JPH06504087A - Thermosetting polyester plastic composition containing blocked polyisocyanate and isocyanate-reactive material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Heat curing containing blocked polyisocyanates and isocyanate-reactive materials polyester plastic composition This application is filed on September 30, 1991 and has patent application serial number o7/767,498. This is a partial continuation application.

field of invention The present invention relates to thermosetting reinforced polyester compositions, and more particularly to blocked polyester compositions. Regarding the above composition containing an isocyanate-reactive substance in addition to an isocyanate. Ru.

Molding assembly based on thermosetting reinforced polyester in the form of a compound (BMC) The composition has been known for many years. These substances contain at least two hydroxy polyols having a group and saturated and unsaturated dicarboxylic acids (or their anhydrides) ) based on unsaturated polyester resins produced from the reaction with mixtures of It is. This initially produced unsaturated polyester resin is one or more monomers capable of crosslinking saturated bonds, a peroxide catalyst and e.g. The monomers are mixed with a reinforcing material such as fibers and then heated to decompose the peroxides. A cross-linking reaction occurs between the polymer and the unsaturated bonds in the polyester molecule. obtained The product is a reinforcing material and a crosslinked polyester composite.

In many patent applications, an alkali such as magnesium oxide is used before crosslinking begins. A lithium-containing thickener is added to the composition. This thickener is the residue of polyester molecules. complex with residual carboxyl groups, thereby increasing the viscosity of the mixture; Achieving uniform dispersion of the reinforcing beam as it flows into its final shape during processing It seems to be. In addition to the materials mentioned above, the molding composition may contain various other fillers, They often also contain mold release agents and various other fillers discussed below.

starting diacids, polyols, crosslinking monomers, catalysts, and other additives used in the production. A great variety of properties of the cured compositions can be achieved by proper selection of their uniqueness and amount used. can do. As a result, these materials are made of strong, relatively lightweight plastics. It has a wide range of applications in the manufacture of rack parts.

Historically, molded composite materials based on thermosetting polyester resins have been It had a point. l) The surface of the molded part is poor and requires expensive services for painting. Such molded parts in internally colored articles that require under-finishing operations and have a high quality appearance. A fiber pattern was developed that precludes the use of the above substances in 2) The part is warped. age), it was not possible to mold to precise tolerances. 3) Molded parts especially It had internal cracks and internal pores in the thickness section. 4) Molded parts have reinforcing ribs and The reinforcement boss had a noticeable depression or sink on the opposite surface.

These problems are caused by the copolymerization of unsaturated polyester resin and crosslinking monomer. It appeared to be a high degree of contraction. The above shrinkage during the crosslinking reaction causes the polymer to become Pull away from surface and fiber reinforcement. This reduces the accuracy of the reproduction of the mold surface. , and leaves a fiber pattern on the surface of the molded part. The strain caused by uneven shrinkage is the final This results in irregularities in molded parts, internal cracks and poor reproducibility of molded dimensions. Noriyoshi It has been shown that curing of conventional unsaturated polyester resin causes a capacity shrinkage of approximately 7%. It was done.

The above-discussed drawbacks can be overcome by adding thermoplastics to the molded composite. Extremely processed. The presence of these thermoplastics in the composition reduce the shrinkage of the area, or if present, cause a small amount of expansion, thereby increasing the A product that more accurately reflects the mold in which the product is made and has a relatively smooth surface. shaped parts are obtained.

The surface smoothness of a molded part can be determined by measuring the surface condition (s) of the molded part using an appropriate surface analyzer. surface profile). the rough surface A smooth surface exhibits a high surface condition, whereas a smooth surface exhibits a low surface condition. Polyes The addition of thermoplastics to tel-based molding compositions increases the A smoother surface is provided on the molded part compared to the case without it. These thermoplastic Plastic resin is a low profile additive. s).

A number of thermoplastic resins have been found to provide varying levels of shrinkage control. those An example is:

a) Poly(vinyl acetate). For example, U.S. Patent No. 3,718,714: No. 4 , 284.736: 4.288.571; and 3,842.142. See specification.

b) Polymethyl methacrylate and copolymers with other acrylates. For example, the United States Patent No. 3.701.748: No. 3, 722.241: No. 4.463.158 No. 4,020,036: and No. 4,161.471 See each specification.

C) Copolymer of vinyl chloride and vinyl acetate.

For example, see U.S. Patent Nos. 4.284.736 and 3.721.642. Light.

d) Polyurethane. For example, U.S. Pat. Nos. 4.035.439 and 4,463. No. 158: British Patent No. 1.451.737; and European Patent No. 074 ．． See each specification of No. 746.

e) Styrene-butadiene copolymers and other elastomers. For example, US patent No. 4.042,036; No. 4.161.471 and No. 4.160.759 See each specification.

f) Copolymers of polystyrene and monomers. For example, U.S. Patent No. 3 ．． 503.921 and 3.674,893, Dutch Patent No. 70-15 No. 386; and German Patent No. 2.252.972.

g) Polycaprolactone. For example, U.S. Pat. See each specification of No. 88.178.

h) Cellulose acetate butyrate. For example, U.S. Patent No. 3.642.672 See specification.

i) Saturated polyesters and varieties of saturated polyesters and poly(vinyl chloride) A mixture of. For example, US Pat. No. 3,489.707: No. 3.736.728: and No. 4,263,199: Japanese Patent No. 4,601,783: and See Landland Patent No. 70-14568.

These polymers are mixed with unsaturated polyester resin and comonomer in appropriate proportions. Provides shrinkage control under standard compression molding conditions and standard injection molding conditions. individual For optimal shrinkage control and therefore mold reproducibility in systems of structure of unsaturated polyester resins and thermoplastic low profile additives. Select a combination of structure and molecular weight.

A wide variety of unsaturated polyester resin structures have been reported in the literature. however, The most commonly used polyester resin contains only 1.0 mol of maleic anhydride. based on condensation with excess polypropylene glycol, and maleic anhydride Similar resins in which 0.35 mole of is replaced with orthophthalic anhydride or isophthalic anhydride It is.

This study on shrinkage control can also be applied to vinyl ester resins. Ru. See US Pat. No. 3,674,893.

The above discussion of composite materials based on molded polyester during curing Progress has been made in overcoming the shrinkage problem for about 25 years. linear shrinkage of parts and/or Progressive improvements were quantified by measuring their surface smoothness.

First generation low profile additives are materials such as polystyrene and polyethylene. It is. Molded parts mixed with such additives are comparable to composites lacking these additives. compared to the 4-5 mils per inch (0.4-0.5%) shrinkage found for It was found that the shrinkage was approximately 2 mils per inch (0.2%). obtained Although the internal colorant was found to be well accepted by the composite, the surface of the part The quality is poor and the degree of shrinkage is lower than that of composites without low profile additives. Although improved relative to the degree of shrinkage, it is still negative for many applications. It was expensive.

Second generation low profile additives include acrylics such as polymethyl methacrylate. is a polymer based on maleic anhydride and propylene glycol. When used with certain unsaturated polyester resins made by combination with The composite material had a shrinkage of about 0.5 mils per inch (0.05%).

These materials develop poor coloration and poor surface smoothness by current standards. Ta.

The third generation of low profile additives are poly(vinyl acetate) polymers. child Additives such as can be used in a wide range of unsaturated polyester resin materials. , and the molded part exhibits virtually no shrinkage. Poly(vinyl acetate) low pro Compositions containing file additives develop poor coloration but molded parts are very It has good dimensional stability and surface smoothness. As a result, these materials are widely used. used.

Fourth generation low profile additives are used in unsaturated polyester resins containing them. The composite material expands slightly during curing, thereby shaping the mold surface with great precision. It is a substance that causes a tendency to reproduce.

Generally, products made using these additives are stored in a mold chamber at room temperature. 0.3 to 0.4 mils per inch larger than the warm dimension. These low profile The surface smoothness of parts manufactured using oil additives is comparable to that of automotive plate steel. is equal to or greater than .

There are several fourth generation low profile additives: l) poly(vinyl acetate) or is another thermoplastic polymer plus at least one shrinkage controlling "synergist".

Examples of shrinkage control synergists are a) epoxide-containing agents such as epoxidized octyl torate; b) Vinyl acetate, which is more reactive with itself than styrene. C) a second monomer such as an epoxide and a second monomer as described above; mixtures, d) lactones such as caprolactone, e) siloxane-alkylene oxide polymer, and f) fatty acid ester.

2) Modified polyesters of the type used with specifically selected unsaturated polyester resins. (vinyl acetate) polymer.

3) A standard low profile material such as poly(vinyl acetate), preferably containing acid. additives obtained from the reaction of polyether polyols with diisocyanates. with the addition of an isocyanate prepolymer that provides a dual thickening mechanism.

Composites based on reinforced polyester due to the use of low profile additives Despite the substantial improvements in material properties achieved in Further improvements in properties such as surface smoothness and surface smoothness are still highly desirable. child Additives which provide one or more of these improvements are the subject of the present invention.

look! Low profile blocked polyisocyanates and isocyanate-reactive materials When added to thermosetting polyester molding compositions containing additives, these Parts manufactured from such polyester molding compositions that do not contain additives and Significantly improved strength, especially flexural strength, as well as better shrinkage control and superior It has been found that final molded parts with surface smoothness can be obtained.

The thermosetting molding composition of the present invention is made of unsaturated polyester, olefinic unsaturated monomer, , a thermoplastic low profile additive, a reinforcing filler, and a block topolymer. isocyanates and isocarbons different from the unsaturated polyesters used in the composition. cyanate-reactive substances. Contains active hydrogen atoms such as polyols An example is a substance that

A method of producing a reinforced thermoset molding composite comprises preparing a thermoset molding composition of the present invention. This composition is molded into a desired shape, and the molded composition is heated to harden. It consists of each process.

Molded articles made using the compositions and methods of the invention are also embodiments of the invention.

detailed description The unsaturated polyesters used in this invention are materials well known in the art. They are polyol and at least one solenoid unsaturated dicarboxylic acid or It is a reaction product with anhydrides and also saturated and/or aromatic dicarboxylic acids and and/or anhydride residues. Olefinic unsaturation is dicarboxylic Preferably in the β position relative to at least one of the carbonyl groups of the acid or anhydride. Yes. Typically, unsaturated polyesters have molecules within the range of 1,000 to 2,000 and also have carboxyl and hydroxyl residues as well as olefinic unsaturation have.

Examples of suitable unsaturated dicarboxylic acids and anhydrides useful in making polyesters Includes maleic acid or anhydride, fumaric acid, tetrahydrophthalic acid or anhydride , hexachloroendomethylenetetrahydrophthalic anhydride (“chlorendic acid anhydride”) ), itaconic acid, citraconic acid, mesaconic acid, and maleic acid or no Diels-Alder adducts with compounds having lefinic unsaturation conjugated to hydrates (Such an adduct is bicyclo[2,2゜11hept-5-ene 3-2,3-di carboxylic acid anhydrides), methylmaleic acid, and itaconic acid There are substances such as Maleic acid or anhydride and fumaric acid are the most widely used commercially. It is used.

Saturated or aromatic dicarboxylic acids or Examples of anhydrides include phthalic acid or anhydride, terephthalic acid, tetrahydrophthalic acid anhydride, hexahydrophthalic acid or anhydride, adipic acid, isophthalic acid, seba These include substances such as sic acid, succinic acid, and trimerized fatty acids.

Polyols useful in making polyester include ethylene glycol, diethylene Glycol, triethylene glycol, propylene glycol, dipropylene Recall, tripropylene glycol, butylene glycols, neopentyl glycol Recall, 1,3- and 1,4-butanediol, l,5-bentanediol , 1. el hexanediol, glycerin, 1,1.1-trimethylolpropyl Substances include bisphenol A1, bisphenol A1, and hydrogenated bisphenol A. Echire It is also possible to use corresponding oxides such as carbon oxide, propylene oxide, etc. Ru. Generally, about 20% or less of the polyols used in polyester production It is a rule.

In addition to the above esters, U.S. Pat. Dicyclopentadiene-modified unsaturated polyester resin described in No. 12 can also be used. can be used.

Other types of unsaturated polyesters useful in making polyester-based molding compositions is a group of substances known as vinyl esters. These are secondary hydroxyls Saturated polyester with functional groups and vinyl groups such as acrylic acid or methacrylic acid It is a reaction product with a containing acid or anhydride. Epoxy based on bisphenol A An example is a reaction product between a resin and an unsaturated carboxylic acid such as methacrylic acid. B Nylesters and methods for their preparation are disclosed in U.S. Pat. No. 3.887.515. ing.

Unsaturated polyesters are in an amount of 20 to 50% by weight, preferably 36 to 45% by weight, based on the weight of the excipient. Generally used in compositions. In fact, the olefinic unsaturation used for crosslinking It is usually used as a 60-65% solution of the Japanese monomer.

The olefinically unsaturated monomer used in the molding composition of the present invention is an unsaturated polyester. It is a substance that can be copolymerized with polyester and produces crosslinking that cures polyester.

The monomer dissolves the polyester and thus allows its interaction with other components of the composition. There is also a function that makes it easier. Use enough monomer to operate conveniently, but monomer Avoid exceeding the necessary amount as too much will have a negative effect on the properties of the final composite material. It should be done.

Monomer depends on the weight of the polyester, monomer, and low profile additives used. Generally included in the composition in an amount of 30 to 70%, preferably 40 to 55% by weight based on used.

Vinyltoluene isomers, methyl methacrylate, acrylonitrile, and chloro Other monomers such as styrene and substituted styrenes such as alpha methylstyrene can also be used, but by far the most commonly used olefinic The saturated monomer is styrene.

Other components of the compositions of the invention are thermoplastic low profile additives, preferably poly( vinyl acetate). A suitable vinyl acetate polymer-based low profile additive is poly( (vinyl acetate) homopolymer and heat containing at least 50% by weight vinyl acetate It is a plastic copolymer. Such as grill acid, maleic acid, fumaric acid, itacon Copolymerization with ethylenically unsaturated carboxylic acids such as acids or anhydrides such as maleic anhydride Carboxylated vinyl acetate polymer that is a combination of vinyl acetate/vinyl chloride/maley There are others such as phosphoric acid terpolymer; and others. Some suitable vinyl acetate polymer bases U.S. Patent Nos. 3,718,714 and 4, which describe profile additives. ．． 284.736, and British Patent No. 1,361.841.

Useful vinyl acetate polymeric low profile additives typically range from 10,000 to 250. 000, preferably within the range of 25.000-175.000. There is. These additives are polyester resins, low profile additives, and Usually in an amount of 5 to 25% by weight, preferably 10 to 20% by weight, based on the total body weight used in compositions.

Other thermoplastic low profile additives other than poly(vinyl acetate) may also be used in the compositions of the present invention. would be helpful. Examples of such materials include poly(methyl methacrylate), Listyrene, polyurethane, saturated polyester, and polyethylene fine powder are available. Ru.

Further components of the compositions of the invention include glass fibers or fabrics, carbon fibers and fabrics, asbestos fibers or textiles, various organic fibers such as those made from the body, and and other reinforcing fillers such as those known in the art. Such materials account for 5% of the total composition. It is generally used in amounts of ~75% by weight, preferably 15-50% by weight.

1-20 pph based on total weight of resin, monomer, and low profile additives , preferably in an amount of 1 to 10 pph. Socyanates are also included in the compositions of the present invention.

Blocked isocyanate is the combination of isocyanate and isocyanate-reactive substances. It is an addition. This adduct is stable at the room temperature at which the operation is carried out, but The isocyanate functional group is regenerated by dissociation at a temperature of 120°C to 250°C, usually 120°C to 250°C. Ru.

Next, the regenerated isocyanate freely reacts with compounds containing active hydrogen to form urea. Tan (hydroxyl + isocyanate) or urea (amine + isocyanate) Bonds form more temperature stable units such as

(However, X=N, O or S).

For use as a starting material for blocked isocyanates useful in the compositions of the present invention. Examples of polyisocyanates that can be used include tetramethylene diisocyanate, xamethylene diisocyanate (HMD I), 1,4-cyclohexane diiso Cyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), xylene diisocyanate), 4,4'-diphenylmethane Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate Simple polyisocyanates, including isocyanate and polyisocyanate substituents and at least one polyol having at least two active hydrogen atoms. There are materials such as linear or branched chain urethane polymers that can be formed. the latter Examples of substances include toluene diisocyanate (TDI), or methylene diphenyl Diisocyanate (MDI) or its polymeric form (polymer MDI) Reacts with polyalkylene oxide diol such as lipropylene oxide diol. There are isocyanate-containing prepolymers produced by three i Substances with isocyanate groups can also be used.

Substances that can be used as blocking groups are compounds with a single active hydrogen. be. Examples of isocyanate blocking agents include:

Phenols: for example, nonylphenol, resorcinol, cresol, and and bisphenol A0 imidazoles: e.g. imidazole, l- or 2- Methylimidazole, 4-phenylimidazole, 2.4.5-1-diphenyl imidazole, 2,2'-bis(4,,5-dimethylimidazole, and 4, 5-diphenylimidazole. .

Pyrazole: For example, pyrazole, 3-methylpyrazole, 3,5-dimethyl pyrazole, and 3,5-pyrazoledicarboxylic acid.

Oximes: For example, 2-butane oxime, dimethylglyoxime, cyclohexime Sanoxime, p-benzoquinone dioxime, pinonic acid oxime, benzopheno oxime, and 4-biphenylcarboxaldehyde oxime.

Commonly carbon-based compounds such as acid esters, diketones, and beta-dicarbonyl compounds Substances with bound acidic hydrogen: e.g. dialkyl malonate, 2,4-penta dione, and ethyl acetoacetate.

Amides: For example, caprolactam.

Hydroxamic acid esters: for example, benzyl methacrylohydroxamate (BM H), and acetohydroxamic acid.

Triazoles: benzotriazole, methylbenzotriazole, and 1, 2.4-Triazole.

Alcohols: for example benzyl alcohol, ethanol, and butanol.

Carbodiimides: For example, carbodiimides react with isocyanates to form urethanes. Generate Nimin.

Furazone N-oxides: These react by opening the heterocycle. Produces isocyanates.

Methods of synthesizing blocked isocyanates are well known to those skilled in the art. Typically, Stoichiometrically equivalent amounts of isocyanate and blocking substance are added separately in a suitable solvent. Dissolve and add one dropwise to the other with stirring and heating under an inert atmosphere. touch A medium may be used, but is not necessarily required. For example, Anagnos Anagnostou and Jaul, Journal O Progress in Organic Coatin Review article by Z. E. Wicks in gs), 9. 3 (19 81) and Yu, 73 (1975), and the original literature.

Generally speaking, the dissociation temperature of blocked isocyanates is Oxime is a function of the structure of the blocking group in relation to the active methylene compound. Yoshi Aromatic blocked isocyanates usually dissociate at lower temperatures than their aliphatic counterparts. do.

Blocked isocyanates have been used in the paint and related industries for many years. Ru. However, most blocked isocyanates are commercially available containing solvents. There is. These solvent-containing raw materials are best used in forming operations for fiber-reinforced plastics. It's inappropriate. This is because this procedure cannot tolerate the presence of non-reactive solvents. It is.

Blocked isocyanates are rarely used in polyester plastics. It seems like there aren't any. Some references using them are mentioned below. Bell.

No. 4,542,177 to Kr1ek et al. stellate and an organic polyisocyanate and at least two isocyanate-reactive groups. thermoplastics consisting of blends with prepolymers obtained by reaction with organic compounds contained in A plastic polyester molding composition is disclosed. This prepolymer is a block toy Contains a isocyanate group. This molding composition is based on unsaturated polyester resin and not olefinically unsaturated monomers or low profile additives. and does not contain the isocyanate-reactive substances used in the present invention. do not have. Products obtained using this molding composition have improved impact performance. It says.

JP-A No. 57-3819 discloses unsaturated polyester resin and blocked isocyanate. Discloses a thermosetting polyester molding composition comprising: This molding composition does not contain isocyanate-reactive substances unlike unsaturated polyester resins. , and do not necessarily contain low profile additives or reinforcing fillers. This formation It is said that products made from the shaped composition have excellent strength.

JP-A No. 56-155216 discloses unsaturated polyester and low molecular weight olefin-based unsaturated polyester. Thermosetting polyester molding composition consisting of a saturated blocked isocyanate crosslinker disclosing something. Molded articles made from this composition develop improved strength they said.

The isocyanate-reactive substance that is suitable for the thermosetting molding composition of the present invention is polyester polyol, which is different from unsaturated polyester resin (polyester polyol) (including those obtained from relactone), hydroxyl group-containing vinyl polymers, amine-terminated Substances that grow active hydrogen atoms such as polyols, diamines, and polyamines It is quality.

Among these substances, primary hydroxyl groups and primary amino groups are preferred. Isocyanene Reactive materials based on total weight of resin, monomer, and low profile additives It is used in an amount of 1 to 20 pph, preferably 1 to 10 pph.

Polyols are the preferred isocyanate-reactive materials. Examples of suitable polyols includes vinyl acetate or other vinyl esters and hydroxyl-containing unsaturated monomers. Copolymers of vinyl chloride and vinyl acetate (or other vinyl esters) and hydride Hydroxyl-containing vinyl polymerization such as terpolymer with roxyl-containing unsaturated monomer Furthermore, hydrides of vinyl ester-containing polymers, DEC/adipate, ethylene -butylene/adipate, diol and dicarbonate with 7 or more carbon atoms Polyesters such as condensates with acids and lactone polyols such as polycaprolactone ster polyols, diols, and triols; polypropylene oxide and and ethylene oxide capped PPO (to obtain the primary hydroxyl compound), etc. polyether polyols, diols, and triols: and amino end groups polypropylene oxide or polypropylene oxide/polyethylene with There are amine-terminated polyols such as oxide polyethers.

The molding compositions according to the invention can be used in customary amounts for their known purposes. It may also contain more conventional additives. The following are such additives: Ru.

1, t-butyl hydroperoxide, 1-butyl perbenzoate, benzoyl peroxide oxide, t-butyl peroctoate, cumene hydroperoxide, methyl ethyl oxide peroxide, and other olefinically unsaturated monomers and olefinically unsaturated monomers known in the art. Polymerization initiator, such as a compound that catalyzes the reaction with lefinic unsaturated polyester. polymerization Initiator is based on the total weight of polyester, monomer, and low profile additives. used in a catalytically effective amount, such as from about 0.3 to about 2-3% by weight; 2. Clay, alumina trihydrate, silica, calcium carbonate, and other products in the industry Fillers such as known ones; 3. Zinc stearate, calcium stearate, and and other mold release agents or lubricants such as those known in the art; 4, a) 4 to 1 per molecule; Conjugated dienes that grow two carbon atoms (such as l,3-butadiene, isoprene, etc.) homopolymers or copolymers of These polymers are described in U.S. Patent No. 4.020. Weight average of 30.000 to 400.000 or more as described in No. 036 b) as described in U.S. Pat. No. 4.101.604; Sea urchin, an ingredient that grows various number average molecular weights (Mn) from 800 to so, ooo. Pihalohydrin homopolymer, copolymer of two or more pihalohydrin monomers Copolymerization or copolymerization of shrimp halohydrin monomer(s) and oxide monomer(s) c) chlorobreath as described in U.S. Pat. No. 4,161,471; at least 5% of the organic monomer composition of the copolymer. 0% by weight of chloroprene and sulfur and/or at least one copolymerizable d) chloroprene polymers, including copolymers with functional organic monomers; d) U.S. Pat. As described in No. 61゜471, ethylene/brobylene dipolymers and and ethylene/propylene/hexadiene terpolymers and ethylene/propylene /1,4-hexadiene/norbornash.

Contains a copolymer of ethylene/propylene such as hydrocarbon polymers; e) as described in U.S. Pat. No. 4,160,759; combined with 15 to 0.5% by weight of a conjugated versatile reflex having 4 to 14 carbon atoms. A copolymer consisting of 85-99.5% by weight of 04-07 olefins, isobutylene Copolymer of tyrene and isoprene (most of the combined isoprene units are copolymers) Conjugated diene butyl elastomers such as those having a large amount of diene unsaturation.

Thickeners are also often used in the compositions of the present invention. These substances are known in the art. Yes, it is the first in the periodic table. 2nd degree and 3rd degree. Contains oxides and hydroxides of group metals. nothing. Specific examples of thickeners include magnesium oxide, calcium oxide, and zinc oxide. , barium oxide, calcium hydroxide, magnesium hydroxide, and mixtures thereof There are things. Thickeners are polyester resins, monomers, and low profile additives. A proportion of from about 0.1 to about 6% by weight, based on total weight, is typically used.

Glossary and substance definitions Alumina trihydrate commercially available filler BMC bulk molding material Gamel white GenStar Stone Products Calcium carbonate filler obtained from 5tone Products) Ca5t Calcium stearate Desmocap lla with ether groups with blocked NGO content of 2.4% branched aromatic urea Tanpolymer. This polymer It is a solid obtained from Mobay Corp.

Desmocap 12a with 1.7% blocked NGO content ether groups Linear aromatic urethane Polymer. This polymer is Mobay Corp.

Gamma Pjas Georgia Marble Calcium carbonate filler obtained from JM 615G 7 Manville Corp, 11 glass fiber LP-4OA 40% acid modified poly(vinyl acetate) in styrene LPS-40AC Solid Acid Modified Poly(vinyl Acetate) MD [Methylene Diphenylene Di isocyanate Microthene USI, Quantum Corp.

Cryogenically ground polyester obtained from tyrene powder Millicarb Calcium carbonate filler from Omya Mo, d E 5% diallyl phthalate solution of rosebenzoquinone MR-13017 manufactured by Aristech Chemical (Ari) containing approximately 35% by weight styrene. Modified isophthalic acid obtained from stech Chemical polyester resin MR-13031 Obtained from Afusutek Chemical containing about 35% by weight styrene. Or Tophthalic acid modified polyester resin Contains approximately 35% by weight styrene obtained from Palapreg P-188ASF. maleic anhydride/ply Ropylene glycol polyester tree fat pBQ Rosebenzoquinone 50% Peroctane obtained from pDO Lucidol Corp. t-butyric acid le PG-9033 Plasticolors [nc, obtained from Mg0 (35% dispersion) PPG-3029 Glass fiber reinforcement (1/2’) from PPG Industries SMC sheet molding material tBPB t-butyl perbenzoate TONE 0301 Union Carbide Chemicals and Plastics Cus CO9, polycaprolactone triol obtained from rnc, Trigonox 29B75 Obtained from Akzo Corp. peroxyketal UCAR■ VYES-4 Union Carbide Chemicals & Plus Chicks CO0, (nc, a terpolymer containing about 29% primary hydroxyl compounds obtained from ZMC Unthickened injection molding material similar to unthickened BMC with glass content of 20% by weight Zn5t Zinc stearate XLP-4022 Union Carbide Chemicals and Plastics CO0, A 37% by weight styrene solution of acid-modified poly(vinyl acetate) obtained from Inc. experiment Nonylphenol (I) was obtained as a 99% mixture of monoargylphenol. . Polyoxyalkylene glycol (II) terminated with MDN in 75% steel Obtained as a solution. The isocyanate content of (IF) Quantitative Organic Analysis Functional Groups) J, John ψ Willie 1 and Sa According to the method presented by Silagia (51gg1a) in Lens, 1962, p.559. Therefore, it was measured. Take 1 mole of (1) and calculate each mole of isocyanate present in (It) React with Nate. Polyoxypropylene glycol with MDI as a terminal group (1) required to cap all of the isocyanate groups present in a given (n). The amount of was calculated as shown below.

Nonylphenol is an inhibitor of peroxide initiators in molding materials (BMC). Therefore, g(I) is multiplied by a factor of 0.98 to obtain the free nonylphenol at the end of the reaction. ensured that the rule does not exist.

The weighed (II) was placed in a three-necked reactor of appropriate size, and then a 1100 pp buffer was added. Labenzoquinone and 1100 pp triethylenediamine were added. reaction mixture The mixture was blanketed with a mixture of 4% oxygen/96% nitrogen and then heated with constant stirring. It was heated to 60°C and this temperature was maintained during the reaction. Next, add phenol (T) It was diluted with styrene to make a 50% solution and added dropwise to the reactor. First time after 4 hours Remove the sample and measure the free isocyanate content as mentioned above. did. Once the free isocyanate content has decreased to 0.1%, add 1-butanol. A slight excess was added to react with the remaining isocyanate. isocyanate When the amount reached 0.0%, the reactor was cooled and the reactant was taken out. The product is manufactured I used it as is.

The blocked isocyanate synthesized in this experiment will be explained below. those are that MDI, nonylphenol (as a blocking agent) and molecular weight, respectively. It consisted of propylene glycol polyol with different Nonylphenol There was no free isocyanate present as the solution was blocked with alcohol.

Following the above procedure, MDI and 2000 molecular weight polypropylene oxide diamide A 75% styrene solution of an ol-based isocyanate prepolymer was prepared.

The free NCO content of this prepolymer solution was 2.4% before blocking. .

Following the above procedure, MDI and 2000 molecular weight polypropylene oxide diamide A 50% styrene solution of an ol-based isocyanate prepolymer was prepared.

The free NGO content of this prepolymer solution was 0.5% before blocking. .

Production of molding compositions About 20°C to about 50° in a suitable device such as a Hobart mixer The compositions of the present invention are prepared by mixing the components at temperatures around C.C. component can be mixed in any convenient order. Commonly used in thermosetting resins and low file additives in styrene or other copolymerizable liquid monomer solutions of these materials. It is preferable to add in liquid form by preparing a liquid. Usually block toiso containing cyanate and an isocyanate-reactive material (preferably a primary polyol). All liquid ingredients are mixed together before adding the filler and thickener. thickener After the addition, add the glass fibers. Once blended, the composition will form the desired shape. It can be molded into thermosetting molded products, especially thermosetting molded products such as automobile body parts. Wear. The actual molding cycle depends on the specific composition being molded and the desired cured molding. Determined by nature. Appropriate molding cycles range from about 0.5 minutes to about 5 minutes. The temperature is about 100°C to about 182°C for a period of time. This is the specific peroxy Depends on the catalyst.

Unsaturated polyester 60 (60-65% in styrene) Low profile additive 40 (33-40% in styrene) 8MC prescription, continued Blocked isocyanate) 1-10 Reactive coupling raw material 2-5 (e.g. polyol) Peroxide catalyst 1.5 (t-butyl benzoate) 5% pBQ o, 4 Off base 4 (zinc stearate) Filler (calcium carbonate) 230 Glass fiber (as a percent of total composition 15.0) weight% *Resins, monomers, and low blob bulk molding materials (BMC) unless otherwise indicated composition All liquid components were individually weighed in Hobart mixed blood placed on a scale. this The dish was attached to a C-100 Hobart mixer placed in the hood. Turn off the stirrer. Start at a slow speed, then increase to maximum speed over a period of 3 to 5 minutes. Allow the liquids to mix thoroughly. Next, after stopping the stirrer, apply the internal mold release agent. added to the liquid. Restart the mixer and add the mold release agent to the liquid until completely wet. mixed with. Next, stop stirring and add the filler to the contents of the dish, then mix it into a uniform paste. The mixture was mixed at high speed with the medium until a mixture was obtained. Re-stop the mixer and weigh thickener and mixed it into the paste at low to medium speed for 2-3 minutes. . Restart the mixer and add about 175g of the paste using a large spatula. Removed from dish and transferred to a wide mouth 4 oz spin.

Cap the bottle and store the paste sample in the capped bottle at room temperature to reduce the viscosity. HBT 5XW Burtskfield installed on He1ipath Synchro-Lectr (Brookfield 5synchro-Lectr) ic) Measured periodically using a viscometer.

After removing the paste sample, reweigh the composition, compensate for the styrene loss, and The glass fibers were slowly added to the dish with the mixer running on low speed. Next, all After the glass fibers were incorporated into the paste, the mixer was run for approximately 3°. this The short mixing time allowed the glass fibers to be wetted without deterioration. Next, the plate Remove from the mixer and divide the BMC mixture into approximately 1200g each. Removed using a patula and transferred to aluminum foil placed on a weighing plate. . Wrap the divided formulations airtight in aluminum foil (to prevent styrene loss due to evaporation). at room temperature until the viscosity of the retained paste sample reaches the appropriate molding viscosity. Stored. The weight of BMC added to the foil will vary depending on the molding application.

Chopped glass fiber (1 inch) 30-25% Based on the total weight of resin, monomer, and low profile additives <I) ph amount. The numbers in the right column indicate the respective percentages of composition and glass fiber. vinegar.

All liquid ingredients (each) in a 5 gallon opening on a Toledo scale. Weighed in a mold container. Next, the contents of the container are poured into a high speed Cowles pear tube. Mixed in a disintegrating hood. Start the agitator at a slow speed, then The speed was increased to maximum and the liquids were thoroughly mixed over a period of 2-3 minutes. next, If desired, a mold release agent was added to the liquid and mixed until completely dispersed. next , gradually add the filler from the cod container until a uniform paste is obtained, and then The contents were further mixed with wheat to a minimum temperature of 90°F. Next, if you use Mix the thickener into the paste over a period of 2-3 minutes, stop the mixer, and 175 g of paste was removed from the container and transferred to a wide mouth 4 oz spin. This page The yeast sample was stored in a capped bottle at room temperature and its viscosity was measured using a Heropus stand. HBT SX type Brookfie installed on (He1opath 5tand) Measurements were made periodically using a Ludo Synchro-Leftric Viscometer. Next, the pace The rest of the fibers are further combined with glass fibers (approximately 1 inch fibers) for SMC composition. Added to the doctor box on the shaping machine. Next, this sheet molding material (SMC) is After aging until it reached a molding viscosity, it was molded into a desired molded product.

Apparatus and method for manufacturing molded test panels A set of 18" x 18# chrome-plated flat panels for surface evaluation. Molding was performed on a 200 ton Lawton molding machine with a die. female Insert the mold cavity at the bottom and the male part at the top. Electrically heat the two gold jars, and controlled by separate circuits, so these can be operated at different temperatures . For this molding, the top and bottom temperatures are 295-305'F and 1200'F. A molding material sample of g was used and the thickness of the molded part was 0.120'. 0～ The molding pressure, which can be varied at 1000 psi, was tested at the highest pressure. panel Place on a flat surface, hold flat, weigh, and allow to cool overnight. Four molded panels Measured corner-to-corner in all directions with a micro caliber and is the average of four readings. Shrinkage was measured. These panels were used to examine the surface smoothness, as described above. A 8'x18' flat panel was machined using a highly polished, chrome plated 200 ton Lawton forming machine. Molded with a solid matte metal die mold. Check the exact dimensions of the four sides of this mold. The temperature was measured with an accuracy of 1/10,000th of an inch. Accurately measure the four sides of a flat molded panel The length was measured with the same precision. These measured values were substituted into the following equation.

(a-b)/a=inch/inch shrinkage (However, a = total length of the four sides of the mold, and b = total length of the four sides of the molded panel. total) In this shrinkage suppression test, the circumference of the cooling panel is compared with the circumference of the cooling mold. cooling mold A positive number indicates expansion compared to , and the opposite is true for a negative number. Unit mil/inch is laminate The amount of expansion (+) or contraction (-) in mils/inch (or panel circumference) show.

Evaluation of surface smoothness The exact reproducibility of the reflection of the l'xl' square light grating on the surface of the molded panel makes it possible to Surface smoothness is visually indicated. Quantitative evaluation of surface quality on two panels at the same time Obtained by comparing and selecting the panel with the best reproducibility of the reflection grating.

Repeat this technique until the surface of each panel in the series has been compared to every other panel. I went back. Surface smoothness is the frequency with which a panel was selected as having the best surface quality, i.e. It was measured as the number of times. Therefore, the highest number indicates the best panel and the lowest number indicates the lowest The panel is shown.

BMC results Making bulk molding compositions with and without Desmocap IIA and test the effect of the presence of blocked polyisocyanates in such compositions. did. The ingredients and their amounts are listed in Table I below.

Table I Flexural properties, #3 #4 *Total weight of resin, monomer and low profile additives unless otherwise noted. Amount expressed in parts per 100 parts based on .

The results shown in Table I indicate that the blocked polyisocyanate was a composite lacking this additive. Regarding the material, it can lead to an increase in the flexural properties of the resulting composite material. This shows that. Control formulation Example 3 contains blocked isocyanates. It is about 20% lower in flexural strength than Example 4, which is a material containing Produces laminates that are approximately 40% lower in energy. in fracture versus flexural strength. The greater increase in It has been shown that greater amounts of deflection can be achieved. Furthermore, this improvement At a relatively low level (standard) of 1 phr (parts per 100 parts of resin) Obtained.

Blocked polyisocyanate and additional amounts of styrene monomer Experimental bulk molding compositions were prepared. And one of these attempts (Example 8 ), an additional reactive polyol UCARVYES-4 was included. child The composition breakdown and test results for these compositions are shown in Table 2 below.

Table■ Blocked isocyanate effect #5 #6 #7 #8 1 Flexural properties: #5 #6 #7 #8 89 Surface properties: #5 #6 #7 # 8 #9* Unless otherwise noted on the side, resins, monomers and low profile additives L expressed in parts per 100 parts based on the total weight a) The material was pre-dissolved in LP-4OA prior to addition to the formulation.

The results shown in Table ■ show that blocked polyisocyanates have increased flexural strength and This further proves that it imparts destructive energy. Blocked polyisotope Control materials #5 and #9 containing no anate contain blocked polyisocyanate. Approximately 33% lower in strength and fracture energy than test composites #6 and #7 containing approximately 60% lower in Rugie. Again, these results are relatively low-level. was achieved in blocked polyisocyanates. blocked polyisocyanate Example #8 containing the reactive polyol UCARVYES-4 in addition to showed an increase in flexural strength over the composites of Test Examples #6 and #7.

Table ■ also includes the surface properties, surface smoothness and shrinkage control of the test composites. Block Polyisocyanate made a small but positive contribution to shrinkage control. . Even more noteworthy in Example #8, reactive polyol UCAR V The addition of YES-4 substantially improves the surface quality of the composite material.

Several test compositions based on the 2MC formulation were prepared. Those compositions are that Each contains one of two blocked polyisocyanates, and three or additional Contains a reactive polyol. Styrene levels also fluctuated.

These compositions and component amounts are shown in Table 2 below.

Table m Blocked isocyanate and various polyol components Example number #lOall #12 #13 114 Surface characteristics: #10 #11 #12 #13 114 Surface smoothness (freg) 10 15 22 27 9 Shrinkage inhibition 1 m (ail/in) 0.263 0.361 0.333 0.374 0. 182 Umbrella Unless otherwise noted, all resins, monomers and low profile additives Amount expressed in parts per 100 parts by weight.

a) The material was pre-dissolved in LP-40A prior to introduction into the formulation.

In Table ■, blocked polyisocyanate Desmocap IIA and 1 2A based on polyester resin for surface quality, shrinkage control and bending properties. It was evaluated in 2MC formulation. Also Desmocap IIA is UCARO Polyisocyanate-reactive polystyrene such as VYES-4 and TONE 0301 mixed with oar. The control formulation contained LP-40A.

In evaluating surface quality, the actual results of compositions containing blocked polyisocyanates were evaluated. All were qualitatively superior to control compositions lacking these additives. On top of that, Reactive Bo IJ t-Luno UCAR@VYES-4 and HiTONE 0301 The panel containing 〇 has a shrinkage control value >+0.300 and also has good gloss. It had excellent surface quality. These were the best panels for surface quality evaluation.

In a flexural characterization study, control laminate #1 containing only LP-40A 4 is a typical BMC flex strength of about 11,000 psi and about 3.4 inch-bond It reached a value slightly higher than the destructive energy of Do. Desmocap IIA and Composition containing both polyol coupling agent UCAR VYES-4 #12 has the highest flex of all compositions containing Desmocap IIA strength and fracture energy, i.e. 17.150 psi and 6.5 psi, respectively. However, a composition containing only Desmocap I]A #IO could corroborate previous results that showed a significant increase in flexural properties. flexural strength of 10.1350 and energy at failure of 2.9 inch-bond. did. To obtain a consistent increase in flex performance from blocked polyisocyanates, The addition of a reactive polyol such as UCAROVYES-4 is necessary for I think that the.

Some residual unreacted polyisocyanate is present in these laminates To determine whether Ki (postbake) Shita. Bending of baked vs. unbaked laminates Comparing the results, it can be seen that there is almost no difference between the two. Therefore, during the production process It is believed that most blocked polyisocyanates will react.

Other block topos in the presence of UCAROVYES-4 of the first polyol Other test compositions for evaluating the effectiveness of lysocyanates are discussed above. The composition was prepared in the same manner as the above composition. Their components and amounts are shown in Table 3 below.

Table■ Blocked isocyanate and first polyol component Example number 115 116 #17 118 g19 120 #21 #22 #23 Kaku Song characteristics: 枦　轻　厀　匪　Muyu　Mukan　bird　Lobs　L】Impact characteristics:　Mudan　1 16 J [Mudan 119 L set bird star type surface characteristics: 115 116 11 7 08 119 120 122 123 pieces Unless otherwise noted, resin, Parts per hundred based on total weight of monomer and low profile additives Therefore, the indicated amount.

a) LPS-40AC, UCARVYES-4 and styrene were introduced into the formulation Both were pre-dissolved before use.

These tests involve synthetic blocked isocyanates combined with reactive polyols. It has been shown that it works well when used. Reactive ports lacking blocked isocyanates Riolu produces unsatisfactory results. Blocked polyisocyanate as described above Nate's Desmocap 12A and polyol's UCAR@VYES- 4 with or without the use of The curing of these additives was tested. The ingredients and amounts are shown in the table SMC below. Confirmation that Example number *Unless otherwise noted, total weight of resin, monomer and low profile additives Amount expressed in terms of number of copies per 100 copies.

a) The material was pre-dissolved in LP-4OA prior to introduction into the formulation.

Table V shows the addition of blocked polyisocyanate and additional polyol in the formulation. 2 shows an increase in physical properties in sheet molding compositions as a result of LP-4 Approximately 55% greater in flexural strength and fracture energy than the OA counterpart, respectively. An increase of 75% was observed. Don't you think Izotsu's results are dramatic? It's higher than that.

Other embodiments of the invention may be found herein or for practicing the invention disclosed herein. It will be clear to those skilled in the art upon consideration of the following. The specification and examples are provided by way of example only. The true scope and gist of the invention should be considered as exemplary only, and the true scope and gist of the invention is determined by the claims. Indicated by

Continuation of front page C08G 18/70 NFM 8620-4JCO8L 67106 MSJ 8933-4JI (72) Inventor Rex, Garry, C

Claims (9)

[Claims] 1. a) unsaturated polyester resin; b) olefinically unsaturated monomer; c) thermoplastic low profile additives; d) reinforcing filler; including and further e) Blocked polyisocyanate; and f) What is the unsaturated polyester resin? different isocyanate-reactive substances; A thermosetting molding composition comprising: 2. The blocked polyisocyanate is tetramethylene diisocyanate, Hexamethylene diisocyanate (HMDI), 1,4-cyclohexane diiso Cyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate ate (IPDI), xylene diisocyanate, 4,4'-diphenylmethane Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate socyanate, and toluene diisocyanate (TDI) or methylene diphenylate Diisocyanate (MDI) or its polymerized form (polymerized MDI) and polyal Isocyanate-containing prepolymer produced by reaction with Kylene oxide diol The claimed block form of a polyisocyanate selected from the group consisting of Molding composition of Range 1. 3. The isocyanate-reactive substance is a polyether polyol, the unsaturated polyol, Polyester polyols different from ester resins, hydroxyl group-containing vinyl polymers from the group consisting of amine-terminated polyols, diamines and polyamines The molding composition of claim 1 selected. 4. The respective amounts are polyester resin excluding reinforcing fillers, monomers and low polymers. The following, expressed in parts per 100 parts based on the total amount of profile additives: Thermosetting molding compositions containing qualities: a) 20 to 50 pph of unsaturated polyester resin; b) 30 to 70 pph of olefinically unsaturated monomer; c) 5 to 25 pp poly(vinyl acetate) thermoplastic low profile additive h; d) 5 to 75% by weight, based on the total composition, of reinforcing fillers; e) Toluene diisocyanate (TDI) or methylene diphenyl diisocyanate Anate (MDI) or its polymerized form (polymerized MDI) and polyalkyleneoxy Selected from isocyanate-containing prepolymers produced by reaction with dodiol. Blocked polyisocyanate, which is a block form of selected polyisocyanate 1 to 20 pph; and f) polyether polyol, a polyester different from the unsaturated polyester resin terpolyols, and hydroxyl groups each having a primary hydroxyl group 1 to 20 pph of a polyol selected from the group consisting of vinyl polymers. 5. the below described: A. a) unsaturated polyester resin; b) olefinically unsaturated monomer; c) thermoplastic low profile additives; d) reinforcing filler; including and further e) Blocked polyisocyanate; and f) What is the unsaturated polyester resin? Different isocyanate reactive substances: B. producing a thermosetting molding composition comprising: B. The molding composition is shaped into a desired shape. a step of molding; and C. heating the molded molding composition to cure it; A method of manufacturing a thermosetting reinforced molded composite comprising: 6. The blocked polyisocyanate is tetramethylene diisocyanate, Hexamethylene diisocyanate (HMDI), 1,4-cyclohexane diiso Cyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate ate (IPDI), xylene diisocyanate, 4,4'-diphenylmethane Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate socyanate, and toluene diisocyanate (TDI) or methylene diphenylate Diisocyanate (MDI) or its polymerized form (polymerized MDI) and polyal Isocyanate-containing prepolymer produced by reaction with Kylene oxide diol The claimed block form of a polyisocyanate selected from the group consisting of Scope 5 method. 7. The isocyanate-reactive substance is a polyether polyol, the unsaturated polyol, Polyester polyols different from ester resins, hydroxyl group-containing vinyl polymers from the group consisting of amine-terminated polyols, diamines and polyamines The method of claim 5 being selected. 8. A molded thermoset reinforced product made with the composition of claim 1. 9. A molded thermoset reinforced product produced by the method of claim 1.