KR910000747B1 - Additives for synthetic resins - Google Patents

Abstract

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Description

[Name of invention]

Modifiers for Synthetic Resin Materials

Detailed description of the invention

The present invention relates to modifiers for curable or thermoplastic synthetic resin materials containing modifiers for synthetic resin materials, in particular liquid rubber-polyester block copolymers (hereinafter referred to as block copolymers of the present invention).

Although many thermosetting resins and thermoplastic resins are widely used in housing materials such as jade tanks and septic tanks, industrial members such as mechanical and electrical products, transport equipment materials such as automobiles and railway vehicles, and also storage tanks and containers, these synthetic resins are used. In general, in order to improve mechanical properties such as mechanical strength, various other synthetic resins, fillers, fiber reinforcing agents, and the like are added. In particular, when the molded article is used as a structural material, it is essential to improve the impact strength. For this reason, it is well known that rubber substances or other polymers are mixed according to the purpose in addition to various reinforcing agents. Moreover, the unsaturated polyester resin which is one of thermosetting synthetic resins produces 7-10% of volume shrinkage by hardening reaction, and the external appearance and the grade of a molded object fall. For this reason, it is also well known that rubber-based substances and other thermoplastic synthetic resins are mixed.

In addition, as the rubber-based material used to improve the impact strength and lower the volume shrinkage as described above, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile terpolymer And modified polybutadiene and the like are also well known.

Thermoplastic unsaturated polyester resins and thermoplastic synthetic resins such as polyethylene terephthalate, polycarbonate and polyamide are widely used in this field as so-called matrix resins, which are the main synthetic resins of reinforced plastics with improved impact resistance. Reinforced plastics are manufactured through various molding methods by mixing rubber materials, reinforcing agents, pigments, fillers and the like. However, since the physical properties of the matrix resin and the rubber-based material are greatly different, for example, polarity and dissolution parameters, it is very difficult to uniformly mix or stably disperse both. The surface state of the molded product obtained from the unstable mixed thermosetting synthetic resin composition is poor, and unevenness and the appearance of rubber-based materials are confirmed, and the intended mechanical strength and shrinkage reduction are also very insufficient. In addition, the use of unstable dispersed thermoplastic synthetic resin composition causes coagulation of one component during molding, resulting in poor moldability and unevenness in the physical properties of the molded article. Therefore, a homogeneous or stable dispersion of thermosetting or thermoplastic matrix resins, good molding workability, excellent surface moldings are obtained, and the appearance of a modifier that can significantly improve the mechanical strength and shrinkage reduction of the moldings is strongly required. .

The present invention relates to a modifier for synthetic resin materials according to this request.

Background Art Conventionally, various proposals have been made for the purpose of improving the compatibility or dispersibility with thermosetting or thermoplastic synthetic resins. In the proposal regarding the modification of the rubber-based substance to be added, there are those obtained by graft polymerization of other monomers, such as styrene, maleic acid, methacrylic acid ester, and acrylic acid ester, on the rubber-based substance (Japanese Patent Application Laid-Open No. 54-18862, Japanese Patent Laid-Open 54 -40846 and the like). These generally have problems of poor graft efficiency and not yet reach sufficient compatibility or dispersibility. In addition, there is a convex copolymer of a styrene-based polymer as a proposal for improving compatibility with thermosetting synthetic resins (Japanese Patent Laid-Open No. 53-74592, Japanese Patent Laid-Open No. 60-99158). This is somewhat improved in compatibility, but inherently lacking in toughness, and uses a styrene-based polymer, there is a problem that is significantly behind in terms of low shrinkage and particularly impact resistance. The proposal that rubber-modified an unsaturated polyester resin has made the dialls alder addition of the conjugated diene type compound, for example, dicyclopentadiene, to the double bond of the unsaturated polyester containing (alpha), (beta)-unsaturated dicarboxylic acid. (Japanese Patent Office 58-2315). This is because the addition amount of the conjugated diene-based compound is expected to be compatible with the unsaturated polyester resin, while the effect is not obtained in terms of low shrinkage and impact resistance.

The present invention solves the conventional problems such as papermaking, to provide a modifier for synthetic resin material that meets the above-described request. Thus, the present inventors have intensively studied from the above point of view, and have found that a block copolymer having a liquid rubber compound portion and a polyester portion as a segment is very suitable and has completed the present invention.

That is, the present invention is a liquid rubber system having at least one liquid rubber compound portion and a polyester portion on a block as a constituting segment thereof, and having one or more polyester portions connected to one liquid rubber compound portion through an ester bond. The present invention relates to a modifier for a synthetic resin material, characterized by containing a polyester-based block copolymer.

The block copolymer of the present invention is a starting material of a liquid rubber compound having a reactive group having an active hydrogen such as a hydroxyl group, a thiol group, a primary or secondary amino group, an imino group or a carboxyl group as a starting material, and an organic dicarboxylic acid in the presence of a catalyst. Anhydrides and 1,2 epoxides are reacted alternately and the polyester ring is condensed through active hydrogen groups of the liquid rubber compound, or a liquid rubber compound having a hydroxyl group in the molecule is used as a starting material, and ε-aliphatic lactone is present in the presence of a catalyst. It is possible to obtain stable industrially by forming a polyester ring through the hydroxyl ring opening polymerization of a liquid rubber compound.

An important point of the block copolymer of the present invention is that the polyester component and the liquid rubber compound compound are shared as segments constituting the block copolymer, and the present invention particularly limits the production method of the block copolymer and other structures. It is not. For example, the active hydrogen 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 atomic group. In addition, the liquid rubber compound constituting the segment does not cause stereoisomerism or structural isomerism due to differences in the polymerization reaction such as radical polymerization, ion polymerization, and living polymerization.

The monomeric diene compound constituting the liquid rubber compound is butadiene, isoprene, chloroprene, 1,3-pentadiene and the like, but 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 semiester (Nisso PB- GM series, the above three points are manufactured by Nippon Corp.), terminal carboxyl-modified 1,4-polybutadiine (Hycar CTB series, manufactured by Udera Corp. or BF Goodrich), terminal hydroxyl-modified 1,4-polybutadiene ( Poly-bd R-45M or R-45HT, manufactured by KKK, or Ako Chemical Co., Ltd.) and partially or completely hydrogenated, for example hydrogenated α, ω-1,2-poly Butadiene glycol (Nisso PB-GI series), hydrogenated α, ω-1,2-polybutadiene dicarboxylic acid (Nisso PB-CI series), Hydrogenated α, ω-1,2-polybutadiene dicarboxylic acid (Nisso PB-CI series, two of which are manufactured by Nippon Corporation), and the like, but moreover, alkylene oxide is added to the carboxyl group of the carboxy-modified liquid rubber compound. It is also possible to provide a hydroxy alkyl esterified, the epoxy group of the epoxy-modified liquid rubber-based compound to open the epoxy group by reacting water, alcohol or monovalent organic acid.

On the other hand, with respect to the formation of the polyester ring in the liquid rubber compound, in the above production example in which free dicarboxylic acid anhydride and 1,2-epoxide are reacted, examples of the organic dicarboxylic acid anhydride include succinic anhydride, maleic anhydride and alkenyl succinic anhydride. Aromatic dicarboxylic acid anhydrides, such as aliphatic dicarboxylic acid anhydride, phthalic anhydride, and naphthalene dicarboxylic acid anhydride, cycloaliphatic dicarboxylic acid anhydride, cyclohexanedicarboxylic acid anhydride, and substituted aliphatic dicarboxylic acid anhydrides, such as an methylene clohexene dicarboxylic acid anhydride, etc. are mentioned. Can be. Moreover, in the said manufacture example, an ethylene oxide, a propene oxide, a 1, 2- butylene oxide etc. are mentioned as 1, 2- epoxide.

Furthermore, in the above production examples, tetraalkyl quaternary ammonium salts such as lithium halides such as lithium chloride and lithium embrittlement, tetramethylammonium bromide, tributylmethylammonium bromide and tetrapropylammonium chloride can be given. On the other hand, regarding the formation of the polyester ring in the liquid rubber-based compound, in the above-described production example in which the ε-aliphatic lactone is ring-opened-polymerized, ε-caprolactone is exemplified as the ε-aliphatic lactone. Moreover, as a catalyst used for sequential ring-opening polymerization of (epsilon) -aliphatic lactone with respect to the hydroxyl group which exists as a functional group of a liquid rubber type compound, "The course polymerization reaction theory 7 ring-opening polymerization (II)" (Issuance of Japanese Chemical, etc., page 108 Anion polymerization catalysts, coordination anion polymerization catalysts, cationic polymerization catalysts and the like described in the above) can be used.

In particular, titanium-based catalysts such as tetrabutyl titanate, tetrapropyl titanate and tetraethyl titanate, tin catalysts such as dibutyltin oxide, octylic acid tin and tin 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 matrix resin while utilizing the inherent properties of the liquid rubber compound.

The terminal group of the polyester ring in the block copolymer of the present invention is usually composed of a hydroxyl group or a carboxyl group or a mixture thereof, but the hydroxyl group and / or carboxyl group as the terminal group react with the terminal group to react with a reactive substance such as an ether bond or an ester bond. Terminal modification can be carried out by adding various reactive groups such as vinyl group, epoxy group, isocyanate group and the like through the linking group, and the terminal hydroxyl group is reacted with dicarboxylic acid, divalent or higher polybasic acid or acid anhydride thereof. Carboxyl degeneration. Furthermore, hydroxyl groups or carboxyl groups as terminal groups may be blocked by ether bonds, ester bonds, or amide bonds to effect non-reactive terminal modification, and alkali metal salts or alkaline earth metal salts of the carboxyl groups for the purpose of inactivating the reactivity of the terminal carboxyl groups. It is also possible to modify | denature with salts, such as these.

The above-mentioned reactive end modifications are often effective for improving the physical properties of moldings because chemical bonds are formed between them and the matrix resin or various fillers or crosslinking agents. In many cases, the compatibility with the resin or the chemical stability is improved.

The block copolymer of the present invention has particularly excellent properties as a modifier for the purpose of improving the impact resistance and / or lowering the curing shrinkage of a molding having a thermosetting resin and various thermocrosslinkable resins as a matrix resin. This is because the block copolymer of the present invention exhibits uniform and stable compatibility or dispersibility with respect to the matrix resin as compared with rubber-based materials or thermoplastic resins conventionally used for the same purpose. The block copolymer of the present invention has a desired property depending on the molecular weight, structure, composition, molecular weight ratio and the like of both the liquid rubber compound portion and the polyester portion. In order to improve the compatibility or dispersibility with the matrix resin, it is possible to increase the molecular weight ratio of the polyester portion. However, when the ratio of the polyester portion is increased relatively, the compatibility with the matrix resin is very good, while the surface properties of the molded product are excellent. The back is not necessarily improved. Therefore, in order to satisfy both compatibility and dispersibility with the matrix resin and surface characteristics of the molded article, the ratio between the liquid rubber compound portion and the polyester portion is a problem, but it is also dependent on the structure of each portion and the type of matrix resin to be applied. Is affected.

For the above reason, when the block copolymer of the present invention is used as a modifier for improving impact resistance or reducing hardening shrinkage, the proportion of the liquid rubber compound portion is preferably 10 to 95% by weight, and is intended for thermosetting synthetic resins. In particular, 40 to 90% by weight is particularly preferable. Less than 5% by weight of the polyester portion is poor in dispersibility with the matrix resin.

As mentioned above, although the main performance of the block copolymer of this invention was demonstrated, this block copolymer is very effective also as a dispersing agent for stably disperse | distributing this and other incompatible thermoplastic resin in a matrix resin.

The modifier according to the present invention is an appropriate addition of an elastomer, prepolymer, thermoplastic resin, vinyl polymerizable monomer, organic solvent, plasticizer, organic or inorganic extender, fibrous reinforcing agent, etc., which are thermosetting synthetic resins, to the block copolymer of the present invention. You can do it. In particular, when the block copolymer of the present invention is used as a thermosetting unsaturated polyester resin, a composition in which the copolymer is diluted at an appropriate concentration with vinyl polymerizable monomers such as styrene, methyl styrene, and methyl methacrylate is very suitable for use.

Hereinafter, in order to clarify the present invention, reference examples and examples of the preparation of the block copolymers of the present invention and evaluation thereof are specifically listed.

[Manufacture Reference Example 1]

[Equivalent to B-1 in the later Table 1]

Phthalic anhydride 52.3 g (0.35 mole), zucchin anhydride 82.5 g (0.82 mole), 0.7 g of lithium chloride as a catalyst and α, ω-1,2-polybutadiene glycol (Nisso PB-G 1000, average molecular weight 1430) 1) 715 g (0.5 mol) was placed in an autoclave, the reaction system was replaced with nitrogen gas, and heated to 130 ° C. while stirring. Next, 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 mucus. The molecular weight of the block copolymer obtained here was 1786 (calculated value, the following molecular weight was computed value), the ratio of the polydiene type segment was 80.0 weight% (hereinafter %% is weight%), the acid value 27, and the hydroxyl value was 38.

The block copolymer (200 g of styrene monomer and 0.1 g of hydrokinone) was added to 800 g of the obtained block copolymer to obtain a pale yellow transparent styrene solution containing 80% of the block copolymer.

[Production Reference Example 2]

[Equivalent to J-1 in Late Table 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 allowed to react for 2 hours in a nitrogen stream at a temperature of 120-125 ° C. The contents were cooled to 50 ° C. and then dissolved by adding 200 g of styrene monomer. A block copolymer in which the acid value of the styrene solution containing the block copolymer was 50.7, the hydroxyl group was 1.9, and the terminal of the polyester ring was carboxy-modified.

Example 1

[Example of Block Copolymer of the Present Invention]

The block copolymer described in Table 1 was obtained in the same manner as in Production Reference Example 1.

[Table 1]

[Table 1-1]

Note) * 3- * 6, PA, SA, MA, HA, TA, PO and EO are the same as the footnotes in the first table.

The numerical value in the table displays g

* 1: organic dicarboxylic anhydride, * 2: 1,2-epoxide, * 3: α, ω-1,2-polybutadiene glycol (Nisso PB-G 1000, manufactured by Nippon Corporation) * 4: α , ω-1,2-polybutadienedicarboxylic acid (Nisso PB-C 1000, the same as before) * 5: terminal carboxy-modified 1,4-polybutadiene (HycarCTB, manufactured by UHB), * 6: terminal carboxy-modified 1, 4-polybutadiene acrylonitrile block copolymer (Hycar CTBN, acrylonitrile content 8 mol%, the same as before).

SA: Succinic anhydride, PA: Succinic anhydride, MA: Maleic anhydride, HA: Cyclohexanedicarboxylic anhydride, TA: Cyclohexene dicarboxylic anhydride, PO: Propylene oxide, EO: Ethylene oxide

Example 2

[Example of Block Copolymer of the Present Invention with Terminal Modification]

The block copolymer which carried out terminal modification of 2nd table | substrate description was obtained for B-1 of description of 1st table | substrate (However, K-1 in 2nd table | surface targeted F-1 of 1st table | surface). .

[Table 2]

Note) * 7:

[Table 2-1]

[Production Reference Example 3]

[Equivalent to B-2 in late third table]

52.3 g (0.35 mole) of phthalic acid, 82.5 g (0.825 mole) of amber anhydride, 0.7 g of lithium chloride as a catalyst and hydrogenated α, ω-1,2-polybutadiene glycol (Nisso PB-GI 1000, average molecular weight 1400, oxo (6), 700 g (0.5 mol) manufactured by Nippon Oil Industries, Ltd. was placed in an autoclave, the reaction system was replaced with nitrogen gas, and heated to 130 ° C. while stirring. Next, 42.7 g (0.74 mol) of fluorophyllene oxide was pressed in for 1 hour. The mixture was aged at 130 ° C. for 2 hours to complete the reaction, to obtain 875 g of a pale yellow transparent slime product.

As for the molecular weight of the block copolymer obtained here, the ratio of the polydiene type segment was 79.8 weight% (following weight%), the acid value was 28, and the hydroxyl value was 39.

[Production Reference Example 4]

[Equivalent to G-2 in Late Table 4]

786 g (0.448 mol) of the block copolymer obtained in Reference Example 3 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 a temperature of 120 to 125 ° C. After the contents were cooled to 50 ° C., 210 g of styrene monomer was added to adjust a styrene solution containing 80 wt% of the block copolymer.

The block copolymer in which the 51.5 and hydroxy group of the styrene solution containing this block copolymer and the hydroxyl group were 0.8, and the terminal of the polyester ring was carboxy-modified was obtained.

Example 3

[Example of Block Copolymer of the Present Invention]

In the same manner as in Production Reference Example 3, a block copolymer described in Table 3 was obtained.

[Table 3]

Note) * 1, * 2, MA, SA, PO: as in Table 1-1.

* 8 Hydrogenated α, ω-1,2-polybutadiene glycol (Nisso PB-GI 1000, manufactured by Nippon Shogyo Co., Ltd.)

Example 4

[Example of Block Copolymer of the Present Invention with Terminal Modification]

The block copolymer which modified | denatured the terminal of B4 of Table 3 as target object was obtained.

[Table 4]

Note 7 * Same as Table 2.

[Production Reference Example 5]

[Equivalent to B-3 in the later Table 5]

Hydrogenated α, ω-1,2-polybutadiene glycol (Nisso PB-GI 1000, average molecular weight 1400, manufactured by Nippon Corporation) 700 g (0.5 mole), 0.7 g of tetrabutyl methate as catalyst and 300 g of epsilon -caprolactone (2.63 mol) was 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 block copolymer obtained here was 2000, the ratio of the polydiene type segment was 70.0 weight%, the acid value 0.3, and the hydroxyl value was 54.6.

[Manufacture Reference Example 6]

[Equivalent to F-3 in Late Table 6]

800 g (0.4 mol) of the block copolymer obtained in Reference Example 5 and 80 g (0.8 mol) of amber anhydride were added to a flask and allowed to react for 2 hours in a nitrogen stream at a temperature of 120 to 125 ° C. After cooling the contents to 50 ° C., 220 g of styrene monomer was added to adjust the styrene solution containing 80 wt% of the block copolymer.

The block copolymer 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 7]

[Equivalent to E-3 in Late Table 5]

760 g (0.5 mole) 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 substituted in the reaction system with nitrogen gas. It was then heated to 130 ° C. while stirring. Next, 48.4 g (1.1 mol) of ethylene oxide was press-fitted under the temperature of 135-145 degreeC over 30 minutes. The mixture was aged at this temperature for 2 hours to complete the reaction, to obtain 805 g of α, ω-1,2-polybutadienedicarboxylic acid dihydroxy ethyl ester. Next, 0.5 g of tetrabutyl titanate and 798 g (97 mol) of epsilon -capurolactone were added as a catalyst, and reacted for 4 hours in a nitrogen stream at a temperature of 145-150 ° C to obtain 1600 g of a pale yellow translucent liquid product.

The block copolymer molecular weight 3204 obtained here was 47.4% of the ratio of the polydiene segment, the acid value 1.2, and the hydroxyl value were 34.7.

Example 5

[Example of Block Copolymer of the Present Invention of Terminal Hydroxyl Type]

Block copolymers described in Table 5 were obtained in the same manner as in Production Reference Examples 5 and 7, using ε-capurolactone as the polyester cyclizing component.

[Table 5]

[Table 5-1]

Example 6

[Example of Block Copolymer of the Present Invention with Terminal Modification]

The block copolymer which carried out terminal modification of Table 6 based on B-3 of Table 5 was obtained.

[Table 6]

Note 7 * Same as Table 2.

[evaluation]

60 parts by weight of a styrene solution of polyunsaturated polyester resin containing 60% solids (Polyser 9107, manufactured by Nippon Chemical Co., Ltd., phthalic ester), 27 parts by weight of styrene monomer, and 13 parts by weight of modifier of the 7-9 labeling material are placed in a beaker. The mixture was uniformly mixed with a propeller stirrer for 5 minutes, transferred to a 100 ml measuring cylinder, and the amount of phase separation (% by volume) was measured over time in a state where it was left at room temperature, and the results are shown in Tables 7-9.

[Table 7]

Note) A-1 to E-1: of the first notation

PBG: α, ω-1,2-polybutadiene glycol (Nisso PB-G 1000, manufactured by Nippon Corporation)

SBS: Styrene-butadiene-styrene block copolymer (Kaliprex TR 1102, manufactured by Cell Chemistry)

SES: A block copolymer of a styrene polymer in which a styrene monomer is suspended and polymerized by terminating a polyester (proposed in Example 1 of Japanese Patent Application Laid-Open No. 60-99158).

[Table 8]

Note) A-2 to G-2: those listed in Tables 3 and 4

HPBG: Hydrogenated α, ω-1,2-polybutadiene glycol (Nisso PB-GI 1000, manufactured by Nippon Corporation)

[Table 9]

Note) A-3 to K-3: those listed in Tables 5 and 6

PCL: Polycapurolactone (Placcel 220, manufactured by Daicel Corporation)

[Evaluation 2]

For each of the four block copolymers of J-1 listed in Table 2, B-2 listed in Table 3, G-2 listed in Table 4, and F-3 listed in Table 6, 33 % 40 parts by weight of styrene solution, 60 parts by weight of unsaturated polyester resin (Yupika 7507, manufactured by Nippon Yu-Pica Co., Ltd.), 1.5 parts by weight of Tasary Butyl Pabenzoate, and 3.0 parts by weight of zinc stearate are placed in a Benbury mixer and 200 parts by weight of carbonic acid After adding the calcium powder to make it uniform, the Benbury mixer was stopped 1 minute after 60 parts by weight of 1/2 inch fiber length was added, and the resulting premixer was molded at 145 ° C. The molded plate gave uniform surface gloss and the molding shrinkage was 0.005% for J-1, 0.004% for B-2, 0.005% for G-2, and 0.003% for F-3.

On the other hand, in the case of premixes made under the same conditions except that PBG described in Table 7 or HPBG described in Table 8 is used instead of the block copolymer, the surface of the molding is notable because the surface of the molding is remarkable. will be.

[Evaluation 3]

40 parts by weight of 33% styrene solution of the modifiers listed in Table 10, parts by weight of unsaturated polyester resin (Polyset 9120, manufactured by Nippon Chemical Co., Ltd.), 3 parts by weight of zinc stearate, 1.5 parts by weight of Tashari-butylpabenzoate, 140 parts by weight of calcium carbonate powder and 0.3 parts by weight of pachinone were mixed. Next, 2 parts by weight of magnesium oxide was added, and a composition including 10% glass fiber having a fiber length of 1 inch was immediately prepared. The surface gloss was visually observed for the SMC obtained by introducing the SMC into the mold by heating at a mold temperature of 140 ° C., and the molding shrinkage ratio was obtained. The results are shown in Table 10.

[Table 10]

A) A-1 to E-1, PBG, SES: same as Evaluation 1

PBA: α, ω-1,2-polybutadiene dicarboxylic acid (Nisso PB-C 1000, manufactured by Nippon Shogaku Co., Ltd.)

Evaluation: ○-Gloss is good.

△-slightly gloss behind.

×-no gloss

Also, for the F-2 listed in Table 3 and F-3 listed in Table 6, the composition for SMC was made, and each was molded at a mold temperature of 140 ° C., so that the surface of the molding was slightly blurred. The uniform shrinkage was 0.05% for F-2 and 0.04% for F-3.

On the other hand, in the composition for SMC made under the same conditions except that HPBG or PCL (all listed in Table 3) are used instead of F-2 or F-3, respectively, the surface of the molding of HPBG is glossy. Remarkable and flow patterns were also confirmed, and the shrinkage rate was -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 in this respect. In the case of PCL, the surface of the molded product was excellent in gloss or smoothness, but the mold shrinkage was 0.45%.

[Evaluation 4]

The polybutylene terephthalate resin (relative viscosity 1.70 of the 0.5% oxocrophenol phenol solution at 25 ° C.) and the modifier described in Table 11 are mixed at 90/10 weight ratio, melt-kneaded with a 40 mm diameter banded extruder, and pelletized. It was done. The obtained pellets were vacuum dried and then injection molded to obtain a molded article. The molded product was measured for the impact resistance (with notch) (ASTM-D 256-56), and the dispersion state of the modifier in the matrix resin was observed under an electron microscope, and the results are shown in Table 11. . In the case of using PBA in the eleventh table, the idle phenomenon caused by poor kneading of the screw of the extruder in the pelletizing step and acupuncture of a small amount of aggregated PBA at the outlet were confirmed.

[Table 11]

Note) A-1 to E-1, PBA, SES: same as Evaluation 1 or Evaluation 3.

Numeric range of PBA: Indicates an imbalance depending on the site.

[Evaluation 5]

Only the block copolymers described in Table 2 were measured and observed in the same manner as in Evaluation 4, in contrast to B-1 of Table 1, and the results are shown in Table 12. And the addition amount of a modifier is 12.5%.

[Table 12]

[Evaluation 6]

3 types of block copolymers, such as B-2 shown in Table 3, G-2 shown in Table 4, and B-3 shown in Table 5, are each thermosetting unsaturated poly As the ester resin, 500 parts of polylite PC-670 (manufactured by Daikoku Ink Chemical Co., Ltd.) was added, and 60 parts of cobalt naphthenate was dissolved to obtain a viscosity 830 centipoise liquid. When the solution 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 import port 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 ℃ in 3 hours thereafter. After another 3 hours, the mold was opened and the molding was lifted. The appearance of each molding was one shape, and there was no glossiness, and the surface was smooth and almost no glass fiber floated compared to the moldings obtained by the same procedure except that the block copolymer was not used.

[Evaluation 7]

The 33% styrene solution of each of 3 types of block copolymers, such as B-2 shown in Table 3, B-3 shown in Table 5, and E-3, was adjusted. 40 parts of this solution and 60 parts of polyset 9127 (manufactured by Kasei Chemical Co., Ltd.) as a thermosetting unsaturated polyester resin and 1.5 parts of Tashabutyl butyl benzoate were mixed uniformly, and MDI was stirred in a dope mixed with 140 parts of calcium carbonate powder. Five parts were added and immediately made a composition for SMC with 27% of 1-inch-long fiberglass, which was formed into a plate at 145 ° C. The surface of each molding is yellowish brown as MDI thickening method, but the gloss is slight and the mold shrinkage is 0.02% for B-2, 0.025% for B-3 and 0.03% for E-3. It was. In addition, the impact strength (with notch) is 17.0 feet / inch for B-2, 15.9 feet / inch for B-3, and 15.7 feet for E-3. / Inches.

On the other hand, except that the α, ω-1,2-polybutadiene dicarboxylic acid dihydroxy ethyl ester (described in Production Reference Example 7) was used instead of the block copolymer in the present invention, all were obtained under the same conditions. Although the surface of the molding was similar in color, it was confirmed that the gloss plaque and glass fiber were broken, and it showed that the molding shrinkage ratio was also high, and the impact resistance (with the notch) of the Isos was 13.2 pounds / inch.

In each example, parts and percentages represent either weight. As is apparent from the Examples and the evaluations, the present invention described above has a good commerciality and dispersion stability, good molding operation, and excellent physical property improvement in terms of surface properties and low shrinkage of the molded article.

Claims (9)

A liquid rubber-polyester having at least one liquid rubber-based compound portion and a polyester portion, all of which are blocks, and one or more polyester portions connected to each other by means of ester bonds. A modifier for a synthetic resin material, comprising a block copolymer. The modifier for a synthetic resin material according to claim 1, wherein the liquid rubber compound is a polybutadiene compound or a partially or completely hydrogenated polybutadiene compound. The modifier for a synthetic resin material according to claim 1, wherein the liquid rubber compound is a polyisoprene compound or a polyisoprene compound partially or completely hydrogenated. The polyester ring according to claim 1, wherein the polyester moiety is a carboxyl group or hydroxyl group in the liquid rubber compound molecule as a starting substrate, and an organic dicarboxylic acid anhydride and 1,2-epoxide are condensed and formed alternately in the presence of a catalyst. Modifiers for synthetic resin materials. The synthetic resin material according to claim 4, wherein the organic dicarboxylic acid anhydride is one or two or more selected from phthalic anhydride, amber anhydride, maleic anhydride, cyclohexanedicarboxylic anhydride, cyclohexenedicarboxylic acid anhydride or endmethylenecyclohexenedicarboxylic acid anhydride. Modifiers. The modifier for synthetic resin materials according to claim 4, wherein the 1,2-epoxide is one or two or more selected from ethylene oxide, propylene oxide or butylene oxide. The modifier for a synthetic resin material according to claim 1, wherein the polyester moiety is obtained by sequentially ring-opening polymerization of ε-aliphatic lactone in the presence of a hydroxyl group present in the liquid rubber compound moiety as a starting substrate. The modifier for a synthetic resin material according to claim 7, wherein the ε-aliphatic lactone is ε-caprolactone. The modifier for a synthetic resin material according to claim 1, wherein 10-95 weight in the liquid rubber-polyester block copolymer is a liquid rubber-based compound moiety.