JPS6343416B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fiber-reinforced unsaturated polyester resin composition. Fiber-reinforced unsaturated polyester compositions are widely used in fields such as fishing boats, bathtubs, tanks, septic tanks, building materials, industrial parts, and automobile parts due to their excellent physical and chemical performance and ease of molding. Recently, there has been a call for higher strength in various fields in terms of design and other aspects. In order to meet these demands, the present inventors conducted extensive studies on high-strength fiber-reinforced unsaturated polyester resin compositions, and found that (a) urethane groups obtained by reacting an unsaturated compound having a hydroxyl group with an isocyanate compound; (b) A compound having a urea group or a biuret group obtained by reacting an unsaturated primary amino compound and an isocyanate compound; (c) A β- compound obtained by reacting an unsaturated epoxy compound and a primary amino compound. A compound having a hydroxyamino group, a nitrogen atom (N-
By using an unsaturated compound containing at least one H) in the molecule alone or in combination of two or more in an unsaturated polyester resin and a fiber reinforcing material, compared to conventional fiber reinforced unsaturated polyester resin compositions, The inventors discovered that it was possible to obtain a molded product with extremely high strength, and 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, chlormaleic 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. Also, (un)
The terminal end of the saturated polyester may be further vinyl-modified with, for example, glycidyl (meth)acrylate, and the unsaturated polyester used in the present invention may include (meth)acrylates of bisphenol A glycidyl ether, polyfunctional It may also contain a terminal vinyl compound such as (meth)acrylates of 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, what can be used together with the unsaturated polyester resin and the fiber reinforcing material to significantly improve the strength of the molded product is "(a) a urethane group obtained by reacting an unsaturated compound having a hydroxyl group with an isocyanate compound" (b) a compound having a urea group or a biuret group obtained by reacting an unsaturated primary amino compound with an isocyanate compound; (c) a β compound obtained by reacting an unsaturated epoxy compound with a primary amino compound. -A compound with a hydroxyamino group, a nitrogen atom (N-) with an active hydrogen selected from
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 when used with fiber reinforcement, the adhesion between the fiber reinforcement and resin is significantly superior to that of conventional materials. It is thought that this makes it possible to give molded products with high strength.The reaction leading to the unsaturated compound is carried out so that the ratio of the number of reacting groups is about 1, and well-known techniques are used to prevent the formation of polymer components as much as possible. It is desirable to design the reaction according to the method used. Unsaturated compounds having a hydroxyl group used to produce an unsaturated compound having a urethane bond include β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, N - Any compound can be used as long as it contains an unsaturated group copolymerizable with an unsaturated polyester resin such as methylol acrylamide, and also contains a hydroxyl group that can react with an isocyanate group. Monoisocyanate compounds such as phenyl isocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate,
Diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and naphthalene diisocyanate; polyisocyanates such as polymethylene polyphenyl isocyanate; and terminal hydroxy groups of glycols, saturated polyester polyols, or polyether polyols with diisocyanate compounds. react,
Molecular weight 500~ with isocyanate group added to the end
5000 isocyanate prepolymers. The unsaturated primary amino compound used in the unsaturated compound having a urea group or a biuret group includes an unsaturated group that can be copolymerized with an unsaturated polyester resin such as acrylamide, and a primary amino group that can react 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. Any compound that can react with commonly used epoxy compounds may be used, such as methylamine,
Ethylamine, propylamine, octylamine, cyclohexylamine, benzylamine, aniline, 3-methoxypropylamine, N-acetylethylenediamine, dimethylaminopropylamine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, ethylenediamine, diethylenetriamine , triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, urea, 1,3-diaminopropane, iminobispropylamine, etc. are used. The number of nitrogen atoms (NH) having active hydrogen contained in the unsaturated compound of the present invention is at least 1
If there are only a few, the strength will be sufficiently improved, but if the number is increased, the strength will be even better. In addition, when an unsaturated compound having a urethane group is used as the unsaturated compound, it not only improves strength but also has excellent fatigue resistance, abrasion resistance, water resistance, and chemical resistance. preferable. In the present invention, the amount of the unsaturated compound used is preferably in the range of 1 to 100 parts by weight, preferably 3 to 50 parts by weight, per 100 parts by weight of the unsaturated polyester resin. As the fiber reinforcing material, glass fibers, carbon fibers, graphite fibers, organic fibers, milled fibers, etc. are suitably used, but in some cases, fibrous substances such as cotton flock and whiskers can also be used. These fiber reinforcement materials are 1 to 10% of the total amount of (1) unsaturated polyester resin and (2) unsaturated compounds that form the resin.
It may be used in an amount of 90% by weight, preferably 10 to 80% by weight. The fiber-reinforced unsaturated polyester resin composition of the present invention can be prepared by adding an unsaturated compound to an unsaturated polyester resin and further mixing or impregnating a fiber reinforcing material, or by mixing all three together. It can be prepared. Furthermore, since the resin composition can be cured by the same curing means as conventional unsaturated polyester resins, any curing agent used for conventional unsaturated polyester resins can be used. Hardening agents include ketone peroxides, diacyl peroxides, hydroperoxides,
Any known organic peroxide such as dialkyl peroxides, alkyl peresters, and percarbonates 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. In addition, the composition of the present invention may contain known additives such as colorants, thixotropic agents, hardening modifiers, and lightweight aggregates such as hollow ceramics, hollow glass, or hollow graphite spheres, depending on the use and purpose. . The fiber-reinforced unsaturated polyester resin composition of the present invention can be applied by hand lay-up method, spray-up method,
filament winding method, resin injecting method, vacuum injecting method,
Matsushidodai method, cold press method, bag method,
It is suitable for manufacturing ships, building materials, housing equipment, transportation equipment, bathtubs, containers, tanks, etc. by all known so-called wet forming methods such as the pultrusion method. 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 98g (1.0 mol), phthalic anhydride
296g (2.0mol), propylene glycol 235.6g
66 parts by weight (hereinafter abbreviated as "parts") of an unsaturated polyester with an acid value of 30 or less obtained by dehydrating (3.1 mol) in an inert gas stream at 200 to 220°C while stirring, 0.005 parts by weight of hydroquinone Styrene with parts
An unsaturated polyester resin [] was prepared by mixing and dissolving in 34 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.
Heat to 200-210°C and react with stirring until the acid value reaches 50 or less, then add propylene glycol 87.4
An unsaturated polyester with an acid value of 30 or less obtained by adding 232 g (2.0 mol) of fumaric acid and 232 g (2.0 mol) of fumaric acid and carrying out a dehydration reaction while heating and stirring at 200 to 220°C.
66 parts of styrene 34 with 0.005 parts of hydroquinone
Unsaturated polyester resin mixed and dissolved in
adjusted. Example 1 Phenyl isocyanate 119 g (1.0 mol), β
-Hydroxyethyl methacrylate 136.5g
(1.05 mol) and 0.06 g of p-benzoquinone are placed in a closed container equipped with a stirrer, heated and stirred at 70 to 80°C while being careful to avoid sudden heat generation, and when the reaction has sufficiently progressed, 1 g of methanol is added and further 1 hour. The reaction was carried out by heating to completely eliminate the remaining isocyanate to obtain a β-hydroxyethyl methacrylate adduct of phenyl isocyanate. Unsaturated polyester resin obtained in Production Example 1 []
100 parts of thixotropic agent silicon oxide (trade name Aerosil)
1 part mechanically dispersed, 6% cobalt naphthenate
0.3 parts were mixed to obtain a reddish-purple formulation. 100 parts of this formulation was added with β of the above phenyl isocyanate.
- Mix 10 parts of hydroxyethyl methacrylate adduct and 1 part of 55% methyl ethyl ketone peroxide and mix with glass fiber tip mat (450g/
^m2 ), glass content 31%, thickness 3.0±
A 0.2 mm laminated molded product was obtained. Example 2 Diphenylmethane diisocyanate 286g (1.0
mole), β-hydroxyethyl methacrylate
273 g (2.1 mol) and 0.65 g of p-benzoquinone were placed in a closed container with a stirrer, heated and stirred at around 90°C while being careful not to cause sudden heat generation, and when the reaction had sufficiently progressed, 1 g of methanol was added and the mixture was further stirred. The reaction was carried out by heating for a period of time to completely eliminate the remaining isocyanate, thereby obtaining a β-hydroxyethyl methacrylate 2-adduct of diphenylmethane diisocyanate. The same recipe as in Example 1 except that the unsaturated polyester resin [] obtained in Production Example 2 was used as the unsaturated polyester resin, and the β-hydroxyethyl methacrylate diadduct of diphenylmethane diisocyanate was used as the unsaturated compound. A laminate molded product with a glass content of 30% and a thickness of 3.0±0.2 mm was obtained. 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 not to generate sudden heat, and quantify isocyanate until the isocyanate is completely disappeared. The reaction yielded an acrylamide diadduct of tolylene diisocyanate. The same recipe was used 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 mentioned above was added as the unsaturated compound, and the glass content was 30% and the thickness was A laminated molded product with a diameter of 3.0±0.2 mm was obtained. Example 4 Glycidyl methacrylate 142 g (1.0 mol),
135 g (1.05 mol) of octylamine and 0.28 g of p-benzoquinone were placed in a closed container with a stirrer.
The reaction was carried out with stirring at room temperature while being careful to avoid sudden heat generation, and the reaction was allowed to proceed until the epoxy group completely disappeared to obtain an octylamine adduct of glycidyl methacrylate. The same formulation was used 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 mentioned above was used as the unsaturated compound, and the glass content was 30% and the thickness was A laminated molded product with a diameter of 3.0±0.2 mm was obtained. Comparative Example 1 1 part of silicon oxide (trade name Aerosil) as a thixotropic agent was mechanically dispersed in 100 parts of the unsaturated polyester resin prepared in Production Example 1, and 0.3 part of 6% cobalt naphthenate was mixed to form a reddish-purple compound. I got something.
One part of 55% methyl ethyl ketone peroxide was mixed with this mixture and impregnated into a glass fiber chop mat (450 g/m ² ) to obtain a laminate molded product having a glass content of 31% and a thickness of 3.0±0.2 mm. Comparative Example 2 Using the unsaturated polyester resin prepared in Production Example 2, and using the same formulation as in Comparative Example 1,
A laminated molded product with a glass content of 30% and a thickness of 3.0±0.2 mm was obtained. Bending strength and tensile strength tests of the laminated molded products of Examples 1 to 4 and Comparative Examples 1 to 2 were conducted according to JIS-K-6911. The test results are shown in Table-1.

[Table] From the results in Table 1, the bending strength of the product of the present invention,
It is clear that the tensile strength is extremely good. 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.

Claims (1)

[Claims] 1. Unsaturated polyester resin. 2 (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;
An unsaturated compound containing at least one H) in its molecule. 3. A fiber-reinforced unsaturated polyester resin composition consisting of a fiber-reinforced material.