JPS6343417B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated polyester resin molding material that is easy to mold and provides a high-strength molded product. In general, sheet molding compound (hereinafter abbreviated as SMC) is a compound made by mixing unsaturated polyester resin with thermoplastic resin, fillers, colorants, hardening agents, thickeners, etc., and is spread on a film and reinforced with fibers. Bulk Molding Compound (hereinafter abbreviated as BMC) is produced by impregnating the material, then covering it with a film and compressing it appropriately to ensure sufficient impregnation and thickening.
The molding material is produced in bulk by kneading these compounds with a fiber reinforcing material and impregnating and thickening the compound. SMC and BMC molding materials are widely used in fields such as bathtubs, tanks, septic tanks, building materials, industrial parts, automobile parts, and electrical parts due to their good moldability and work environment. For these reasons, there is a call for higher strength in each field. Conventional methods for obtaining high-strength molded products include increasing the content of fiber reinforcing material and using long fibers. However, these methods have the disadvantage that fluidity and impregnation properties are poor, leading to deterioration of molding processability, and furthermore, the appearance of the molded product is poor. As a result of intensive research into high-strength molding materials that eliminate these drawbacks and have excellent molding processability and molded product appearance, the present inventors have determined that certain unsaturated compounds can be added to unsaturated polyester resins, thickeners, and fibers. The present inventors have discovered that this object can be achieved when used in combination with a reinforcing agent, and have completed the present invention. The unsaturated polyester resin used in the present invention is an aromatic saturated dibasic acid or its acid anhydride, α, β-
Unsaturated polyester produced by polycondensation of an unsaturated dibasic acid or its acid anhydride and glycol, and in some cases using an aliphatic or alicyclic saturated dibasic acid as the acid component. obtained by dissolving α,β-unsaturated monomer. Aromatic saturated dibasic acids as acid components of unsaturated polyesters include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride,
Halogenated phthalic anhydride and esters thereof are used, and aliphatic or alicyclic saturated dibasic acids include succinic acid, adipic acid, sebacic acid,
Hexahydrophthalic anhydride and esters thereof are used. As the α,β-unsaturated dibasic acid, maleic anhydride, maleic acid, fumaric acid, itaconic acid, citraconic acid, chloromalenic acid, and esters thereof are used. Glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol,
1,4-butanediol, neopentyl glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, 2,2-di(4-hydroxypropoxyfluoride) ethylene oxide, which is an oxide,
Propylene oxide and the like are also useful. Each reaction component is not particularly limited to the above substances as long as it can be polycondensed with the unsaturated polyester. Furthermore, the ends of the unsaturated polyester may be further vinyl-modified with glycidyl (meth)acrylate, etc., and (meth)acrylates of bisphenol A glycidyl ether are included in the unsaturated polyester used in the present invention. , a terminal vinyl compound such as (meth)acrylates of polyfunctional alcohols. The unsaturated polyester used in the present invention preferably has a molecular weight in the range of 1000 to 4000, an acid value in the range of 1 to 50, and a hydroxyl value in the range of 1 to 60, but (meth)acrylates of bisphenol A glycidyl ether, When using a terminal vinyl compound such as (meth)acrylates of polyfunctional alcohols, a molecular weight in the range of 100 to 1000 is sufficient. The α,β-unsaturated monomer used in unsaturated polyester resins is generally styrene, but is not limited to styrene, and includes vinyltoluene, α-methylstyrene, chlorostyrene, and methylmethane. Vinyl monomers or vinyl oligomers capable of crosslinking with unsaturated polyesters such as acrylic compounds such as acrylates and allyl compounds such as triallyl cyanurate may be used alone or in combination. In the unsaturated polyester resin, the appropriate proportion of the unsaturated polyester and the α,β-unsaturated monomer is in the range of 30 to 80 parts by weight of the former and 70 to 20 parts by weight of the latter. In the present invention, the unsaturated compound that can be used together with the unsaturated polyester resin, thickener, and fiber reinforcement material to significantly improve the strength of the molded product is as follows:
“(a) A compound having a urethane group obtained by reacting an unsaturated compound having a hydroxyl group with an isocyanate compound, (b) A urea group or a biuret group obtained by reacting an unsaturated primary amino compound with an isocyanate compound. (c) a compound having a β-hydroxyamino group obtained by reacting an unsaturated epoxy compound with a primary amino compound
H) in its molecule.The unsaturated group in the unsaturated compound means an ethylenic bonding group that can be copolymerized with an unsaturated polyester resin. It can be copolymerized with unsaturated polyester resin to impart excellent adhesion and strength to the resin, but it does not deteriorate moldability even when used together with thickeners and fiber reinforcing materials.
Furthermore, since the adhesion between the fiber reinforcing material and the resin is significantly better than that of the conventional method, it is thought that it is possible to provide a high-strength molded product with an excellent molded product appearance. It is desirable that the reaction leading to the unsaturated compound be carried out so that the ratio of the number of reacting groups is approximately 1, and that the reaction be designed according to well-known technical means so as to prevent the formation of polymer components as much as possible. Unsaturated compounds having hydroxyl groups used to produce unsaturated compounds having urethane bonds include unsaturated polyester resins such as β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, N-methylolacrylamide, etc. Any compound can be used as long as it contains a copolymerizable unsaturated group and also contains a hydroxyl group that can react with an isocyanate group. In addition, isocyanate compounds include monoisocyanate compounds such as phenyl isocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, xylylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, 2,4
-Diisocyanates such as tolylene diisocyanate, 2,6-tolylene diisocyanate, and naphthalene diisocyanate; polyisocyanates such as polymethylene polyphenyl isocyanate;
and isocyanate prepolymers having a molecular weight of 500 to 5,000, which are obtained by reacting the terminal hydroxy groups of glycol, saturated polyester polyol, or polyether polyol with a diisocyanate compound and adding isocyanate groups to the terminals. The unsaturated primary amino compound used in the unsaturated compound having a urea group or Biuret group contains an unsaturated group copolymerizable with an unsaturated polyester resin such as acrylamide, and also contains a primary amino group capable of reacting with an isocyanate group. Any compound can be used as long as it contains it. Unsaturated compounds having a β-hydroxyamino group can be obtained by an addition reaction between an unsaturated epoxy compound and a primary amino compound. Examples of unsaturated epoxy compounds include glycidyl (meth)acrylate, allyl glycidyl ether, etc. Methylamine, ethylamine, propylamine, octylamine, cyclohexylamine, benzylamine, aniline, 3-methoxypropylamine, N-acetylethylenediamine, dimethylaminopropyl, as long as the compound can react with commonly used epoxy compounds. Amine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, ethylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, urea, 1,3-diaminopropane,
Iminobispropylamine and the like are used. If the number of nitrogen atoms (N-H) with active hydrogen contained in the unsaturated compound of the present invention is at least one, the strength will be sufficiently improved, but if the number is increased, the strength will be even better. Become. In addition, when an unsaturated compound having a urethane group is used as the unsaturated compound, it is possible to obtain a product with improved strength as well as excellent fatigue resistance, abrasion resistance, water resistance, and chemical resistance. is preferable. In the present invention, the amount of the unsaturated compound used is preferably 1 to 100 parts by weight, preferably 3 to 50 parts by weight, per 100 parts by weight of the unsaturated polyester resin. Thickeners include inorganic thickeners such as alkaline earth metal oxides or hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide, as well as tolylene diisocyanate (TDI), 4, Organic thickeners of the polyisocyanate type such as 4'-diphenylmethane diisocyanate (MDI) and crude MDI can be used. The amount of thickener used is the total amount of (1) unsaturated polyester resin and (2) unsaturated compound that form the resin.
0.1 to 20 parts by weight per 100 parts by weight, preferably 0.5
~10 parts by weight is good. As the fiber reinforcing material, glass fibers, carbon fibers, graphite fibers, organic fibers, milled fibers, etc. are preferably used, but in some cases, fibrous substances such as cotton flock and whiskers can also be used. These fiber reinforcements form a resin, preferably 1 to 90% by weight of the total amount of (1) unsaturated polyester resin and (2) unsaturated compound.
It may be used within a range of % by weight. The unsaturated polyester resin molding material of the present invention can be prepared by any suitable means, and can be cured by the same means as conventional unsaturated polyester resins. The curing agent is a known organic peroxide used in ordinary unsaturated polyester resins, such as ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, alkyl peresters, and percarbonates. Any of these can be used, and in some cases, a known curing accelerator may be used in combination. As hardening accelerators, naphthenic acids cobalt, potassium, calcium, barium, tin, zinc,
Copper, nickel, zirconium, etc. salts, octenoic acid salts of cobalt, calcium, tin, vanadium, manganese, etc., polyvalent metal organic acid salts such as oleic acid cobalt salts, dimethylaniline, diethylaniline, ethylenediamine, Tertiary amines such as ethylenediamine are also used.
The curing agent and curing accelerator are appropriately selected depending on the molding temperature. Moreover, various additives can be used in the molding material of the present invention depending on the use and purpose. For example, thermoplastic resins such as polystyrene polyethylene, polyacrylate, polyvinyl acetate, and saturated polyester are used alone or in combination as low-shrinkage agents in order to prevent curing shrinkage during molding and obtain dimensional stability of molded products. Fillers also improve processing properties, reduce shrinkage, lower cost, and improve physical properties. Various fillers are compatible, such as calcium carbonate, aluminum hydroxide, kaolin, barium sulfate, zinc stearate, as well as hollow ceramic, hollow glass or hollow graphite spheres to reduce the density of the final molding. be able to. In addition, colorants, additives for curing adjustment, etc. may be used depending on the use and purpose, and these may be those used in conventional unsaturated polyester resin molding materials. The unsaturated polyester resin molding material of the present invention is molded at high temperature by compression molding, transfer molding, injection molding, etc., and has a wide range of uses in fields such as bathtubs, building materials, industrial parts, electrical parts, and automobile parts. The invention will be more easily understood with reference to the following examples. It should be noted that these Examples merely illustrate the present invention and do not limit it in any way. Production example 1 (Production of unsaturated polyester resin []) Maleic anhydride 196g (2 mol), phthalic anhydride
148g (1 mol), propylene glycol 239g
65 parts by weight (hereinafter abbreviated as "parts") of unsaturated polyester with an acid value of 30 obtained by dehydrating (3.15 mol) in an inert gas stream at 200 to 220°C while stirring were mixed with 0.005 part of hydroquinone and 35 parts by weight of styrene. The unsaturated polyester resin [] was prepared by mixing and dissolving the two parts. Production Example 2 (Production of unsaturated polyester resin) 166 g (1.0 mol) of isophthalic acid and 152 g (2.0 mol) of propylene glycol were added in an inert gas stream.
While heating and stirring at 200-210℃, react until the acid value reaches 50 or less, then add propylene glycol.
87.4 g (1.15 mol), fumaric acid 232 g (2.0 mol) were added, and the unsaturated polyester 65 with an acid value of 30 was obtained by dehydrating the mixture while heating and stirring at 200 to 220°C.
1 part was mixed and dissolved in 35 parts of styrene together with 0.005 parts of hydroquinone to prepare an unsaturated polyester resin. Example 1 Phenyl isocyanate 119 g (1.0 mol), β
-Hydroxyethyl methacrylate 136.5g
(1.05 mol) and 0.06 g of p-benzoquinone were placed in a closed container equipped with a stirrer, heated and stirred at 70 to 80°C while being careful not to suddenly generate heat, and when the reaction had sufficiently progressed, 1 g of methanol was added and further The reaction was carried out by heating for 1 hour to completely eliminate the remaining isocyanate, thereby obtaining a β-hydroxyethyl methacrylate adduct of phenyl isocyanate. A blend obtained by kneading 95 parts of the unsaturated polyester resin prepared in Production Example 1 with 1 part of t-butyl perbenzoate as a curing agent, 2 parts of zinc stearate, and 2 parts of magnesium oxide as a thickener.
100 parts plus the β-hydroxyethyl methacrylate adduct of phenyl isocyanate described above 10
After mixing the parts, the SMC impregnating machine produces 1 inch glass roving chips with 60% SMC content.
was manufactured. SMC is rolled into a roll with 40 to 50
A SMC molding material was produced by aging at ℃ for 24 hours. Example 2 Diphenylmethane diisocyanate 286g (1.0
mole), β-hydroxyethyl methacrylate
273g (2.1mol) and 0.65g p-benzoquinone
Pour the mixture into a closed container with a stirrer, heat and stir at around 90℃ while being careful not to suddenly generate heat, and when the reaction has sufficiently progressed, add 1 g of methanol and heat the reaction for another 1 hour to completely remove the remaining isocyanate. β of diphenylmethane diisocyanate by annihilation
-Hydroxyethyl methacrylate diadduct was obtained. Same as Example 1 except that the unsaturated polyester resin () obtained in Production Example 2 was used as the unsaturated polyester resin, and the above β-hydroxyethyl methacrylate diadduct of diphenylmethane diisocyanate was used as the unsaturated compound. An SMC molding material with a glass content of 60% was obtained using the following recipe. Example 3 Tolylene diisocyanate 174g (1.0mol),
Charge 145.6 g (2.05 mol) of acrylamide and 0.32 g of p-benzoquinone in a closed container with a stirrer, heat and stir at 70 to 80°C while being careful to avoid sudden heat generation, and quantify isocyanate until the isocyanate is completely destroyed. The reaction was carried out to obtain an acrylamide diadduct of tolylene diisocyanate. Example 1 except that the unsaturated polyester resin [] obtained in Production Example 2 was used as the unsaturated polyester resin, and the acrylamide diadduct of tolylene diisocyanate was used as the unsaturated compound.
An SMC molding material with a glass content of 60% was obtained using the same recipe. Example 4 Glycidyl methacrylate 142 g (1.0 mol),
135 g (1.05 mol) of octylamine and 0.28 g of p-benzoquinone are placed in a sealed container equipped with a stirrer, and stirred at room temperature while being careful to avoid sudden heat generation. An octylamine adduct of was obtained. Glass was prepared in the same manner as in Example 1, except that the unsaturated polyester resin [] obtained in Production Example 2 was used as the unsaturated polyester resin, and the octylamine adduct of glycidyl methacrylate was used as the unsaturated compound. An SMC molding material with a content of 60% was obtained. Comparative Example 1 95 parts of the unsaturated polyester resin prepared in Production Example 1 was mixed with 1 part of t-butyl perbenzoate as a hardening agent, 2 parts of zinc stearate, and 2 parts of magnesium oxide as a thickener. A 1-inch glass roving chop content of 60% SMC was produced using an SMC impregnation machine using the same formulation.
The SMC was wound into a roll and aged at 40 to 50°C for 24 hours to produce an SMC molding material. Comparative Example 2 Using the unsaturated polyester resin prepared in Production Example 2, and using the same formulation as shown in Comparative Example 1 below, a 1-inch glass roving chop with a content of 60
% of SMC molding materials were produced. SMC obtained in Examples 1 to 4 and Comparative Examples 1 to 2
The molding material was heated at a temperature of 140℃, a pressure of 100Kg/cm ² , and a time of 3.
The mixture was heated and compression molded for 30 minutes to obtain a flat plate measuring 30 cm x 30 cm x 3 mm. A test piece was prepared from this flat plate and subjected to bending strength, tensile strength, and Izot impact tests. The test results are summarized in Table-1.

[Table] Table 1 shows that the molding material of the present invention provides significantly superior strength. Furthermore, the molded products obtained in Examples 1 and 2 had good fatigue resistance, abrasion resistance, water resistance, and chemical resistance, and were highly durable. Example 5 35 parts of the unsaturated polyester resin prepared in Production Example 2, 10 parts of a 40% styrene monomer solution of polystyrene with a degree of polymerization of 2500, 50 parts of calcium carbonate,
To 100 parts of a blend obtained by dispersing and kneading 0.5 parts of t-butyl perbenzoate, 2 parts of zinc stearate, and 0.5 parts of magnesium oxide, 10 parts of β-hydroxyethyl methacrylate of phenyl isocyanate used in Example 1 was added. After adding and mixing,
SMC was produced by dispersing 1-inch glass roving chops to a glass content of 30% using an SMC impregnation machine. This was aged at 40 to 50°C for 24 hours to obtain an SMC molding material. Example 6 β of phenyl isocyanate used in Example 5
-The same recipe as in Example 5 except that 10 parts of β-hydroxyethyl methacrylate 2 adduct of phenylmethane diisocyanate used in Example 2 was used in place of 10 parts of hydroxyethyl methacrylate, with a glass content of 30. % SMC molding material was obtained. Example 7 β of phenyl isocyanate used in Example 5
-SMC with a glass content of 30% using the same recipe as in Example 5 except that 10 parts of the acrylamide diadduct of tolylene diisocyanate used in Example 3 was used in place of 10 parts of hydroxyethyl methacrylate.
A molding material was obtained. Example 8 β of phenyl isocyanate used in Example 5
-The same formulation as in Example 5 except that 10 parts of the octylamine adduct of glycidyl methacrylate used in Example 4 was used in place of 10 parts of hydroxyethyl methacrylate, and a glass content of 30% was used.
An SMC molding material was obtained. Comparative Example 3 Unsaturated polyester resin 35 prepared in Production Example 2
parts, 10 parts of 40% styrene monomer solution of polystyrene with a degree of polymerization of 2500, 50 parts of calcium carbonate, 0.5 parts of t-butyl perbenzoate, 2 parts of zinc stearate.
SMC
An impregnation machine disperses 1 inch glass roving chops to a glass content of 30%.
Manufactured SMC. This was aged at 40 to 50°C for 24 hours to obtain an SMC molding material. The SMC molding materials of Examples 5 to 8 and Comparative Example 3 were heat compression molded at a temperature of 140° C., a pressure of 100 Kg/cm ² , and a time of 3 minutes to obtain flat plates of 30 cm x 30 cm x 3 mm. Test pieces were cut out from this molded product, and the bending strength, tensile strength, and strength of the Izot impact test were measured.
The test results are summarized in Table 2.

[Table] It is clear that the molding material of the present invention has significantly superior strength. Furthermore, the molding materials obtained in Examples 5 and 6 had good fatigue resistance, abrasion resistance, water resistance, and chemical resistance, and were highly durable.

Claims (1)

[Scope of Claims] 1. An unsaturated polyester resin, 2. (a) A compound having a urethane group obtained by reacting an unsaturated compound having a hydroxyl group and an isocyanate compound, (b) An unsaturated primary amino compound and an isocyanate compound. (c) a compound having a β-hydroxyamino group obtained by reacting an unsaturated epoxy compound with a primary amino compound, and having an active hydrogen selected from Nitrogen atom (N-
An unsaturated compound containing at least one H) in its molecule. 3. An unsaturated polyester resin molding material consisting of a thickener and 4. a fiber reinforcement.