KR810001791B1 - Elastimer modified unsaturated molding composition - Google Patents

Abstract

Filled unsatd. polyester bulk and sheet molding compds. were modified with elastomers to give products with improved impact strength and surface characteristics. Thus, a polyester paste was prepd. by mixing polyester resin 600, CaCO3 760, Zn stearate 40, and tert-butyl perbenzoate 6g. A modifier paste of 20% chloroprene polymer in styrene was similarly prepd. A mixt. of polyester paste 400, modifier 48, MgO 4, and chopped glass fibers 92g was molded 6 min at 150≰C to give specimens having compressive impact crack roting 0.5-0.7J.

Description

Modified Unsaturated Elastomer Molding Composition

The present invention relates to a unsaturated elastic composition of the present invention, and relates to a composition capable of bulk molding, plate molding, premixing, or mat molding. Typical of such compositions are polyester-styrene resin based components and thermosetting formulations based on vinyl ester-styrene resins. The composition is reinforced by containing at least one fiber material such as glass fiber or cut glass fiber.

Conventional unsaturated ester molding compositions have various disadvantages depending on the specific composition and the particular application. In order to minimize or eliminate these shortcomings, various efforts have been made to modify the basic composition.

For example, the thermosetting properties of polyester molding compositions pose various difficulties in manufacturing plants, and various attempts have been made to overcome these difficulties by adding solid propylene polymers to these compositions, but the adhesion of the compositions to glass is poor. As a way of eliminating this drawback, there is a method of partially modifying the propylene polymer in the composition by reacting with other ethylenically unsaturated compounds.

As another example, the final product made of polyester molding composition utilizing unsaturated polyester had a defect such as cracking, cracking, or pore, which was destroyed when the product became porous or subjected to severe impact. (Iii) A method of minimizing or eliminating these drawbacks is also shown by adding a small amount of a polymer such as diene, for example butadiene.

It is well understood that the impact strength of the final product is improved by adding butadiene polymer to the polyester molding composition, but the surface properties obtainable by using the composition according to the present invention are not improved but remain in a deficient state. Furthermore, the addition of fillers greatly improves these properties.

Another example is that polyester molding compositions have a high degree of volumetric shrinkage during curing and poor surface properties of the final product even if they are reinforced with fibres. To remove these difficulties, thermoplastic resins such as polymethacryl are incorporated into the polyester composition. There is a method of adding and a method of adding a thermoplastic ethylene copolymer. Indeed, it can be seen here that the surface properties of the final product with the polyester molding composition can be greatly improved by using thermoplastic polymers such as polyethylene and polymethacrylic, but products with such compositions are generally weak in high impact strength. . Even if the conventional method for improving the unsaturated polymerizable molding composition was used, it was not possible to obtain a final product having high impact strength and excellent surface properties.

Accordingly, the present invention is to impart a high impact strength and excellent surface properties to the final product by subjecting the water-saturated ester molded composition with the filler to be used in various moldings such as polyester resin and vinyl ester resin composition with an elastic body opening . Elastomeric modifiers are used among chloroprene polymers and hydrocarbon polymers.

Suitable hydrocarbon polymers include ethylene / propylene dimers, trimers or tetramers. The composition may be reinforced by adding one or more fibrous materials to the composition. Suitable fiber materials include continuous glass fibers or chopped glass fibers.

Improving impact strength results in a combination of impact resistance (e.g. the final product does not crack when subjected to heavy impacts) and crack propagation resistance (e.g. it does not spread far from the point of impact even if a crack occurs). do.

If the surface characteristics are excellent, the longitudinal section is reduced and the surface smoothness is increased, making it easy to coat paint and lacquer on the car body.

In addition to the polymerizable unsaturated ester impurities, the molding composition of the present invention generally contains a polymerizable monomer. When such a composition is formulated for use, a reaction initiator and an inorganic granular filler are added, and sometimes a demolding agent is also formulated. In addition to the polymerizable water saturated ester material and the polymerizable monomer, the composition according to the present invention includes an elastomeric modifier selected from a material consisting of a chloroprene polymer and a hydrocarbon polymer. It is used in combination with the composition according to the present invention and the polymerization initiator and the inorganic filler in a similar manner to the conventional molding composition.

To improve the impact strength, up to 2.5% by weight of a preparation such as dimaleimide or triallyl cyanurate is added. Suitable as dimaleimide are N, 'N-m-phenylenedimaleimide and N,' N-m-tolylene dimaleimide.

The composition according to the invention thus consists of a polymerizable ester material, a polymerizable monomer and an elastomeric modifier in a material consisting of chloroprene and a hydrocarbon polymer. In particular, the composition according to the present invention is 10 to 60% by weight of the polymerizable ester substance, preferably 20 to 50% by weight and 39 to 89% by weight of the polymerizable monomer, preferably 45 to 70% by weight and the elastomer 1 30 wt%, preferably 5-15 wt%. Furthermore, the composition according to the invention comprises 10 to 60% by weight of α, β-ethylenically unsaturated polymerizable esters, generally 20 to 50% by weight and 39 to 89% by weight of polymerizable monomers, in a polyester and vinyl ester material. 45 to 70% by weight and from 1 to 30% by weight, generally weight%, of chloroprene polymer and hydrocarbon polymer, wherein the hydrocarbon polymer is ethylene / propylene dimer, trimer or dimer).

When formulated for use, about 0.1 to 5 parts by weight of a polymerization initiator is added to 100 parts of the composition according to the present invention. In addition, 15 to 50 parts of inorganic filler (powder) is added to 100 parts of composition, and the crude agent is 2.5% by weight, preferably 0.3 to 0.7%, and about 0.5% based on the total amount of monomers and polymers. Add.

The polymerizable ester material and the polymerizable monomer are used in the composition according to the present invention, and the polymerization catalyst and the inorganic filler (powder) are likewise used in the composition according to the present invention, all of which are known α, β-saturated ester molding compositions. Although typically used for polymerizable polyester compounds, unsaturated water (eg molecular weight of double bond sugars) should be about 150-250. The polymerizable polyester compound is subjected to a condensation reaction of at least one α, β-ethylenically unsaturated dicarboxylic acid having 4 to 5 carbon atoms or an ester-producing derivative of these acids with a dihydroxy compound having 2 to 8 carbon atoms. In which case (1) at least one saturated aliphatic darcarboxylic acid having 4 to 10 carbon atoms or (2) an aromatic or cycloaliphatic dicarboxylic acid having 8 to 10 carbon atoms or (3) an ester-generating derivative of these acids The mixture is optionally reacted with up to 90 mol% of the unsaturated acid component. Other suitable unsaturated dicarboxylic acids or those belonging to these derivatives are maleic acid or maleic anhydride and fumaric acid. However, mesaconic acid, citraconic acid itaconic acid or chloromaleic acid may also be used.

Aromatic, cycloaliphatic or water-saturated aliphatic dicarboxylic acids or derivatives thereof include phthalic acid or phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid or tetrahydrophthalic acid or anhydrides thereof, endomethylenetetrahydrophthalic acid or anhydrides thereof, succinic acid or Succinic anhydride and succinic acid esters and chlorides, adipic acid and sebacic acid. Hexachloroendomethylenetetrahydrophthalic acid (helic acid: Het-acid), tetrachlorophthalic acid, or tetrabromophthalic acid is used to prepare a resin with low flammability.

In order to exhibit flame retardancy, halogen-containing compounds which are not co-condensed in polyester, for example, chloroparaffin may be added. In the polyester which can be used preferentially, up to about 25 mol% of a maleic acid unit or a fumaric acid unit is contained and replaced with a portal acid or an isophthalic acid unit.

As the dihydric alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol-diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentylglycol, 1,6-hexane Diol, perhydrobisphenol, etc. Among these, ethylene glycol, 1,2-propanediol, diethylene glycol and dipropylene glycol are preferable.

Monohydric and dihydric alcohols (e.g. butanol, benzyl alcohol, cyclohexanol and pentaerythritol), monoallyl ether, diallyl ether, triallyl ether, and trihydric alcohol polyhydric alcohols; The benzyl ether may be modified by adding up to 10 mole%, or may be modified by adding monobasic acids such as benzoic acid, oleic acid, linoleic acid and ricinoleic acid.

At high temperatures (140 ° to 160 ° C), polyesters must have a high degree of crosslinking during molding or demolding, and therefore must have a high heat deformation temperature.

The acid number of polyester should be between 1 and 100, preferably 5 to 70, OH should be 10 to 100, preferably 20 to 50, and molecular weight of about 500 to 1000 Preferably, 700-3000 (things more than 5000 are measured by vapor pressure osmosis method in dioxane and acetone) is used.

When the molecular weight is different from each other when measuring the molecular weight, the lower molecular weight is regarded as more accurate.

Above 5000 are measured by a diaphragm osmosis method in acetone.

Various suitable vinyl ester compounds have already been described. Among them, (1) a compound in which half of the reaction product of hydroxy substituted ethylenically unsaturated polyester and anhydrous polycarboxylic acid which is a reaction product of polyepoxide and ethylenically unsaturated organic carboxylic acid is ester And (2) a mixture with a catalytic polymer having many epoxy groups.

To prepare these vinyl esters, (A) react by mixing a suitable amount of polycarboxylic anhydride with a headoxy substituted unsaturated polyester having the following general structural formula, or (B) polyepoxide and unsaturated monocarboxylic acid. In this case, when the reaction is substantially completed, the acid anhydride is added to continue the reaction until the acid anhydride reacts.

However, in the above formula

R ₁ : aromatic group R: hydrogen or alkyl group

n: at least 2 as integers, preferably 2 to 6;

As another method of preparing a vinyl ester compound, a reaction product having some of the following groups is formed by a reaction between a polyepoxide and an ethylenic water-bonded monocarboxylic acid by interaction between a carboxyl group and an epoxide period.

A condensation reaction is further carried out with the secondary hydroxy group and dicarboxylic anhydride contained in the reaction product to prepare a compound having an ester group as an accessory.

Good polyepoxides during the reaction include glycidylpolyethers of 150 to 2000 polyhydric phenols or polyhydric alcohols by weight per epoxide group. At least 2 moles of epihalohydrin or glycerol dihalohydrin One mole of polyhydric alcohol or polyhydric phenol is reacted, in which caustic soda is sufficiently added to react with halogen in halohydrin to prepare polyepoxide. The product will contain at least one epoxide, i.e. at least one 1,2-epoxy equivalent.

Ethylenic unsaturated monocarboxylic acids reactive with polyepoxides include hydroxyalkylacrylic acid or methacrylic acid half esters of α, β-unsaturated monocarboxylic acids and dicarboxylic acids.

α, β-unsaturated monocarboxylic acids include acrylic acid methacrylic acid, crotonic acid, cinnamic acid and the like.

The hydroxyalkyl group belonging to the acrylic acid half ester or the methacrylic acid half ester has 2 to 6 carbon atoms, and there are ones such as hydroxyethyl-β-hydroxypropyl and β-hydroxybutyl. It may also contain a hydroxyalkyl group with ether oxygen. Examples of the dicarboxylic acid include phthalic acid, chloric acid, tetrabromophthalic acid, adipic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, halogenated maleic acid, halogenated fumaric acid and mesaconic acid. There is this.

Ethylenically unsaturated carboxylic acid mixtures are also used. Examples of the dicarboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrabromophthalic anhydride, and chloric anhydride. A half ester is prepared at high temperature by adding a polymerization inhibitor such as hydroquinone or methyl ether of hydroquinone.

Polymerizable monomers are unsaturated compounds commonly used in polyester synthesis, which have α-substituted vinyl groups or β-substituted allyl groups and also contain styrene but are hechlorinated and nucleoalkylated styrenes. Contains 1 to 4 pieces. Examples include vinyl toluene, divinylbenzene, α-methylstyrene, t-butylstyrene, and clostyrene, and vinyl acetate of carboxylic acids having 2 to 6 carbon atoms is preferably vinyl acetate, and vinylpyridine, Vinylnaphthalene, vinylcyclohexane, acrylic acid and methacrylic acid or their esters having 1 to 4 carbon atoms in the alcohol component, maleic acid half-ester and diester having 1 to 4 carbon atoms in the alcohol component, maleic acid half- Amides and diamides or cyclic imides such as N-methylmaleimide or N-cyclohexylmaleimide, allyl compounds such as allylbenzene and allyl acetate, allyl acrylate, allyl phthalic acid diallyl ester, isophthalic acid diallyl ester, Eggs such as fumaric acid diallyl ester, allyl carbonate, diallyl carbonate, triallyl phosphate and triallyl cyanurate There is an ester.

Polymerization initiators include organic oxides, which are styrene-soluble group generators, which are used in the presence of a reducing agent. 0.1 to 5% of these polymerization initiators are added to the composition according to the present invention by weight. Examples of such polymerization initiators include diacyl peroxide compounds such as diacetyl peroxide, dibenzoyl peroxide and di-p-chlorobenzoyl peroxide, peroxy esters such as t-butyl peroxide, t-butyl perbenzoate and dicyclohexyl dicarbonate. , Bis- (t-butylperoxy) butane, dicumyl peroxide, alkyl peroxide compounds such as t-butyl cumyl peroxide, hydroperumene, hydro and hydroperoxides such as t-butyl peroxide or azoisobutyronidine nitrile. .

In addition, peroxy ketal compounds such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclohexane are also used as polymerization catalysts. .

Suitable inorganic fillers have been described above, but usually inert minerals are used, such as clay, talc, calcium carbonate, silica, calcium silicate and the like.

As the fiber reinforcing material, glass fibers are used in various forms, that is, glass cloth, cut glass yarn, cut or continuous glass cloth, asbestos, cotton, synthetic fiber (organic), metal, and the like. Furthermore, hydrated alumina or mineral fibers, rock wool or the like can also be used in the composition according to the present invention.

As described above, the elastomeric modifiers used in the compositions according to the present invention are used in materials consisting of chloroprene polymers and hydrocarbon polymers. The "chloroprene polymers" are not limited to homopolymers of chloroprene, but are not limited to homopolymers of chloroprene and sulfur or at least one polymer. Copolymerization with an acidic organic monomer includes chloroprene to form a copolymer at least 50% by weight of the organic monomer.

The chloroprene polymer used in the composition of the present invention may be made by polymerizing chloroprene alone or by polymerizing chloroprene and at least one other component in an emulsion in the presence of a chain transfer agent containing sulfur or organic sulfur. Make. These chloroprene polymerization methods and special polymerization products have been talked about. The best chloroprene polymers contain polychloroprene in a branched view. The most commonly used chain transfer agents include alkyl mercaptans and dialkyl xanthogen disulfides.

Representative compounds that can be copolymerized with chloroprene include vinylaromatic compounds such as styrene, vinyltoluene and vinyl naphthylene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and 2,3- Aliphatic conjugated diolefin compounds such as dichloro-1,3-butadiene, vinyl ethers such as methylvinylether, vinyl acetate and methylvinyl ketone, esters and ketones, acrylic acid such as ethyl acrylate, methyl methacrylate, methylacrylamide and acrylonitrile And esters of methacrylic acid, amides and nitriles.

Among other chloroprene polymers are low molecular weight chloroprenes.

The hydrocarbon polymer is an elastomer modifier used in the polyester molding composition according to the present invention.

As described above, such hydrocarbon polymers include ethylene / propylene copolymers, among which at least one of ethylene / propylene dimers and ethylene / propylene copolymers and non-conjugated dienes is included. These copolymers can be prepared according to conventional methods for interpolymerizing monomers in the presence of a coordination catalyst system.

Preferred ethylene / propylene copolymers contain, by weight, about 30-70% ethylene, about 20-60% propylene and up to about 10% at least one nonconjugated diene. Non-conjugated dienes include cyclic dienes such as dicyclopentadiene and 5-alkenyl-substituted-2-norbornene (eg, 5-ethylidene-2-norbornene and 5-methylene-2-norbornene). There is this. Among the cyclic dienes, ethylidene norbornene is particularly preferred.

Open chain nonconjugated dienes include 1,4-hexadiene. The best hydrocarbon polymer is ethylene / propylene / hexadiene trimer, which is prepared by thermal decomposition as in Example 6.

Ethylene / propylene / diene trimers are prepared by copolymerizing monomers using coordination catalyst systems such as diisobutyl aluminum chloride and vanadium oxychloride in an inert solvent.

Especially useful are branched tetramers, which are prepared by copolymerizing ethylene, propylene, monoreactive nonconjugated dienes and direactive nonconjugated dienes. Of the tetramers, those consisting of ethylene / propylene / 1,4-hexadiene / norbornadiene are preferred. It belongs to the elastomeric ethylene-propylene copolymer.

The composition as described above in the present invention is used for mass forming, plate forming, premixing or mat forming. In the bulk and plate forming operations, a resin paste is produced and the polyester resin paste containing the impact modifier is produced according to a known method. In other words, the resin, the filling agent, the colorant, the thickener, the lubricant, and the polymerization initiator are added to the container, followed by thorough dispersion mixing with a high speed mixer. In this case, since the impact modifier and the polyester resin are too incompatible, it is difficult to obtain a homogeneous mixture with this method. That is, in the first case, if the septum modifier solution is not too viscous, pastes containing polyester and impact modifier are separately prepared as described above, and then the modifier paste is added to the polyester resin paysheet to mix these pastes.

In the second case, it is rather simple and is applied when the impact modifier is extremely viscous. It is made by the method described above without adding the modifier to the polyester paste, and when it is in the mixer, the appropriate amount of the modifier solution is added and then the appropriate amount of filler and demolding agent is added. Mix. When mixing in the mixer, make sure that the mixture is evenly uniform enough to be used. The fibrous reinforcement is then added with paste in a known manner to enter the special molding process.

In the bulk forming operation, the paste is mixed by glass fiber in a low-speed mixer and compressed or injection molded. At this time, the molding conditions are performed by processing at a temperature of 100 to 180 ° C. and a pressure of 0.7 to 10 MPa for 15 seconds to 15 minutes. In the hot state, it is injected into the final product to make the final product. In the plate-forming compound, the glass fiber is added and molded, usually after impregnating the plate-like state or aging (in this case, 1-5 days at a temperature slightly higher than room temperature). Cut to a suitable size and compression molding in the mold as in the bulk molding condition.

In the premix molding, all the components (including glass fibers) are thoroughly mixed in a mixer and molded in the same manner as the bulk molding. In the mat molding, the resin is mixed with an inert filler in a state that has sufficient flow viscosity. Glass fiber cloth may be used alone or in combination with a glass fiber mat.

Colorants, pigments, demolders and polymerization initiators may also be added in the mixture. It is poured onto a glass fiber mat (which contains a binder for glass bonding) that has a certain shape beforehand, placed in a mold to allow the resin mixture to flow and to crosslink under appropriate temperature and pressure.

The following examples are for various compositions according to the present invention and their relative impact strengths are divided into compression impact kinematic grades and Izod impact grades. The compression shock crack test was made with a Gardner type high load impact tester. Place the specimen between the upper surface of the weight and the punch and drop the weight several times at different points to measure the minimum impact force that caused the crack to penetrate between the cracks using dyes to determine the impact rating. joule).

Izod impact rating was expressed as notch (m) (joule / m notch) and the intrinsicity of the EDPM elastomer was measured at 30 ° C. using 0.1 g of sample in 100 cm 3 of tetrachloroethylene.

The intrinsic viscosity of polychloroprene was measured at 30 ° C. using 0.2 g of sample in 100 cm 3 of tetrahydrofuran. Unsaturated value is calculated as the molecular weight for each double bond and all amounts expressed in parts or parts are by weight or percentage by weight unless otherwise specified.

The component used in the Example is as follows.

(1) Chloroprene polymer A: spot viscosity [Mooney viscosity ML 1 + 2.5 (100 ° C.) 36-44, intrinsic viscosity about 1.5 dl / g] DuPont (EIdu Pont de Nemours and Co) as polychloroprene Neoprene WM-1

(2) Chloroprene polymer B: Neoprene AF of Dupont as a copolymer with chloroprene / methacrylic acid [Money viscosity ML 1 + 2.5 (100 degreeC) 45-55]

(3) Chloroprene polymer C: polychloroprene of low viscosity (ηinh 0.46dl / g)

(4) Chloroprene polymer D: Sulfur-modified polychloroprene stabilized with thiuram disulfide (Mooney viscosity ML 1 + 2.5 (100 ° C.) 55-56; intrinsic viscosity about 1.4 dl / g) Neoprene GN

(5) Hydrocarbon polymer A: Ethylene / 47% propylene / 3.3% 1,4-hexadiene polymer with Mooney viscosity 20ML 4 (100 ° C) and intrinsic viscosity 1.6 dl / g

(6) Hydrocarbon polymer B: Ethylene / 31% propylene / 4.4% 1,4-hexadiene / 1.3% norbornadiene polymer as Mooney viscosity ML 4 (100 占 폚) about 25, intrinsic viscosity 1.2 dl / g

(7) polyester resin I; Highly reactive resin containing about 70% propylene glycol maleate and about 30% styrene Unsaturated value = 154 Paraplex p340 of Rohm Hss Co.

(8) Polyester resin II: High temperature reactive styrene type polyester resin unsaturated value = 176. GR63003 of Grace Corporation (W.R. Grace Co)

(9) polyester resin III; Unsaturated Value = 220

OCF E606 from Owens-Corning Fiberglas Corp

(10) Polyester resin IV; Polyester unsaturated value containing melt or dispersion thermoplastic resin which can adjust shrinkage and longitudinal section = 224

Selectron 50344 from PPG Industries, Inc.

(11) Magnesium Oxide Dispersion: 33% Magnesium Oxide Grace's Marco modifier M dispersed in unsaturated polyester

(12) free radical catalysts; 45% 2.5-dimethyl-2.5-bis (t-butylperoxy) hexyne-3, contained in an inert medium,

(13) chopped glass fiber crude product I; 1.27 cm slub

(14) cut glass. . Slubber II: Slubber 1.27cm

(15) chopped glass fiber raw material III: spinning yarn of 1.27 cm

(16) Vinyl ester resin: Contain about 40% of styrene in the compound having the following structural formula.

However, in the above formula

n: 1 ~ 2

R: hydroxy group or semi-ester group

Example 1

A mixture of calcium carbonate, 760 g, 40 g of zinc stearate, and 6 g of t-butyl perbenzoate and 600 g of polyethane resin I600 were mixed uniformly and dissolved in a high speed mixer to prepare poly paste (A). Modifier paste (B) is made in the same manner as above by adding 20% chloroprene synthesis A solution in styrene.

Paste A 400 is mixed with 48 g of paste B and 4G magnesium oxide dispersion and then 367 g of this is mixed with 92 g of chopped fiberglass crude I in a mixer.

Remove the sample from the mixer, chemically thicken it in a sealed container, and place it in a 15.2 × 15.2 × 0.25cm sheet for 6 minutes at 150 ℃. Make two more samples, one with chloroprene polymer B and the other without chloroprene polymer.

The test results are as follows.

Example 2

600 parts of polyester resin I, 760 parts of calcium carbonate, 40 parts of zinc stearate, 6 parts of t-butyl perbenzoate, 3 parts of N, N'-m-phenylenedimaleimide and 3 parts of free radical catalyst according to the method of Example 1 To make the resin paste (A). The modifier paste (B) was prepared by dissolving 20% solution of hydrocarbon polymer A in styrene.600 parts, calcium carbonate 760 parts, zinc stearate 40 parts, perbenzoic acid t-butyl 6 parts, N, N'-m-phenylenemaleic Made using 3 parts of mid and 3 parts of free radical catalyst. Paste A (100 g) was mixed with Paste B (150 g) and 4 g of magnesium oxide dispersion 208 g were mixed with 32 g of chopped glass fiber crude I according to the method of Example 1 and concentrated as in Example 1 Mold.

The compressive impact rating of the molded specimens was 2.3J.

Example 3

A resin paste (A) is produced according to the method of Example 2, except that polyester resin II is used instead of polyester resin I. Similarly, the modifier paste (B) is made according to the method of Example 2, except that a 20% solution in which polychloroprene polymer A is dissolved in styrene is used in place of the hydrocarbon polymer A solution.

Paste A (150g) was mixed with Paste B (100g) and 4g of magnesium oxide dispersion. 212g was again mixed with 42.44g of cut glass fiber I, aged, and molded. The result of the Izod impact test was 250J / m. It was shown as a notch, which is comparable to the impact test value of 170 J / m notch for containing no chloroprene polymer modifier.

Example 4

The procedure is carried out as in Example 3, using polyester resin III instead of polyester resin II and hydrocarbon polymer A instead of chloroprene polymer. The Izod impact test result of the sample according to this example was 180 J / m notch, and the result of not modifying was notch.

Example 5

The resin paste was prepared by using 600 parts of polyester resin I, 776 parts of calcium carbonate, 24 parts of zinc stearate, 6 parts of t-butyl perbenzoate, 3 parts of N, N'-m-phenylenemaleimide, and 3 parts of free radical catalyst. A), and 600 parts of 20% solution added with hydrocarbon polymer B in styrene, 776 parts of calcium carbonate, 24 parts of zinc stearate, 6 parts of t-butyl perbenzoate, N, N'-m-phenylenemaleimide 3 The resin paste (B) was made using 3 parts and free radical catalyst.

Paste A (200 g), Paste B (300 g) and 8.75 g of magnesium oxide dispersion are mixed and 450 g of this is mixed with 90 g of chopped glass fiber and aged at 150 ° C. The sample of this example was 250 J / m notch of the Izod impact test results, but 170 J / m notched without the modifier.

Example 6

Hydrocarbon polymer A is passed through a Brabender extruder (1.90 cm) with a static mixer A acting as a pyrolyzer to make a pyrolyzed hydrocarbon polymer. The extruder is operated at 50 rpm in the following temperature range.

Extruder (1, 2 and 3): 190,260,340 ℃

Static Mixers (1, 2 and 3): 310,315,320,330 ° C

The average residence time of the polymer is 3 minutes 10 seconds.

The intrinsic viscosity of the polymer is reduced from 1.64 dl / g to 0.88 dl / g.

600 parts of 40% solution, 760 parts of calcium carbonate, 40 parts of zinc stearate, perbenzoic acid t which were made of the resin paste (A) according to the method of Example 2, and to which the pyrolyzed hydrocarbon polymer was added as described above. 6 parts of -butyl, 3 parts of N, N'-m-phenylenedimaleimide, and 3 parts of free radical catalyst are mixed to form a resin paste (B).

249 g of paste A (150 g), paste B (150 g), and 4 g of magnesium oxide dispersion were again mixed with chopped organic fiber I49.8 g, aged, and molded at 150 ° C. for 6 minutes. This sample had a particularly smooth surface and the Izod impact test result was 200 J / m notch.

Example 7

The hydrocarbon polymer A was decomposed as in Example 6, but under the following conditions.

That is, 42 rpm, 3 minutes 15 seconds (ret. Time), extrusion temperature (190 °, 260 °, 348 ° C), mixer temperature (320 °, 330 °, 335 °, 345 ° C), and inherent viscosity of the decomposed polymer is 0.43 dl. / g.

A polymer (A) and a modifier (B) paste were prepared in the same manner as in Example 6, and paste A (300 g), paste B (42.9 g), and 4 g of magnesium oxide dispersion were mixed, and 301.5 g of the cut glass fiber I 60.3 g and After mixing, aged and molded.

The surface of the molding was extremely smooth and the Izod impact test result was 200 J / m notch.

Example 8

A large batch of resin paste (A) is produced according to the method of Example 5, and a modifier paste is made into a large batch in the same manner as in Example 5, except that in this case, the hydrocarbon polymer B Use A. 20 parts of cut glass fiber I is added per 100 parts of the mixture of Paste A (220 g), Paste B (200 g), 7 g of magnesium oxide dispersion and a suitable amount of the curing agent shown below, mixed, aged and molded.

Example 9

A resin paste (A) was made according to the method of Example 5 using a vinyl ester resin. In addition, 36.6 g of this resin paste, 156.6 g of a 30% solution in which a hydrocarbon polymer was added to styrene, 203.1 g of calcium carbonate, 6.3 g of zinc stearate, 1,56 g of per-benzoic acid t-butyl, 0.78 g of N, N'-m-phenylenedimaleimide , 0.78 g of free radical catalyst, and 19.2 g of magnesium oxide dispersion were added to mix in a high speed dissolver, and then 548.7 g of this mixture and 137 g of chopped glass fiber II were mixed in a low speed mixer. The mixture is aged and shaped at 150 ° C.

The Izod impact test result of the sample of this example was 280 J / m notch, which is larger than the 200 J / m notch of no hydrocarbon polymer added.

Example 10

Polyester resin IV was used instead of resin I to produce a resin paste (A) according to the method of Example 5. Into 300 g of this resin paste, 64.3 g of a 30% solution in which chloroprene polymer A was added to styrene, 83.1 g of calcium carbonate, 2.6 g of zinc stearate, 5.6 g of magnesium oxide dispersion, 0.643 g of perbenzoic acid, N, N'-m Add 0.32 g of phenylenedimaleimide and 0.32 free radical catalyst to dissolve and mix 507 g of the mixture in a high speed mixer. Place it in a low speed mixer, mix with 126.7 g of chopped glass fiber III, and mold at 150 ° C. The Izod impact test results of the sample of this example were 260 J / m notch, which is much larger than the 140 J / m notch of not adding chloroprene polymer solution.

Example 11

300 g of resin paste (A) was prepared according to the method of Example 5, 64.3 g of a 30% solution of chloroprem polymer C in styrene, 83.1 g of calcium carbonate, 2.6 g of zinc stearate, 5.6 g of magnesium oxide dispersion, fur 0.64 g of t-butyl benzoate, 0.32 g of N, N'-m-phenylenedimaleimide and 0.32 g of a free radical catalyst were added to disperse and dissolve in a high speed mixer, of which 488 g were taken in a low speed mixer and mixed with 922 g of cut glass fiber. After aging, it is molded at 150 ° C.

Example 12

Chloroprene polymer D was milled at 50 ° C. for 30 minutes to reduce the pattern viscosity to ML-10 = 17.7 and then the polymer was added to styrene to form a 30% solution. Polyester paste using 600 parts of polyester resin I, 776 parts of calcium carbonate, 24 parts of zinc stearate, 6 parts of t-butyl perbenzoate, 3 parts of N, N'-m-phenylenemaleimide and 3 parts of free radical catalyst A), 400 g of which was taken and milled in a high speed mixer, 87.5 g of chloroprene polymer D solution, calcium carbonate 110.9 g, zinc stearate 3.4 g, magnesium oxide dispersion 10.5 g, perbenzoate t-butyl 0.875 g, N, N Mix with 0.438 g of '-m-phenylenedimaleimide and 0.438 g of free radical catalyst.

A mixture of 510 g of the mixture and 127.5 g of chopped glass fiber II in a low speed mixer was aged for several days at room temperature, and then molded at 150 ° C. for 2 minutes in a 3 × 150 × 150 mm flat plate. The surface of the sample according to the present example was smooth enough to be suitable for the exterior of an automobile and was 208 J / m notched as a result of the Izod impact test. The result of the Izod impact test resulted in 187 J / m notch and severely blotches of the curved shape and surface without the addition of the elastomer and N, N'-m-phenylenedimaleimide. In another example, 114 g of a commercially available acrylic acid product (the solution of copolymerization of methyl methacrylate in styrene) was added with 400 g of paste A, 147 g of calcium carbonate, 4.6 g of zinc stearate, 11.7 of magnesium oxide dispersion, and 1.14 g of t-butyl perbezo. To mix; The IZOD impact test of 507g of 126.7g of chopped glass fiber II and mixing and aging in a low speed mixer and molding at 150 ° C. for 2 minutes was 150 J / m notch and the surface was good, but it should be somewhat polished for automotive use. Was.

The following examples are figures of relative impact strength of various compositions measured by the Gardner impact crack area test method. In this test, a Gardner-type high-load impact tester was used, and the cracks formed on the back surface were stained with dye by dropping weights at different positions. The impact energy is expressed in joules by calculating the crack area in mm² by measuring the length and width of uniformity with a rectangular equilibrium quadrilateral lamp around each crack.

The components used in this example are as follows.

(1) Hydrocarbon polymer A: consisting of ethylene / 47% propylene / 3.3% 1.4 hexadiene polymer with a Mooney viscosity of 20ML 4 (100 ° C) and an intrinsic viscosity of 1.6 dl / g

(2) Polyester Resin I: Highly reactive resin comprising about 70% propylene glycol maleate and 30% styrene.

(3) Hydrocarbon polymer C: thing having a Mooney viscosity ML 10 = 65 as plyoprene.

(4) Hydrocarbon polymer D: Liquid polybutadiene viscosity: 46 poise (30 degreeC), hydroxy value: 0.81 mg / g).

(5) Cutting glass fiber III: roughness of 1.27cm.

(6) free radical catalysts; 45% 2,5-dimethyl-2,5-bis (t-butylperoxy) hexan-3 in an inert medium.

(7) magnesium oxide dispersions; 33% dispersion of magnesium oxide in unsaturated polyester.

(8) Hydrocarbon polymer E: Fine powder polyethylene

(9) Hydrocarbon polymer F: 48% ethylene / 52% propylene copolymer Mooney viscosity ML 4 (121 ° C) 31,

(10) Hydrocarbon polymer G: Copolymer molecular weight 1900 of butadiene (95) / styrene (5)

Example 13

600 parts of polyester resin I, 776 parts of calcium carbonate, 24 parts of zinc stearate, 6 parts of t-butyl perbenzoate, 3 parts of N, N'-m-phenylene dimalide and 3 parts of free radical catalyst are dispersed and dissolved in a high speed mixer. Polyester paste A is made. A portion of paste A is taken and the modifier solution, fillers and other curing agents are mixed in the order as shown in Table 1 in a high speed mixer.

In the plates of Table 1, the amounts indicated in the "perbenzoic acid t-butyl", "N, N'-m-phenylenedimaleimide" and "free radical catalysts" all refer to the total amount, i.e., the amount supplied from paste A. . Transfer the mixture (expressed in weight) to a slow mixer and mix with the appropriate amount of chopped glass fiber II in Table 1. The amount of addition of all substances in Table 1 is in grams (g).

After aging for several days, the sample was molded in a mold of 150 × 150 × 3mm, and the physical test results are shown in Table 2.

TABLE 1

Modifier B: Hydrocarbon polymer C 30% added to styrene

Modifier C: 20% hydrocarbon polymer C added to styrene

Modifier D: Hydrocarbon Polymer D

Modifier E: Hydrocarbon polymer D 30% added to styrene

Modifier F: Hydrocarbon polymer A 30% added to styrene

Filler: Mixture of 1000 parts of calcium carbonate and 31 parts of zinc stearate

* Similar to Paste A, but without N.N'-m-phenylenedimaleimide and free radical catalyst.

TABLE 2

* These samples had a sticky area and had many voids and extremely poor surface condition. Satisfactory test results could not be obtained.

Example 14

Resin paste A was prepared in the same manner as in Example 12 using 760.5 parts of calcium carbonate and 39.5 parts of zinc stearate. The remaining method was as in Example 12 using chopped fiberglass III. The amount of the various components added is as shown in Table 3 in the same manner as in Table 1. Physical test results are shown in Table 4.

TABLE 3

Modifier B: Hydrocarbon Polymer E

Modifier C: Hydrocarbon polymer F 20% added to styrene

Modifier D: Hydrocarbon G

Modifier E: Hydrocarbon polymer A 30% added to styrene

Modifier G: Chloroprene polymer A 30% added to styrene

Filler: Mixture of 1000 parts of calcium carbonate and 52 parts of zinc stearate

* Similar to Paste A but does not contain N, N'-m-phenylenedimaleimide and free radical catalyst.

TABLE 4

* This sample had adhesive area and had many voids and extremely poor surface condition. Satisfactory test results could not be obtained.

Commercial uses

The composition according to the present invention is particularly strong, lightweight, and can be used in automobile parts, furniture, home appliances, dishes, etc. as having a glass fiber reinforcement.

Optimal conditions of use

The optimum conditions of use of the molding compositions modified with elastomers according to the present invention will depend on the particular properties consistent with the particular use and purpose of use, but the optimum single composition according to the present invention is as in sample number 5 of Example 14.

This composition is the most comprehensive combination of properties and processability and is particularly suitably used in automobiles.

Claims (1)

As described above, the composition ranges from 10 to 60 weight percent of the polymerizable molding resin of α, β-ethylenically unsaturated ester, 39 to 89 weight percent of the polymerizable monomer, and 1 to 30 weight percent of the elastomeric modifier. Modified unsaturated elastomer molding composition.