the said manufacture example, ethylene oxide, a propylene oxide, a 1, 2- butylene oxide etc. are mentioned as 1, 2- epoxide. Furthermore, in the same said preparation example, tetraalkyl quaternary ammonium salts, such as lithium halides, such as lithium chloride and a brittle lithium, tetramethylammonium bromide, tributylmethylammonium bromide, and tetrapropylammonium chloride, are mentioned. On the other hand, in the above-mentioned production example of ring-opening polymerization of ε-aliphatic lactone with respect to the formation of a polyester ring in a liquid rubber-based compound, ε-capurolactone is exemplified as ε-aliphatic lactone. In addition, as a catalyst used for sequential ring-opening polymerization of ε-aliphatic lactone to a hydroxyl group present as a functional group of a liquid rubber-based compound, the course polymerization reaction is described in Volume 7 Ring Opening Polymerization (II) (published on page 108). The same anionic polymerization catalyst, coordination anion polymerization catalyst, cationic polymerization catalyst and the like can be used. In particular, titanium-based catalysts such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, and tin-based catalysts such as dibutyltin oxide, tin octylate and first tin chloride are advantageous.

Needless to say, the present invention is not limited to any of the above examples.

The basic idea of the present invention is to use a block copolymer in which a polyester is bonded as a segment to the liquid rubber compound in order to improve compatibility or dispersibility with the thermosetting unsaturated polyester resin while utilizing the inherent properties of the liquid rubber compound.

In the said block copolymer, the content of the polyester segment can be suitably selected from the relationship with the content of the thermosetting unsaturated polyester resin used together. Generally, as polyester segments, poly (propylene glycol phthalate), poly (ethylene glycol phthalate, succinate), poly (butylene glycol succinate) and the like are relatively widely compatible with various thermosetting unsaturated polyester resins and have good dispersibility. In some cases, it is also effective to have an unsaturated group based on α, β-ethylenically unsaturated dicarboxylic acid in the polyester segment.

Tests on the compatibility or dispersibility of the thermosetting unsaturated polyester resin will be described later. However, even if there is a slight lack of compatibility or dispersibility of the resin and the block copolymer, the terminal group of the polyester segment ring is carboxylic acid type. Sufficient compatibility or dispersibility can be obtained by adding magnesium oxide or magnesium hydroxide as the thickener. In the same manner, when the terminal group of the polyester segment ring is in the hydroxyl group type, diisocyanates such as methylene-di (4-phenylisocyanate) can be sufficiently used as a thickener to sufficiently compensate for the lack of compatibility or dispersibility. In addition, the content of the polyester segment in the block copolymer is also involved in compatibility or dispersibility with the thermosetting unsaturated polyester resin. In general, increasing the content of the polyester segment increases the compatibility or dispersibility, and conversely, lowers the compatibility or dispersibility. When the main purpose of co-existing the block copolymer with the thermosetting unsaturated polyester resin is to improve the impact resistance and surface properties of the molding, as long as the copolymerization ratio of polybutadiene or other monomers is possible in the liquid rubber compound part of the block copolymer. The low polybutadiene-based one is preferable, and in this case, the polyester segment content in the block copolymer is reduced as much as possible while considering compatibility or dispersibility with the thermosetting unsaturated polyester resin. Further, when the main purpose is to improve the hot strength of the molding, that is, to lower the temperature dependence of the bending and tensile strength of the molding, and to maintain the surface properties of the molding, the content of polyester segments in the block copolymer is slightly increased, or In addition, it is preferable to have an unsaturated group in the polyester segment.

In general, the polyester segment content in the block copolymer used in the composition according to the present invention is preferably 10 to 60% by weight.

In the present invention, the block copolymer is usually a 25-40% polymerizable monomer, for example, a styrene monomer solution, and is usually used by mixing 20-50% of the solution with respect to the thermosetting unsaturated polyester resin. Of course, depending on the type of the block copolymer, it is not necessary to dissolve the thermosetting unsaturated polyester in a polymerizable monomer such as styrene monomer before adding it to the resin, and a required amount of the polymerizable monomer is added thereto to the thermosetting unsaturated polyester resin. You may add a block copolymer to the.

Thermosetting unsaturated polyester resin that can be advantageously used in the composition according to the present invention is a conjugated diene compound of the unsaturated group contained in the condensed polyester of α, β-ethylenically unsaturated dicarboxylic acid and glycols or its condensed polyester Although it is a novolak-type unsaturated polyester or vinyl ester type unsaturated polyester besides the added modified and unsaturated polyester, this invention does not add a restriction | limiting to the content of a thermosetting unsaturated polyester resin. As the solvent contained in these resins, there are polymerizable monomers such as styrene, methacrylic acid ester, and diaryl phthalate, but usually styrene is used, and a solid content of 60 to 65% is easy to use.

As described above, the solvent in the composition according to the present invention is usually a styrene monomer, but in order to impart flame retardance to the molded article, part or all of the solvent may be used as a crawl styrene monomer. Moreover, in order to improve the weather resistance and gloss of a molding, a part of styrene monomer can also be made into methyl methacrylate. In addition, various polymerizable monomers can be present in the composition, depending on the purpose.

The simplest composition of the composition according to the invention is a mixture of a block copolymer as described above with a thermosetting unsaturated polyester resin. When the molding method is a matched die method, a resin indentation method (RIM method), a hand lay-up method, a filament and an inflation method, those which have been added with an appropriate curing catalyst or a microadditive such as a release agent are used for this simplest composition. Therefore, you may add a conventionally well-known high molecular compound. As premix molding materials such as SMC and BMC, in addition to so-called resins such as calcium carbonate as fillers, alkali earth metal oxides, hydroxides or diisocyanates as thickeners, metal soaps as release agents, glass fibers as reinforcing agents, etc. However, their mixing ratios and mixing methods are not particularly different from those of conventionally known compositions.

Hereinafter, in order to make the present invention more specifically, reference examples and examples of the preparation of the block copolymer are given, but the present invention is not limited thereto. Changes and modifications within the basic idea based on the present invention described above including these examples are included in the present invention.

[Manufacture Reference Example 1]

52.3 g (0.35 mole) of phthalic anhydride, 82.5 g (0.825 mole) of amber anhydride, 0.7 g of lithium chloride as a catalyst, and α, β-1,2-polybutadiene glycol (Nisso PB-G 1000, average molecular weight 1430, Nippon Corporation) First, 715 g (0.5 mol) was placed in an autoclave, the reactant was replaced with nitrogen gas, heated to 130 DEG C while stirring, and then 42.7 g (0.74 mol) of propylene oxide was pressed in for 1 hour. After aging at 130 ° C. for 2 hours, the reaction was completed to obtain 890 g of a pale yellow transparent slime product. The molecular weight of the polybutadiene-polyester block copolymer obtained here was 1786 (calculated value, the following molecular weight was computed value), the ratio of the polyester segment was 20.0 weight% (following% weight%), acid value 27, and hydroxyl value 38.

[Production Reference Example 2]

800 g (0.448 mol) of the block copolymer obtained in Reference Example 1 and 54.2 g (0.54 mol) of anhydrous amber acid were placed in a flask and reacted for 2 hours in a nitrogen stream at 120-125 ° C. After the contents were cooled to 50 ° C., 214 g of styrene monomer was added to adjust a styrene solution containing 80% by weight of the block copolymer. The acid value 50.7 and hydroxyl value of the styrene solution containing this block copolymer were 1.9, and the polybutadiene-polyester block copolymer in which the terminal of the polyester ring was carboxy-modified was obtained.

[Production Reference Example 3]

130.2 g (1.3 mole) of amber anhydride, 105.2 g (0.71 mole) of phthalic anhydride, 35.8 g (0.365 mole) of maleic anhydride, 1,430 g (1 of α, β-1,2-polybutadiene glycol (as described in Production Reference Example 1) Mole) and 0.6 g of lithium chloride were placed in an autoclave, the reaction system was replaced with nitrogen gas, heated to 130 ° C. under stirring, and 86.3 g (1.49 mole) of propylene oxide was indented at a temperature of 125-130 ° C. over 40 minutes. It was. Aged at this temperature for 2 hours and the reaction was completed to obtain a polybutadiene-polyester block copolymer. After cooling, 447 g of styrene monomer was added thereto, diluted to dissolve, and a styrene solution containing 80% by weight of the block copolymer was adjusted.

The polybutadiene-polyester block copolymer obtained here had a molecular weight of 1787, a proportion of 20% of a polyester ester segment portion, an acid value of 25, 6, and a hydroxyl value of the styrene solution.

[Production Reference Example 4]

98 g (1 mol) of maleic anhydride, 148 g (1 mol) of phthalic anhydride, and 159.6 g (2.1 l mol) of propylene glycol were heated and reacted at 215 ° C in a nitrogen stream, and the condensation reaction was stopped when the acid value of the reactant became 60. An unsaturated polyester was obtained. The number average molecular weight of this unsaturated polyester was 754, and the hydroxyl value was 89.3.

151 g (0.2 mole) of unsaturated polyester and 300 g (0.1 mole) of α, β-1,2-polybutadiene glycol (Nisso PB-G 3000, number average molecular weight 3000, manufactured by Nippon Corporation) were dissolved in 1000 ml of toluene. 50 g (0.2 mol) of methylene-di (4-phenylisocyanate) was added, and it was made to react at 50 degreeC for 1 hour, stirring. Toluene was filtered off from the reaction under reduced pressure to give a yellow viscous liquid product.

What is obtained here is a block copolymer mainly bridge | crosslinked with the methylene di (4-phenylisocyanate) hydroxyl groups in each of unsaturated polyester and (alpha), (beta) -1, 2- polybutadiene glycol. Some of the by-products include crosslinked unsaturated polyesters or polybutadiene glycols, but in the present invention, a block copolymer obtained by removing these by-products from the reaction mixture may be used or the reaction mixture may be used as it is. The purified block copolymer had an average of two polyester segments per polybutadiene segment connected through urethane bonds, and the proportion of polyester segments was 30%.

Example 1

The 33% styrene solutions of the two block copolymers obtained in Production Reference Examples 1 and 2 were adjusted, and the compatibility and dispersibility with the following thermosetting unsaturated polyester resins were tested for each solution. The thermosetting unsaturated polyester resins used were five kinds of Eupica 7507 (manufactured by Nippon Yupica), Polyset 9120, Polyset 9107, Polyset 2212, and Polyset 6200 (four of which are manufactured by Nippon Chemical Co., Ltd.). Only the combination of the block copolymer of the Preparation Reference Example 2 and the polyester 9107 confirmed phase separation of about 10% at 24 hours, but none of the other combinations showed a phase separation without a thickener.

Therefore, it was expected that the composition of the above combinations would give a beautiful molded product having a uniform gloss on the surface by various molding methods. Thus, for each of the two block copolymers, 60 parts of Eupica 7507, 40 parts of Rashari-butylpabenzoate and 3.0 parts of zinc stearate were placed in a Bamboberry mixer for 40 parts of 33% styrene solution, respectively. After adding more calcium carbonate powder to make it more uniform, 60 parts of 1 / 2-inch-long glass fibers were added, and after 1 minute, the Bambory mixer was stopped to make a premix. Although this premix was based on the composition of this invention, it was shape | molded at the mold temperature of 140 degreeC, and the molded article with uniform surface gloss was obtained, and the shaping | molding shrinkage rate is the case where the block copolymer of manufacture reference example 1 is used. It was 0.005% when the block copolymer of 0.004% and manufacture reference example 2 was used.

On the other hand, all of the premixes made under the same conditions are known except that α, β-1,2-polybutadiene glycol (described in Preparation Reference Example 1) is used instead of the block copolymer, but the surface of the molded article is glossy. The class was remarkable and bad to see.

Example 2

A 33% styrene solution of the block copolymer obtained in Production Reference Example 3 was adjusted, and 60 parts of Poly 9 9120, 3 parts of zinc stearate, 1.5 parts of Tashari-butylpabenzoate, 140 parts of calcium carbonate powder, and 40 parts of this solution were used. After mixing 0.3 parts of parabenzokinone uniformly, 2 parts of magnesium oxide was added, and the composition for SMC containing 10% of 1-inch-long glass fiber was produced immediately. This composition was based on the present invention, which was molded at a mold temperature of 140 ° C., although the surface of the molded article was slightly blurred, but the glossiness was uniform, the mold shrinkage was 0.06%. On the other hand, except for using α, β-1,2-polybutadiene glycol (as described in Production Reference Example 1) instead of the block copolymer, all the compositions for SMC made under the same conditions are known, The surface was marked with gloss spots and the flow pattern was confirmed, and the mold shrinkage was -0.20%. In this case, the dope stability before the addition of magnesium oxide was also poor and apparent phase separation, and it became clear that industrial operation was also very difficult in this respect.

Example 3

To 500 parts of 33% styrene solution of each of the two block copolymers obtained in Production Reference Example 1 and 2, 500 parts of polylite PC-670 (manufactured by Daiko-Ink Ink Company) was added as a thermosetting unsaturated polyester resin, and naphthalic acid was again added. 60 parts of cobalt were melt | dissolved and the liquid of viscosity 830 centipoise was obtained. When the solution was fed into a resin injection mold (known as RIM or RTM) in which a glass mat was set in advance, acetyl acetone peroxide was pumped into the mold while mixing to be 1% of the feed liquid. At that time, the liquid inlet of the mold was 20 mm in diameter, and the mold temperature at the time of feeding was 25 ° C. After 2 hours, the mold temperature started to rise with the combined heat and reached a maximum temperature of 70 ℃ in 3 hours. After another 3 hours, the mold was opened and the molding was removed. The appearance of the moldings was the same shape, especially no glossiness, and the surface was smoother and the glass fiber was hardly observed compared to the moldings obtained in the same manner except that the block copolymer was not used.

Example 4

The 33% styrene solution was adjusted using the block copolymer obtained by the manufacture reference example 4 as it was unpurified. 40 parts of this solution, 60 parts of polyset 9127 (manufactured by Nippon Kasei Co., Ltd.) and 1.5 parts of Tashari-butylpabenzoate as a thermosetting unsaturated polyester resin were mixed uniformly, and MDI5 part was added to the dope mixed with 140 parts of calcium carbonate powder. Immediately upon addition, a composition for SMC with 27% of 1 inch long glass fibers was made. This composition is based on the present invention, which was molded into a plate at 145 ° C. The surface of the molding was yellowish brown due to the MDI thickening method, but the gloss was slight, the mold shrinkage was 0.03%, and the impact resistance (with the notch) was 16.5 feet / lbs / inch.

In contrast, all of the moldings obtained under the same conditions except for using polystyrene grafted unsaturated polyester (described in Example 1 of Japanese Patent Application Laid-Open No. 60-99158) instead of the block copolymer in the present invention. Although the surface was slightly low in color, the appearance of gloss plaque or glass fiber was confirmed to be poor, and in this respect, a large fact of the mold shrinkage was observed, and the impact strength (with the notch) was 12.0 pounds / lb.

[Production Reference Example 5]

52.3 g (0.35 mole) of phthalic anhydride, 82.5 g (0.825 mole) of amber anhydride, 0.7 g of lithium chloride as a catalyst and hydrogenated α, β-1,2-polybutadiene glycol (Misso PB-GI 1000, molecular weight 1400, oxo (6), 700 g (0.5 mole) manufactured by Nippon Shoku Co., Ltd.) were placed in an autoclave, the reaction system was replaced with nitrogen gas, heated to 130 ° C. with stirring, and then 42.7 g (0.74 mole) of propylene oxide was pressed in for 1 hour. After aging at 130 ° C. for 2 hours, the reaction was completed to give 875 g of a pale yellow transparent slime product. The molecular weight of the hydrogenated polybutadiene-polyester block copolymer obtained here was 1755 (calculated value, the following molecular weight was computed value), the ratio of the polyester segment was 20.2 weight% (following% weight%), the acid value 28, and the hydroxyl value was 39.

[Manufacture Reference Example 6]

786 g (0.448 mol) of the block copolymer obtained in Production Reference Example 5 and 54.2 g (0.54 mol) of amber anhydride were added to a flask and allowed to react for 2 hours in a nitrogen stream at 120-125 ° C. After the contents were cooled to 50 ° C., 210 g of styrene monomer was added to adjust a styrene solution containing 80% by weight of the block copolymer. The hydrogenated polybutadiene-polyester block copolymer in which the acid value 51.5 and the hydroxyl value of the styrene solution containing this block copolymer are 0.8, and the terminal of a polyester ring was carboxy-modified was obtained.

[Manufacture Reference Example 7]

130.2 g (1.3 mole) of amber anhydride, 105.2 g (0.71 mole) of phthalic anhydride, 35.8 g (0.365 mole) of maleic anhydride, 1400 g of hydrogenated α, β-1,2-polybutadiene glycol (as described in Production Reference Example 5) (1 mol) and 0.6 g of lithium chloride were placed in an autoclave, the reaction system was replaced with nitrogen gas, and heated to 130 ° C. with stirring. Next, 86.3 g (1.49 mol) of propylene oxide was press-fitted under the temperature of 125-130 degreeC over 40 minutes. Aged at this temperature for 2 hours to complete the reaction to obtain a hydrogenated polybutadiene-polyester block copolymer. After cooling, 439 g of styrene monomer was added thereto, diluted to dissolve, and the styrene solution containing 80% by weight of the block copolymer was adjusted. The hydrogenated polybutadiene-polyester block copolymer obtained here had a molecular weight of 1758, a ratio of 20.4% of a polyester segment part, an acid value of 26.0 of the styrene solution, and a hydroxyl value of 26.7.

[Manufacture Reference Example 8]

98 g (1 mole) of maleic anhydride, 148 g (1 mole) of phthalic anhydride, and 159.6 g (2.1 mole) of propylene glycol were heated and reacted at 215 ° C. in a nitrogen stream, and the condensation reaction was stopped when the acid value of the reactant became 60. Polyester was obtained. The number average molecular weight of this unsaturated polyester was 754, and the hydroxyl value was 89.3.

Toluene was obtained by obtaining 151 g (0.2 mole) of unsaturated polyester and 300 g (0.1 mole) of hydrogenated α, β-1,2-polybutadiene glycol (Nisso PB-GI3000, number average molecular weight 3000, oxo number 10, manufactured by Nippon Corporation). After dissolving in 1000 ml, 50 g (0.2 mol) of methylene-di (4-phenylisocyanate) was added, and the mixture was reacted at 50 ° C for 1 hour while stirring. Toluene was filtered off from the reaction under reduced pressure to give a yellow viscous liquid product.

What is obtained here is a block copolymer in which the hydroxyl groups which exist in each of unsaturated polyester and hydrogenated (alpha), (omega) -1, 2- polybutadiene glycol each bridge | crosslinked by methylene-di (4-phenyl isocyanate). Some of the by-products include crosslinked unsaturated polyesters or hydrogenated polybutadiene glycols, but in the present invention, a block copolymer purified by removing these by-products from the reaction mixture may be used, or the reaction mixture may be used as it is. The purified block copolymer had an average of two polyester segments per one hydrogenated polybutadiene segment and a urethane bond, and the proportion of polyester segment was 30%.

Example 5

The 33% styrene solutions of the two block copolymers obtained in Production Reference Example 5 and 6 were adjusted, and the compatibility and dispersibility with the following thermosetting unsaturated polyester resins were tested for each solution. The thermosetting unsaturated polyester resins used were five kinds of Eupicer 7507 (manufactured by Nippon Eupicer Co., Ltd.), Polyset 9120, Polyset 9107, Polyset 2212, and Polyset 6200 (the above four points are manufactured by Nippon Seiki Co., Ltd.). In the case of the combination of the block copolymer of Preparation Reference Example 6 and the polyester 9107, phase separation of about 10% was observed at 24 hours, but no phase separation was observed in any of the other combinations without a thickener. Therefore, it was expected that the composition of the combination as described above would give a beautiful X-shaped object with uniform gloss on the surface by various molding methods.

Then, 60 parts of Eupicer 7507, 1.5 parts of Tashari-butylpabenzoate and 3.0 parts of zinc stearate were placed in a Bamboberry mixer for 40 parts of 33% styrene solution, respectively, for the two block copolymers. After 200 parts of calcium carbonate powder was added to make it well uniform, 60 parts of 1/2 inch length glass fibers were added, and after 1 minute, the Bambory mixer was stopped to make a premix. This premix was based on the composition of the present invention, but was molded at a mold temperature of 145 ° C., whereby a molded product having uniform surface gloss was obtained, and the molding shrinkage was 0.004 when the block copolymer of Preparation Reference Example 5 was used. % Was about 0.005% when the block copolymer of Preparation Reference Example 6 was used.

On the other hand, hydrogenated α, ω-1,2-polybutadiene glycol (described in Preparation Reference Example 1) is used instead of the block copolymer. In the case of premixes made under the same conditions, the surface of the molding is glossy. The class was remarkable and ugly.

Example 6

A 33% styrene solution of the block copolymer obtained in Production Reference Example 7 was adjusted, and 40 parts of this solution consisted of 60 parts of polyester 9120, 3 parts of zinc stearate, 1.5 parts of Tashari-butylpabenzoate, 140 parts of calcium carbonate powder, and After mixing 0.3 parts of parabenzokinone uniformly, 2 parts of magnesium oxide was added, and the composition for SMC containing 10% of 1-inch-long glass fiber was produced immediately.

Although this composition was based on this invention, it was shape | molded at the mold temperature of 140 degreeC, Although the surface of the molded object was a little cloudy, the state of gloss was uniform and molding shrinkage rate was 0.05%.

In contrast, hydrogenated α, ω-1,2-polybutadiene glycol (described in Production Reference Example 5) is used instead of the block copolymer. Silver gloss plaque was remarkable and the flow pattern was also confirmed, and the shrinkage rate was -0 25%.

In this case, the dope stability before the addition of the magnesium oxide is also poor and clearly phase-separated, and in this respect, it became clear that industrial operation is very difficult.

Example 7

To 500 parts of 33% styrene solution of each of the two types of block copolymers obtained in Production Reference Example 5 and 6, 500 parts of polylite PC-670 (manufactured by Daiko Ink Co., Ltd.) was added as a thermosetting unsaturated polyester resin, and cobalt naphthenic acid was again added. 60 parts were melt | dissolved and the liquid of viscosity 830 centipoise was obtained. When the liquid was fed into a resin injection mold (commonly referred to as RIM or RTM) in which a glass mat was set in advance, acetyl acetone peroxide was pumped into the mold while mixing to be 1% of the feed liquid.

At that time, the liquid inlet of the mold was 20 mm in diameter, and the mold temperature at the time of feeding was 25 ° C. After 2 hours, the mold temperature started to rise with the heat of polymerization, and reached the maximum temperature of 70 ℃ after 3 hours. After 3 hours, the mold was opened and the molding was taken out. The appearance of the moldings was the same shape, and there were no glossiness, but the surface was smoother than the moldings obtained without the block copolymer, and the glass fiber was the same. The expression of was hardly confirmed.

Example 8

The 33% styrene solution was adjusted using the block copolymer obtained by the manufacture reference example 8 as it was not refined. 40 parts of this solution, 60 parts of polyset 9127 (manufactured by Nippon Kasei Co., Ltd.) and 1.5 parts of Tashari-butylpabenzoate as a thermosetting unsaturated polyester resin were mixed uniformly, and again mixed with 140 parts of calcium carbonate powder, MDI while stirring. To 5 parts was added, a composition for SMC having 27% of 1-inch-long glass fibers was soon made.

This composition is based on the present invention, but it was molded into a plate at 145 ° C. Although the surface of the molding was MDI thickening method, the degree of coloring was slight and there was almost no glossiness, and the molding shrinkage rate was 0.02%, the impact strength (with the notch) was 16.8 feet / lb / inch.

In contrast, α, ω-1,2-polybutadiene glycol (Nisso PB-G 3000, number average molecular weight 3000, manufactured by Nippon Corporation) was used instead of the hydrogenated LGP used in the preparation of the block copolymer in the present invention. Except for using the prepared block copolymer, the surface of the molded article obtained under the same conditions was colored yellowish brown without showing glossiness or glass fiber. The impact of the I-resort (with notches) was about the same as 16.5 feet, pounds per inch.

[Manufacture Reference Example 9]

Hydrogenated α, ω-1,2-polybutadiene glycol (Nisso PB-GI 1000,1000, average molecular weight 1400, manufactured by Nippon Corporation) 700 g (0.5 mol), 0.7 g of detrabutyl titanate and ε-capu as catalysts 300 g (2.63 mol) of rockactone were placed in a reaction tube and reacted at 150 ° C. for 3 hours under a nitrogen gas atmosphere to obtain 997 g of a pale yellow transparent slime product.

The molecular weight of the hydrogenated polybutadiene-polycapurolactone block copolymer obtained here is 2000 (calculated value, below molecular weight is computed value), and the ratio of the polyester segment which becomes polycapurolactone is 30.0 weight% (hereinafter%% is weight%) acid value 0.3 And the hydroxyl value was 54.6.

[Manufacture Reference Example 10]

800 g (0.4 mol) of the block copolymer obtained in Reference Example 9 and 40 g (0.4 mol) of succinic anhydride were placed in a flask and reacted for 2 hours in a nitrogen stream at a temperature of 120-125 ° C. After the contents were cooled to 50 ° C, 210 g of styrene monomer was added to adjust a styrene solution containing 80% by weight of the block copolymer. A hydrogenated polybutadiene-polyester block copolymer was obtained in which the acid value of the styrene solution containing this block copolymer was 50.2, the hydroxyl group was 1.2, and the terminal of the polyester ring was carboxy-modified.

[Manufacture Reference Example 11]

760 g (0.5 mol) of α, ω-1,2-polybutadiene dicarboxylic acid (Nisso PB-C 1000, average molecular weight 1520, manufactured by Nippon Corp.) and 1.5 g of lithium chloride were placed in an autoclave and reacted with nitrogen gas in a reaction system. Subsequently, the reaction mixture was heated to 130 ° C while stirring, and then 48.4 g (1.1 mol) of ethylene oxide was press-fitted at a temperature of 135-145 ° C over 30 minutes.

After aging at this temperature for 2 hours, the reaction was completed to obtain 805 g of α, ω-1,2-polybutadiene dicarboxylic acid dihydroxy ethyl ester. Next, 0.5 g of tetrabutyl titanate and 798 g (7 mol) of epsilon -capurolactone were added thereto, and the mixture was reacted for 4 hours in a nitrogen stream at a temperature of 145-150 ° C to obtain about 1600 g of a color of a transparent transparent slime product.

The polybutadiene-polycapurolacton block copolymer obtained here had a molecular weight of 3204, a ratio of 52.6% of the polyester segment, an acid value of 1.2, and a hydroxyl value of 34.7.

Example 9

The 33% styrene solution of the block copolymer obtained in Production Reference Example 10 was adjusted, and the solution was tested for compatibility to dispersibility with the following thermosetting unsaturated polyester resin.

The thermosetting unsaturated polyester resins used were five types of Eupica 7507 (manufactured by Yupika Co., Ltd.), polyset 9120, polyset 9107, polyset 2212, and polyset 6200 (four of which are manufactured by Nippon Chemical Co., Ltd.). In the case of Polyset 9107, phase separation of about 5% was observed at 24 hours, but phase separation was not found in any other combination without thickener.

Therefore, it was expected that the composition of the above combinations would give a beautiful molded article having a uniform gloss on the surface as various molding methods. Then, 60 parts of Eupica 7507, 1.5 parts of Tashari-butylpabenzoate and 3.0 parts of zinc stearate were placed in a Bamberberry mixer for 40 parts of the 33% styrene solution to the block copolymer of Preparation Reference Example 10. After adding 200 parts of calcium carbonate powder to make it more uniform, 60 parts of l / 2 inch length glass fibers were added, and after 1 minute, the Bambory mixer was stopped to make a premix.

Although this premix was based on the molding of the invention of the invention, it was molded at a mold temperature of 145 ° C., whereby a molding giving uniform surface gloss was obtained, and the molding shrinkage was 0.003%.

On the other hand, except that the hydrogenated α, ω-1,2-polybutadiene glycol (described in Production Reference Example 9) is used instead of the block copolymer, all premixes made under the same conditions are known but the surface of the molded article The gloss board was remarkable and it was not good to see.

Example 10

A 33% styrene solution of the block copolymer obtained in Production Reference Example 10 was adjusted, and 60 parts of Poly 9 9120, 3 parts of zinc stearate, 1.5 parts of Tashari-butylpabenzoate, 140 parts of calcium carbonate powder, and 40 parts of this solution After mixing 0.3 parts of parabenzokinone uniformly, 2 parts of magnesium oxide was added, and the composition for SMC containing 10% of 1-inch-long glass fiber was produced immediately.

Although this composition was based on this invention, it was shape | molded at the mold temperature of 140 degreeC, Although the surface of the molded object was a little cloudy, the glossiness was uniform and the molding shrinkage rate was 0.04%.

On the other hand, in the case of compositions for SMC made under the same conditions except that hydrogenated α, ω-1,2-polybutadiene glycol (described in Preparation Reference Example 9) was used instead of the block copolymer, the surface of the molded product Glossy plaques were remarkable and flow patterns were also confirmed, resulting in a shrinkage rate of -0.25%. In this case, the dope stability before the addition of magnesium oxide was also poorly and clearly phase-separated, and it became clear that industrial operation was also very difficult from the back side.

Example 11

To 500 parts of 33% styrene solution of the block copolymer obtained in Reference Example 9, 500 parts of polylite PC-670 (manufactured by Daiko-Ink Co., Ltd.) was added as a thermosetting unsaturated polyester resin, and 60 parts of cobalt naphthenic acid was dissolved again. A solution of 30 centipoise was obtained.

When the liquid was fed into a resin injection mold (commonly referred to as RIM or RTM) in which a glass mat was set in advance, acetyl acetone peroxide was pumped into the mold while mixing 1% of the feed liquid. At that time, the liquid inlet of the mold was 20 mm in diameter and the mold temperature at the time of feeding was 25 ° C. The mold temperature started to rise with polymerization heat for 2 hours, and reached the maximum temperature of 70 ° C in 3 hours thereafter.

After 3 hours, the mold was opened and the molding was removed. The appearance of the moldings was consistently the same shape, especially the surface was smooth compared to the moldings obtained by the same thing except that the glossiness and the block copolymer were not used.

Example 12

Each 33% styrene solution of the two block copolymers obtained in 9 and 11 was prepared for the reference of manufacture. 40 parts of this solution, 60 parts of polyset 9127 (manufactured by Nippon Chemical Co., Ltd.), and 1.5 parts of Tashari-Butyl Pabenzoate as a thermosetting unsaturated polyester resin were mixed uniformly, and again, 140 parts of calcium carbonate powder were mixed with dope. Addition was made immediately and a composition for SMC with 27% of 1 inch long glass fibers was made.

This composition is based on the present invention, but it was molded into a plate at 145 ° C. The surface of the moldings were yellowish brown as MDI thickening method, but the glossiness was slight and molding shrinkage was 0.025% when the block copolymer of Preparation Reference Example 1 was used and 0.032% when the block copolymer of Preparation Reference Example 3 was used. % The impact strength (with the notch) was 15.9 pounds / inch for the former, and 15.7 pounds / inch for the latter. In contrast, the use of α, ω-1,2-polybutadiene dicarbonic acid hydroxyethyl ester (described in Production Reference Example 11) instead of the block copolymer in the present invention is a molded article obtained under the same conditions. The surface of the surface has the same degree of pigmentation, but the appearance of the gloss board and the glass fiber is confirmed and it is poor, and it shows that the molding shrinkage rate is large, and the impact resistance (with the notch) is 13.2 feet. It was.

In each example, parts and percentages represent either weight.

As is apparent from each of the embodiments, the present invention described above has an effect of having sufficient commercial or dispersion stability and good molding operation, and improving the physical properties of the molded article in terms of surface properties and low shrinkage properties.

Claims (12)

An unsaturated polyester curable resin composition comprising both a block copolymer and an unsaturated polyester that share a polyester portion and a liquid rubber compound portion as a segment constituting the same. The unsaturated polyester curable resin composition for SMC or BMC according to claim 1, further comprising a polymerizable monomer, a filler, a curing catalyst, a releasing agent and a fiber for reinforcement. The unsaturated polyester curable resin composition according to claim 2, further comprising a thickener. The unsaturated polyester curable resin composition according to claim 1, wherein the liquid rubber compound is a polybutadiene compound or a partially or fully hydrogenated polybutadiene compound. The unsaturated polyester curable resin composition according to claim 1, wherein the liquid rubber compound is a polyisoprene compound or a partially or completely hydrogenated polyisoprene compound. The method of claim 1, wherein the polyester moiety is a carboxyl group or a hydroxyl group present in the liquid rubber compound moiety as a starting substrate, and the organic dicarboxylic anhydride and 1,2-epoxide are condensed and formed alternately in the presence of a catalyst. Unsaturated polyester curable resin composition. 8. The unsaturated polyunsaturated polyunsaturated polyunsaturated polyanhydride according to claim 6, wherein the organic dicarboxylic acid anhydride is one or two or more selected from phthalic anhydride, amber anhydride, maleic anhydride, cyclohexanedicarboxylic anhydride, cyclohexenedicarboxylic anhydride and end methylene cyclohexenedicarboxylic anhydride. Ester curable resin composition. The unsaturated polyester curable resin composition according to claim 6, wherein the 1,2-epoxide is one or two or more selected from edylene oxide, furopropylene oxide and butylene oxide. The unsaturated polyester curable resin composition according to claim 1, wherein the polyester portion is a starting group having a hydroxyl group present in the liquid rubber compound portion and successively ring-opening-polymerized ε-aliphatic lactone in the presence of a catalyst. The unsaturated polyester curable resin composition of Claim 9 whose (epsilon) -aliphatic lactone is (epsilon)-capurolactone. The unsaturated polyester curable resin composition according to claim 1, wherein 10 to 60% by weight of the block copolymer is a polyester moiety. The unsaturated polyester curable resin composition according to claim 1, which is one or two or more selected from unsaturated polyesters α, β-ethylenically unsaturated polyesters, novolak-type unsaturated polyesters and vinyl ester-type unsaturated polyesters.