JPS6343415B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an unsaturated polyester resin composition that has high strength and excellent adhesion. Unsaturated polyester resins are used as paints, as their cured products have good electrical insulation, heat resistance, solvent resistance, and chemical resistance, and are relatively easy to mold.
It is widely used in decorative boards, putty, cast molding, buttons, resin concrete, etc., but recently there has been a demand for unsaturated polyester resins with excellent adhesion and strength. In view of these points, the present inventors have conducted intensive studies on unsaturated polyester resin compositions having excellent adhesion and strength, and have found that (a) a composition obtained by reacting an unsaturated compound having a hydroxyl group with an isocyanate compound; (b) a compound having a urea group or biuret group obtained by reacting an unsaturated primary amino compound with an isocyanate compound; (c) a compound having a urethane group obtained by reacting an unsaturated epoxy compound with a primary amino compound; The resulting compound having a β-hydroxyamino group, a nitrogen atom (N-
It has been discovered that a resin with excellent adhesion and strength can be obtained by adding an unsaturated compound containing at least one H) in the molecule alone or in combination of two or more to an unsaturated polyester resin, and the present invention I was able to complete it. 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 their esters are used, and the aliphatic or alicyclic saturated dibasic acids include succinic acid, adipic acid, sebacic acid, hexahydrophthalic anhydride and their esters. 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) Oxides such as ethylene oxide and propylene oxide are also useful. Each reaction component is not particularly limited to the above substances as long as it is capable of polycondensing unsaturated polyester. In addition, (the terminal end of the unsaturated polyester may be further vinyl-modified with glycidyl (meth)acrylate, etc., and (meth)acrylate of bisphenol A glycidyl ether may be added to the range of the unsaturated polyester used in the present invention. The unsaturated polyester used in the present invention has a molecular weight in the range of 1000 to 4000, an acid value of 1 to 50, and a hydroxyl value. is preferably in the range of 1 to 60, but when using terminal vinyl compounds such as (meth)acrylates of bisphenol A glycidyl ether and (meth)acrylates of polyfunctional alcohols, a molecular weight in the range of 100 to 1000 is sufficient. The α,β-unsaturated monomer used in the unsaturated polyester resin is generally styrene, but is not limited to styrene, and includes vinyltoluene, α-methylstyrene, Vinyl monomers or vinyl oligomers capable of crosslinking with unsaturated polyesters such as acrylic compounds such as chlorostyrene and methyl methacrylate, and allyl compounds such as triallyl ciaslate may be used alone or in combination. The appropriate ratio of the saturated polyester and α,β-unsaturated monomer is 30 to 80 parts by weight for the former and 70 to 20 parts by weight for the latter. Those that can impart adhesion and strength are those that have a functional group selected from an isocyanate group, an epoxy group, a carboxylic acid group, a hydroxyl group, and an amino group and that contain one unsaturated group in the molecule. A nitrogen atom with active hydrogen obtained from a compound and a compound containing a group that can react with the above functional group (
In the unsaturated compound, the unsaturated group means an ethylenic bonding group that is copolymerizable with an unsaturated polyester resin. Examples of the unsaturated compound containing at least one nitrogen atom (NH) having an active hydrogen in the molecule include an unsaturated compound having a urethane group obtained by a reaction between an unsaturated compound having a hydroxyl group and an isocyanate compound; An unsaturated compound having a urea group or a biuret group obtained by the reaction of an unsaturated primary amino compound and an isocyanate compound, or an unsaturated compound having a β-hydroxyamino group obtained by the reaction of an unsaturated epoxy compound and a primary amino compound In addition, the reaction leading to the unsaturated compound is preferably carried out so that the ratio of the number of reacting groups is about 1, and the reaction is designed according to well-known technical means so as to prevent the formation of polymer components as much as possible.Urethane bond The unsaturated compound having a hydroxyl group used to produce an unsaturated compound having a Any compound can be used as long as it contains a possible unsaturated group and a hydroxyl group that can react with an isocyanate group.
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, Diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and naphthalene diisocyanate; polyisocyanates such as polymethylene polyphenyl isocyanate; and the terminal hydroxy groups of glycols, polyester polyols, or polyether polyols are reacted with diisocyanate compounds. Examples include isocyanate prepolymers having a molecular weight of 500 to 5,000 and having isocyanate groups added to the ends. Unsaturated primary amino compounds used in unsaturated compounds having urea groups or biuret groups include unsaturated groups that can be copolymerized with unsaturated polyester resins such as acrylamide, and also contain primary amino groups that can react with isocyanate groups. Any compound that can be used can be used. Unsaturated compounds having a β-hydroxyamino group can be obtained by an addition reaction between an unsaturated epoxy compound and a primary amino compound, and unsaturated epoxy compounds include glycidyl (meth)acrylate, allyl glycidyl ether, etc. The primary amino compound may be one that can react with an epoxy compound, such as methylamine, ethylamine, propylamine, octylamine, cyclohexylamine, benzylamine, aniline, 3-methoxypropylamine, N-acetylethylenediamine, dimethylaminopropylamine. , N-aminopropyl-2-pipecoline, ethylenediamine,
Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, urea, 1,3-diaminopropane,
Iminobispropylamine and the like are used. Nitrogen atom (NH) with active hydrogen as described above
The amount of the unsaturated compound having at least one compound in the molecule ranges from 1 to 100 parts by weight, preferably from 3 to 50 parts by weight, per 100 parts by weight of the unsaturated polyester resin. The unsaturated polyester resin composition of the present invention can be cured by the same curing means as conventional unsaturated polyester resins, so any curing agent used for ordinary unsaturated polyester resins can be used. can. Any known organic peroxides such as ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, alkyl peresters, and percarbonates can be used as the curing agent. A known curing accelerator may also be used in combination.
As hardening accelerators, naphthenic acids cobalt, potassium, calcium, barium, tin, zinc, copper,
Salts of nickel, zirconium, etc., or octenoic acid cobalt, calcium, tin, vanadium,
Salts such as manganese, organic acid salts of polyvalent metals such as cobalt salts of oleic acid, and tertiary amines such as dimethylaniline, diethylaniline, ethylenediamine, and triethylenediamine are also used. The curing agent and curing accelerator are appropriately selected depending on the molding temperature. Additionally, known additives may optionally be added according to known techniques, such as calcium carbonate, clay, talc, barium sulfate, zinc stearate, etc.
Wood powder, bamboo grass, paper, pulp, rice husk, cotton, hollow ceramic, hollow glass, or hollow graphite spheres, as well as coloring agents and additives for curing adjustment, are used. When the unsaturated polyester resin composition of the present invention is used in paints, decorative boards, putty, etc., a strong coating film or putty with good adhesion to the substrate can be obtained.
Furthermore, when used in resin concrete, molded products with good adhesion to the filling aggregate and excellent strength can be obtained. 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 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.
was mixed and dissolved in 34 parts of styrene together with 0.005 part of hydroquinone to prepare an unsaturated polyester resin liquid. Production Example 2 (Production of unsaturated compound) Phenyl isocyanate 119g (1.0 mol), β
-Hydroxyethyl methacrylate 136.5g
(1.05 mol) and 0.06 g of p-benzoquinone were placed in a sealed container equipped with a stirrer, heated and stirred at 70 to 80°C while being careful not to cause sudden heat generation, and when the reaction had sufficiently progressed, 1 g of methanol was added, and then 1 g of methanol was added. The reaction was carried out by heating for a period of time to completely eliminate the remaining isocyanate, thereby obtaining a β-hydroxyethyl methacrylate adduct of phenyl isocyanate. Production Example 3 (Production of unsaturated compound) 286 g (1.0 mol) of diphenyl diisocyanate,
β-hydroxyethyl methacrylate 723g
(2.1 mol) and 0.65 g of p-benzoquinone were placed in a closed container equipped 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 for another 1 hour. The reaction was carried out by heating to completely eliminate the remaining isocyanate, thereby obtaining a β-hydroxyethyl methacrylate 2-adduct of diphenylmethane diisocyanate. Production example 4 (Production of unsaturated compound) Tolylene diisocyanate 174g (1.0 mol),
145.6 g (2.05 mol) of acrylamide and 0.32 g of p-benzoquinone were placed in a closed container with a stirrer.
The mixture was heated and stirred at 70 to 80°C, the amount of isocyanate was determined, and the reaction was carried out until the isocyanate completely disappeared to obtain an acrylamide diadduct of tolylene diisocyanate. Production Example 5 (Production of unsaturated compound) Glycidyl methacrylate 142g (1.0 mol),
135 g (1.05 mol) of octylamine and 0.28 g of p-benzoquinone are placed in a closed container equipped with a stirrer, stirred and reacted while being careful to avoid rapid heat generation, and reacted until the epoxy group completely disappears. An adduct was obtained. Comparative Example 1 Unsaturated polyester resin prepared in Production Example 1
Mix 0.3 parts of 6% cobalt naphthenate with 100 parts,
Furthermore, 1 part of 55% methyl ethyl ketone peroxide was stirred and mixed to obtain a casting plate with a thickness of 3 mm. Examples 1 to 4 10 parts of the unsaturated compounds obtained in Production Examples 2 to 5 were added and mixed to 100 parts of the unsaturated polyester resin obtained in Production Example 1, and further 6% cobalt naphthenate and 0.1% by weight were added. , 55% and 1.0% by weight of methyl ethyl ketone peroxide were added and mixed to prepare a casting plate with a thickness of 3 mm. The bending strength of the cast plate was measured in accordance with JIS standards. The test results are summarized in Table-1.

[Table] It is clear from Table 1 that the strength of the unsaturated polyester resin composition of the present invention is significantly improved. Comparative Example 2 Unsaturated polyester resin obtained in Production Example 1
Mix 100 parts with 1 part of 55% methyl ethyl ketone peroxide, 200 parts of silica sand No. 4, 150 parts of silica sand No. 8, and 50 parts of calcium carbonate with a cement mixer, pour into a mold, and vibrate with a vibrator for 3 minutes to defoam. After filling, the concrete was immediately heated and cured in a heating furnace at 60°C for 1 hour, and the mold was demolded to obtain resin concrete in the shape of a rectangular parallelepiped measuring 4 x 4 x 16 (cm). Example 5 10 parts of the β-hydroxyethyl methacrylate 2-adduct of diphenylmethane diisocyanate obtained in Production Example 3 was added to 100 parts of the unsaturated polyester resin obtained in Production Example 1, and the same procedure as in Comparative Example 2 was carried out. Rectangular parallelepiped resin concrete measuring 4 x 4 x 16 (cm) was obtained according to the recipe. The bending strengths of the resin concrete obtained in Comparative Example 2 and Example 5 were 350 Kg/mm 2 and 500 Kg/mm ² , respectively.
It was Kg/ ^mm2 . Furthermore, the resin concrete obtained in Example 5 was strong against impact, had good fatigue resistance, abrasion resistance, water resistance, and chemical resistance, and was highly durable. Comparative Example 3 Unsaturated polyester resin obtained in Production Example 1
2 parts of 6% cobalt naphthenate and talc in 100 parts
200 parts were sufficiently stirred and mixed to prepare a putty. One part of 55% methyl ethyl ketone peroxide was added to the putty obtained, and the mixture was stirred and mixed quickly and uniformly.The putty was coated on a sanded metal plate to a thickness of about 1 mm and cured at room temperature. Example 5 Add 10 parts of the acrylamide diadduct of tolylene diisocyanate obtained in Production Example 4 to 100 parts of the unsaturated polyester resin obtained in Production Example 1, and add enough 2 parts of 6% cobalt naphthenate and 200 parts of talc. The mixture was stirred and mixed to prepare putty, and a metal plate coated with putty to a thickness of about 1 mm using the same formulation as in Comparative Example 3 was obtained. When the putties obtained in Comparative Example 3 and Example 6 were tested for adhesion to a metal plate by bending, the adhesion of Example 6 was much better than that of Comparative Example 3.

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 polyester resin composition with high strength and good adhesion, comprising an unsaturated compound containing at least one -H) in the molecule.