JPH07103207B2 - Modifier for synthetic resin materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a modifier for synthetic resin materials, particularly a partially or completely hydrogenated polydiene-polyester block copolymer (hereinafter referred to as water. (Referred to as an added LGP-PES block copolymer), and a modifier for a thermosetting or thermoplastic synthetic resin material.

Many thermosetting resins and thermoplastic resins are widely used in housing equipment such as bathtubs and septic tanks, industrial materials such as machinery and electric appliances, transportation equipment materials such as automobiles and railway vehicles, and storage tanks and containers. However, in the case of processing using these synthetic resins, generally, various other synthetic resins, fillers, fiber reinforcing agents, etc. are added in order to improve physical properties such as mechanical strength. Especially when the molded product is used as a structural material, it is essential to improve the impact strength. For this reason, it is well known that rubber-based substances and other polymers are blended according to the purpose in addition to various reinforcing agents. Further, an unsaturated polyester resin, which is one of thermosetting synthetic resins, undergoes a volume contraction of 7 to 10% along with the curing reaction, and the appearance and dimensional accuracy of the molded product deteriorate.
For this reason, it is well known that rubber-based substances and other thermoplastic synthetic resins are blended. And as the rubber-based substance used for improving impact strength and reducing volume shrinkage as described above, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-styrene-acrylonitrile ternary copolymer It is also well known that there are polymers and modified polybutadiene.

Thermosetting unsaturated polyester resin and polyethylene terephthalate, polybutylene terephthalate, polycarbonate, as a so-called matrix resin which is a synthetic resin as a main material of reinforced plastics having improved impact resistance,
Thermoplastic synthetic resins such as polyamides are widely used in this field, and rubber compounds, reinforcing agents, pigments, fillers, etc. are mixed with these synthetic resins, and reinforced plastics are manufactured through various molding methods. Is done.

However, the physical properties of the matrix resin and the rubber-based substance, such as polarity and solubility parameter, differ greatly, so it is extremely difficult to uniformly mix or stably disperse the two. The surface condition of the molded product obtained from the thermosetting synthetic resin composition in an unstable mixed state is poor, and unevenness and protrusion of rubber-based material are observed, and the desired mechanical strength and reduction of shrinkage are also extremely poor. It will be enough. In addition, when a thermoplastic synthetic resin composition in an unstable dispersed state is used, one of the components agglomerates during molding, resulting in problems such as poor moldability and large variations in physical properties of the molded product.

Therefore, it is uniformly mixed or stably dispersed in a thermosetting or thermoplastic matrix resin, and the molding workability is good,
There is a strong demand for a modifier capable of obtaining a molded product having an excellent surface and capable of remarkably improving the mechanical strength and reduction of shrinkage of the molded product.

The present invention relates to a modifier for synthetic resin materials that meets such a demand.

<Prior Art and Problems Thereof> Various proposals have been conventionally made for the purpose of improving compatibility or dispersibility with a thermosetting or thermoplastic synthetic resin. As a proposal regarding the modification of the rubber-based substance to be added, there is one in which another monomer such as styrene, maleic acid, methacrylic acid ester, or acrylic acid ester is graft-polymerized to the rubber-based substance (JP-A-54-54). 18862, JP-A-54-40846
etc). These materials generally have poor grafting efficiency, and have a problem that they do not yet exhibit sufficient compatibility or dispersibility. Further, as a proposal for improving the compatibility with a thermosetting synthetic resin, there is a block copolymer of a styrene-based polymer (JP-A-53-74592, JP-A-60-99158). Although this compound has improved compatibility to some extent, it essentially uses a styrene-based polymer having poor toughness, and therefore has a problem that it is significantly inferior in terms of low shrinkage and impact resistance. In the proposal of modifying the unsaturated polyester with a rubber, there is one in which a conjugated diene compound such as dicyclopentadiene is added to the Diels Alder addition to the double bond of the unsaturated polyester containing an α, β-unsaturated dicarboxylic acid (special feature: 58-2315). Since this compound has a small amount of the conjugated diene compound added, compatibility with the unsaturated polyester resin can be expected, but there is a problem in that it is not effective in terms of low shrinkage and impact resistance.

<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention provides a modifier for a synthetic resin material, which solves the above-mentioned conventional problems and meets the above-mentioned demand.

However, the present inventors, as a result of earnest research from the above viewpoint,
The present inventors have found that a specific block copolymer sharing a polyester portion and a partially or completely hydrogenated polydiene compound portion as a segment is properly suitable, and has completed the present invention.

That is, the present invention is a block copolymer which shares a polyester part and a partially or completely hydrogenated polydiene compound part as a segment constituting the block copolymer, wherein One or two or more polyester moieties are linked via an ester bond, and the polyester moiety uses a carboxyl group or a hydroxyl group in a polydiene compound molecule as a starting substrate, and an organic dicarboxylic acid anhydride, 1,2-epoxide and a catalyst are present therein. A modifier for a synthetic resin material, which is a polyester chain formed by alternately condensing underneath, and is composed of a polydiene-polyester block copolymer in which 10 to 95% by weight of the whole is a polydiene compound portion. Pertain to.

In the present invention, the hydrogenated LGP-PES block copolymer is a partially or completely hydrogenated polydiene compound having one or more active hydrogen groups such as hydroxyl groups and carboxyl groups in the molecule ( (Hereinafter, abbreviated as hydrogenated LGP) is used as a starting material, and in the presence of a catalyst, an organic dicarboxylic acid anhydride and 1,2 epoxide are alternately reacted to condense a polyester chain via an active hydrogen group of hydrogenated LGP. By forming it, it can be obtained industrially advantageously and stably.

The important point in the hydrogenated LGP-PES block copolymer of the present invention is that it shares a polyester portion and a hydrogenated LGP portion as a segment constituting the same, and the present invention is the structure of the block copolymer and the like. Is not particularly limited. For example, the active hydrogen group present in the hydrogenated LGP may be in the chain of the compound or at the terminal, directly linked to the chain or indirectly linked through any atomic group. May be. In addition, hydrogenated LGP that constitutes a segment
Is a polydiene compound obtained by radical polymerization, ionic polymerization, living polymerization, or the like, which is hydrogenated, and does not cause stereoisomerism or structural isomerism due to the difference in the polymerization method.

The monomeric diene compound that will make up the hydrogenated LGP is
Hydrogenated LGP such as butadiene, isoprene, chloroprene, and 1,3-pentadiene, which can be advantageously used in the present invention
Examples of hydrogenated α, ω-1,2-polybutadiene glycol (Nisso PB-GI series), hydrogenated α, ω
1,2-polybutadiene dicarboxylic acid (Nisso PB-CI series, the above two points are manufactured by Nippon Soda Co., Ltd.) and the like.

Further, in the above Production Examples, as the organic dicarboxylic acid anhydride, succinic acid anhydride, maleic acid anhydride, aliphatic dicarboxylic acid anhydride such as alkenyl succinic acid anhydride, phthalic acid anhydride, naphthalenedicarboxylic acid anhydride, etc. Examples thereof include alicyclic dicarboxylic acid anhydrides such as aromatic dicarboxylic acid anhydrides, cyclohexanedicarboxylic acid anhydrides, cyclohexene dicarboxylic acid anhydrides, and endomethylene cyclohexene dicarboxylic acid anhydrides.

Furthermore, in the above Production Example, as the 1,2-epoxide,
Examples thereof include ethylene oxide, propylene oxide, and 1,2-butylene oxide.

In the above Production Examples, examples of the catalyst include lithium halides such as lithium chloride and lithium bromide, and tetraalkyl quaternary ammonium salts such as tetramethylammonium bromide, totibutylmethylammonium bromide and tetrapropylammonium chloride.

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

The basic idea of the present invention is to increase the compatibility or dispersibility with the matrix resin while utilizing the inherent characteristics of the polydiene compound having improved heat resistance and light resistance by hydrogenation. A hydrogenated LGP-PES block copolymer in which polyester is bonded to hydrogenated LGP as a segment is used.

Next, the method for producing the hydrogenated LGP-PES block copolymer of the present invention will be described more specifically. In the presence or absence of an inert solvent, the reaction vessel is charged with a predetermined molar amount of an organic dicarboxylic acid anhydride and a catalyst with respect to 1 mol of hydrogenated LGP having an active hydrogen group described above, and a predetermined mol under normal pressure or pressure. Introduce a quantity of 1,2-epoxide, 50-200 ℃, preferably 120-150 ℃
The reaction is performed under heating to obtain a hydrogenated LGP-PES block copolymer.

The terminal group of the polyester chain in the hydrogenated LGP-PES block copolymer of the present invention thus obtained is usually a hydroxyl group or a carboxyl group or a mixture thereof, but the ratio of the hydroxyl group and the carboxyl group as the terminal group is It depends on the molar ratio of the organic dicarboxylic acid anhydride and 1,2-epoxide involved in the reaction. Therefore, the ratio of the hydroxyl group as the terminal group to the carboxyl group can be changed by selecting the reaction molar ratio of the both.

The hydroxyl group and / or carboxyl group as the terminal group as described above is reacted with a substance reactive with the terminal group, and various reactive groups such as a vinyl group through a linking group such as an ether bond or an ester bond. It is possible to modify the terminal by adding an epoxy group, an isocyanate group, etc., and to modify the terminal hydroxyl group by reacting the terminal hydroxyl group with a dicarboxylic acid, a dibasic or higher polybasic acid or an acid anhydride thereof. You can also do it. Further, a hydroxyl group or a carboxyl group as a terminal group can be blocked through an ether bond, an ester bond, an amide bond or the like to carry out a non-reactive terminal modification to inactivate the reactivity of the terminal carboxyl group. For the purpose, the carboxyl group can be modified into a salt such as an alkali metal salt or an alkaline earth metal salt.

Regarding the terminal group of the hydrogenated LGP-PES block copolymer of the present invention, magnesium oxide or isocyanates is used as a thickener in the production of SMC (plate-shaped molding material) or BMC (bulk molding material), When magnesium is used, the ratio of the carboxyl group as the terminal group is increased, and when diisocyanates are used, the ratio of the hydroxyl group is increased as the terminal group, and the stability of the unsaturated polyester resin composition as the molding material is improved. It is extremely effective for improving the physical properties of the obtained molded product. In addition, as described above, those subjected to reactive terminal modification form a chemical bond between themselves and the matrix resin or various fillers and cross-linking agents, which is extremely effective for improving the physical properties of molded articles. In many cases, the non-reactive terminal modification as described above often improves the compatibility with the matrix resin or the chemical stability.

The hydrogenated LGP-PES block copolymer of the present invention is a modifier for the purpose of improving impact resistance and / or reducing curing shrinkage of a molded product containing a thermosetting resin and various thermoplastic resins as a matrix resin. As a particularly excellent performance. The reason is that the hydrogenated LGP-PES block copolymer exhibits uniform and stable compatibility or dispersibility with the matrix resin, as compared with rubber-based substances and thermoplastic resins used for the same purpose as before. This is because The hydrogenated LGP-PES block copolymer has desired performance depending on the molecular weight, structure, composition and molecular weight ratio of both the polydiene compound portion and the polyester portion. To improve the compatibility or dispersibility with the matrix resin, it is possible to increase the molecular weight ratio of the polyester portion,
More specifically, depending on the type of matrix resin, an organic dicarboxylic acid and 1,2-
By appropriately changing the type of epoxide and the ratio of their use, it is possible to obtain those having the respective desired performances. Further, when the ratio of the polyester portion is relatively increased, the compatibility with the matrix resin becomes extremely good, but the surface characteristics of the molded product are not necessarily improved. Therefore, in order to satisfy both the compatibility or dispersibility with the matrix resin and the surface characteristics of the molded product, the ratio of the polydiene compound portion to the polyester portion becomes a problem, but it depends on the structure and application of each portion. It is also affected by the type of matrix resin used.

For the above reasons, when the hydrogenated LGP-PES block copolymer of the present invention is used as a modifier for the purpose of improving impact resistance, reducing curing shrinkage, etc., the ratio of the polydiene compound portion is 10 to. The weight is 95 weights, but when the thermosetting synthetic resin is intended, the weight is preferably 40 to 90 weights.
When the polyester portion is less than 5% by weight, the dispersibility with the matrix resin becomes poor.

The main performance of the hydrogenated LGP-PES block copolymer of the present invention has been described above.The block copolymer is used to stably disperse other thermoplastic resin which is incompatible with this in the matrix resin. It is also extremely effective as a dispersant for

When the hydrogenated LGP-PES block copolymer of the present invention is used in a thermosetting unsaturated polyester resin, the copolymer is added to a vinyl polymerizable monomer such as styrene, methylstyrene, or methylmethacrylate at an appropriate concentration. The diluted composition is very convenient to use.

Hereinafter, in order to further clarify the present invention, evaluation examples of production examples of hydrogenated LGP-PES block copolymers and examples using them will be specifically described.

<Examples, etc.>-Production Reference Example 1 (corresponding to B in Table 1 below) phthalic anhydride 52.3 g (0.35 mol), succinic anhydride 82.5 g
(0.825 mol), 0.7 g of lithium chloride as a catalyst and hydrogenated α, ω-1,2-polybutadiene glycol (Nisso P
700 g (0.5 mol) of B-GI1000, average molecular weight 1400, iodine value 6, manufactured by Nippon Soda Co., Ltd. was charged into the autoclave, the reaction system was replaced with nitrogen gas, and then heated to 130 ° C. with stirring. Then, 42.7 g (0.74 mol) of propylene oxide was injected under pressure over 1 hour. Aged at 130 ℃ for 2 hours to complete the reaction, 875g of pale yellow transparent viscous product
Got

The molecular weight of the hydrogenated polybutadiene-polyester block copolymer obtained here was 1755 (calculated value, the following molecular weight was calculated value), and the ratio of polydiene-based segment was 79.8% by weight.
(The following% is% by weight), the acid value was 28 and the hydroxyl value was 39.

-Production Reference Example 2 (corresponding to G in Table 2 below) 786 g (0.448) of the block copolymer obtained in Production Reference Example 1
Mol) and 54.2 g (0.54 mol) of succinic anhydride were charged into a flask and reacted at a temperature of 120 to 125 ° C. in a nitrogen stream for 2 hours. After cooling the content to 50 ° C., 210 g of styrene monomer was added to prepare a styrene solution containing 80% by weight of the block copolymer.

Acid value of styrene solution containing this block copolymer 51.5,
A hydrogenated polybutadiene-polyester block copolymer having a hydroxyl value of 0.8 and having a polyester chain terminal carboxyl-modified was obtained.

-Production Reference Example 3 (corresponding to F in Table 1 below) 130.2 g (1.3 mol) of succinic anhydride, 105.2 g of phthalic anhydride
(0.71 mol), maleic anhydride 35.8 g (0.365 mol), hydrogenated α, ω-1,2-polybutadiene glycol (described in Production Reference Example 1) 1400 g (1 mol) and lithium chloride 0.6 g were put in an autoclave. After charging, the inside of the reaction system was replaced with nitrogen gas, and the mixture was heated to 130 ° C with stirring. Then, 86.3 g (1.49 mol) of propylene oxide was injected under pressure at a temperature of 125 to 130 ° C over 40 minutes. The reaction was completed by aging at this temperature for 2 hours to obtain a hydrogenated polybutadiene-polyester block copolymer. After cooling, 439 g of styrene monomer was added to this and diluted and dissolved to prepare a styrene solution containing 80% by weight of the block copolymer.

The hydrogenated polybutadiene-polyester block copolymer obtained here had a molecular weight of 1758, a polydiene segment ratio of 79.6%, an acid value of the styrene solution of 26.0, and a hydroxyl value of 26.7.

-Example 1 (Example of hydrogenated LGP-PES block copolymer) In the same manner as in Production Reference Examples 1 and 3, hydrogenated LG described in Table 1 was used.
A P-PES block copolymer was obtained.

-Example 2 (Example of hydrogenated LGP-PES block copolymer with terminal modification) Terminalized hydrogenated LGP-PES block copolymer with terminal modification shown in Table 2 with B in Table 1 being symmetrical A polymer was obtained.

-Evaluation 1 60 parts by weight of a styrene solution of an unsaturated polyester resin containing 60% of solid content (Polyset 9107, manufactured by Hitachi Chemical Co., Ltd., phthalate ester type), 27 parts by weight of styrene monomer, and modifier shown in Table 3. 13 parts by weight was placed in a beaker, uniformly mixed and stirred with a propeller stirrer for 5 minutes, transferred to a 100 ml graduated cylinder and allowed to stand at room temperature, and the amount of phase separation (volume%) was measured with time. Shown in the table.

Evaluation 2 Modifier B shown in Table 1 and Modifier G shown in Table 2
For each of the two block copolymers of (3), 60 parts of UPICA 7507 (manufactured by Nippon Yupica Co.) as a thermosetting unsaturated polyester resin, 40 parts of 33% styrene solution, 1.5 parts of tertiary butyl perbenzoate and zinc stearate are used. Prepare 3.0 parts of liquid in a Banbury mixer, add 200 parts of calcium carbonate powder to it and homogenize well, then add 60 parts of 1/2 inch long glass fiber and stop the Banbury mixer after 1 minute I made a premix. When this was molded at a mold temperature of 145 ° C., a molded product exhibiting a uniform surface gloss was obtained, and its molding shrinkage ratio was a little less than 0.004% when the block copolymer of modifier B was used. When the G copolymer was used, it was slightly less than 0.005%.

On the other hand, hydrogenated α, ω instead of the block copolymer
In the case of a premix made under the same conditions except that -1,2-polybutadiene glycol (described in Production Reference Example 1) was used, the surface of the molded product had remarkable gloss unevenness and could not be seen. Met.

-Evaluation 3 A 33% styrene solution of the block copolymer of the modifier F shown in Table 1 was prepared, and 40 parts of this solution was used as Polyset 9120 (manufactured by Hitachi Chemical Co., Ltd.) as a thermosetting unsaturated polyester resin. 60 parts, 3 parts of zinc stearate, 1.5 parts of tert-butyl perbenzoate, 140 parts of calcium carbonate powder and 0.3 parts of parabenzoquinone, and then 2 parts of magnesium oxide are added. Immediately 1 inch long glass fiber
A composition for SMC containing 10% was made. When this was molded at a mold temperature of 140 ° C., the surface of the molded product was slightly clouded, but the glossiness was uniform, and the molding shrinkage was 0.05%.

On the other hand, hydrogenated α, ω instead of the block copolymer
All were made under the same conditions except that -1,2-polybutadiene glycol (described in Production Reference Example 1) was used.
In the case of the composition for SMC, the surface of the molded product had remarkable gloss unevenness, a flow pattern was also observed, and the molding shrinkage was -0.25%. Further, in this case, the stability of the dope before addition of magnesium oxide was also poor, and the phases were clearly separated, and from this aspect, it was obvious that industrial operation was difficult.

Evaluation 4 Modifier B shown in Table 1 and Modifier G shown in Table 2
To 500 parts of each 33% styrene solution of the above two block copolymers, 500 parts of Polylite PC-670 (manufactured by Dainippon Ink and Chemicals) as a thermosetting unsaturated polyester resin was added, and further 60 parts of cobalt naphthenate was added. It was dissolved to obtain a liquid having a viscosity of 830 centipoise. When this solution is fed into a resin injection mold (commonly called RIM or RTM) in which a glass mat is set in advance, acetylacetone peroxide is mixed so as to be 1% of the fed solution, and the gold is mixed. Pumped into mold. At that time, the inlet of the mold had a diameter of 20 mm, and the mold temperature at the time of feeding was 25 ° C. After 2 hours, the mold temperature began to rise due to the heat of polymerization, and reached the maximum temperature of 70 ° C within 3 hours. After a further 3 hours, the mold was opened and the molded product was taken out. The appearance of the molded product is uniform and there is no particular unevenness in gloss, and the surface is smoother than that of the molded product obtained by making all the other parts identical without using the block copolymer. There wasn't.

-Evaluation 5 A 33% styrene solution of modifier B shown in Table 1 was prepared. 40 parts of this solution, 60 parts of Polyset 9127 (manufactured by Hitachi Chemical Co., Ltd.) as a thermosetting unsaturated polyester resin and 1.5 parts of tertiary butyl perbenzoate are uniformly mixed,
Further, 5 parts of MDI was added to a dope mixed with 140 parts of calcium carbonate powder while stirring to immediately prepare a composition for SMC having 27% of 1-inch-long glass fiber, which was formed into a flat plate at 145 ° C. The surface of the molded product is yellowish brown because both are MDI thickening method, but the unevenness of the gloss is slight, the mold shrinkage is 0.02%, and the Izod impact strength (with notch) is
It was 17.0 ft / in.

On the other hand, in place of the hydrogenated LGP used for the production of the block copolymer in the present invention, α, ω-1,2-polybutadiene glycol (Nisso PB-G1000, average molecular weight 1430, manufactured by Nippon Soda Co., Ltd.) was used. The surface of the molded article obtained under the same conditions except that the block copolymer produced by the above method was used was colored yellowish brown, although neither glossy spots nor protruding glass fibers were observed. Also, Izod impact strength (with notch)
It was about the same as 16.5 ft / p.

In each example, parts and% are by weight.

<Effects of the Invention> As is clear from each example and evaluation, the present invention described above has sufficient compatibility or dispersion stability, good molding workability, and surface characteristics and low There is an effect that excellent physical properties can be improved in terms of shrinkability and the like.

Claims (8)

[Claims] 1. A block copolymer which shares a polyester part and a partially or completely hydrogenated polydiene compound part as a segment constituting the block copolymer, and is based on one polydiene compound part. One or more polyester moieties are linked via an ester bond,
The polyester portion is a polyester chain obtained by alternately condensing an organic dicarboxylic acid anhydride and a 1,2-epoxide in the presence of a catalyst, using a carboxyl group or a hydroxyl group in a polydiene compound molecule as a starting substrate, Ten~
A modifier for synthetic resin materials, comprising 95% by weight of a polydiene-polyester block copolymer having a polydiene compound portion. 2. The organic dicarboxylic acid anhydride is one or two selected from phthalic anhydride, succinic acid anhydride, maleic acid anhydride, cyclohexanedicarboxylic acid anhydride, cyclohexene dicarboxylic acid anhydride or endomethylene cyclohexene dicarboxylic acid anhydride. The modifier for a synthetic resin material according to claim 1, which comprises at least one kind. 3. The modification for synthetic resin materials according to claim 1 or 2, wherein the 1,2-epoxide is one kind or two kinds or more selected from ethylene oxide, propylene oxide and butylene oxide. Agent. 4. The modifier for synthetic resin materials according to claim 1, wherein the terminal of the polyester portion is modified with a reactive group selected from a vinyl group, an epoxy group, an isocyanate group or an amino group. 5. The modifier for synthetic resin materials according to claim 1, wherein the end of the polyester portion is modified with a non-reactive group through an ester bond, an ether bond, an amide bond or a urethane bond. . 6. The modifier for synthetic resin material according to claim 1, wherein 25% or more of the terminal groups of the polyester portion are carboxyl groups or hydroxyl groups. 7. The modifier for synthetic resin materials according to claim 1, wherein the polydiene compound is a polybutadiene compound. 8. The modifier for synthetic resin materials according to claim 7, wherein the polybutadiene compound is a homopolymer of butadiene.