JPH0411567B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed to the production of radically curable resins having a novel structure that is hard and has excellent strength and is useful for various uses such as paints, adhesives, coating agents, lining agents, molding materials, and FRP. Regarding the method. [Conventional technology] Currently, unsaturated polyester resins and vinyl ester resins (epoxy acrylate resins) are typical as radical-curing resins that can be cured at room temperature.
It is widely used in various fields such as paint and casting. However, as the range of applications expands, new demands arise, or improvements in productivity and
Cutting costs is a continuing challenge. Therefore, the demands for improving the physical properties of resins are severe and there is no end in sight. To give one example, there is always a demand for gel coats that form the surface layer of FRP molded products, which are harder, more scratch resistant, more heat resistant, and have better color stability. . By increasing the viscosity of vinyl ester resin, high performance
There are also requests to use it as SMC and BMC,
In this case, diisocyanate and hydroxyl groups present in the vinyl ester resin are reacted. However, although the reason is not clear, even when a small amount (5% or less) of diisocyanate is added to vinyl ester resin, gelation may occur during the reaction.
It is also known that the moldability of the SMC and BMC produced is not stable. [Problems to be Solved by the Invention] The present invention addresses the above-mentioned problems, for example, by using diisocyanate to stably maintain the physical properties of a resin system, making it possible to produce a modified resin, and also by improving the physical properties of FRP as much as possible. It is intended to increase. For example, in terms of hardness, even the most reactive hard type of unsaturated polyester resin is about 110 on the Rockwell hardness M scale and about 2H on the pencil hardness scale. Furthermore, even the hardest type of vinyl ester resin has a hardness of 105 to 106 on the Rockwell M scale, which is far below the hardness of melamine resin, which is 115 to 120 on the Rockwell M scale and 4H in pencil hardness. . [Means for Solving the Problems] As a result of repeated studies to eliminate the drawbacks of existing radical-curing resins and expand their use, the present inventors found that (A) two or more phenols in one molecule; A monoepoxy compound is reacted with a polyhydric phenol or novolak having a phenolic hydroxyl group (hereinafter referred to as polyhydric phenols) so that the epoxy group and the phenolic hydroxyl group are substantially equimolar in one molecule. (B) A polyhydroxyl compound having two or more alcoholic hydroxyl groups (hereinafter referred to as hydroxyl group), and (B) a saturated monoepoxy compound having one epoxy group in one molecule, acrylic acid or methacrylic acid (hereinafter referred to as hydroxyl group). (meth)acrylic acid)
An unsaturated monohydroxyl compound having one acryloyl group or methacryloyl group (hereinafter referred to as (meth)acryloyl group) and a hydroxyl group in each molecule, which is obtained by reacting substantially equimolar amounts of is reacted with (C) diisocyanate to bond components (A) and (B) with component (C) through at least four urethane bonds, resulting in a hard curable resin. Moreover, it was discovered that it has excellent strength, and the method of the present invention was developed. [Function] First, in order to aid understanding of the present invention, the chemical structural formula of the curable resin of the present invention will be shown using representative examples.

〔Example〕

Next, examples will be shown below to help understand the present invention. Example 1 Production of polyhydroxyl compound [1] 1 equipped with a stirrer, reflux condenser, and thermometer
228g of bisphenol A in a three-necked flask,
Prepare 300g of phenyl glycidyl ether and 1.5g of trimethylbenzyl ammonium chloride.
When the temperature rises, it rapidly generates heat once it exceeds 120℃. Cool and keep at 150-160℃, then reheat.
After reacting at 150-160°C for 5 hours, infrared analysis showed that free epoxy groups had completely disappeared. The polyhydroxyl compound [1] cooled to room temperature was a light yellowish brown semi-solid. Production of isocyanate adduct [] In a similar apparatus, polyhydroxyl compound [1]
520g, styrene 250g, parabenzoquinone 0.01
Weigh out 2,4g of
-Add 350g of tolylene diisocyanate and 60℃
After reacting for 5 hours, infrared analysis showed that the free isocyanate groups had decreased by about 55%. 250 g of styrene was added to obtain an isocyanate adduct [] in the form of a pale yellowish brown liquid. Production of unsaturated monohydroxyl compound [] 1 equipped with a stirrer, reflux condenser, and thermometer
Into a three-necked flask, charge 300 g of phenyl glycidyl ether, 172 g of methacrylic acid, 2 g of triphenylphosphine, and 0.2 g of hydroquinone.
When the reaction was heated to ~130°C for 3 hours, the acid value became 4.1, so 260 g of styrene was added to produce an unsaturated monohydroxyl compound (styrene solution). Production of curable resin [A] Add unsaturated monohydroxyl compound [] (styrene solution) 730 to the total amount of isocyanate adduct []
Transfer g to a three-necked flask equipped with a stirrer, reflux condenser, and thermometer. After raising the temperature to 60°C, 4 g of dibutyltin dilaurate was added and the mixture was reacted at 60°C for 3 hours. As a result of infrared analysis, it was confirmed that the isocyanate group had disappeared. Furthermore, 585 g of styrene was added to obtain a curable resin [A] having a reddish brown color and a viscosity of 8.7 poise. A system in which 100 parts of resin [A], 1.5 parts of #328E from Kayaku Nouri Co., Ltd. as a curing agent, and 0.3 parts of cobalt naphthenate were mixed together gelled in 31 minutes and rapidly generated heat, reaching a maximum temperature of 170°C. did. The physical properties of the cured resin were as follows. Bending strength 15.7Kg/mm ^2Heat distortion temperature 116℃ Rockwell hardness M-116 Shalpy impact value 2.6Kgcm/cm ^2Example 2 Production of isocyanate adduct [] Equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube Into a two-four-necked flask, 350 g of Asahi Denka's brand name BPX-11, which has 1 mole of propylene oxide added to bisphenol A, and styrene were added.
After uniformly dissolving 250 g of parabenzoquinone and 0.01 g of parabenzoquinone, 500 g of diphenylmethane diisocyanate was added.
g and reacted for 5 hours at 60℃ under dry air,
As a result of infrared analysis, the isocyanate group is approximately 59 (%)
It was determined that the amount had decreased. The produced isocyanate adduct [ ] was a slightly cloudy yellowish brown viscous liquid. Production of curable resin [B] In the isocyanate adduct [] equipped with the above-mentioned equipment, 288 g of 2-hydroxypropyl methacrylate, which is a reaction product of propylene oxide and methacrylic acid, 615 g of styrene, and 0.1 g of parabenzoquinone are added. , dibutyltin dilaurate (3 g) was added, and the mixture was reacted at 60° C. for 5 hours. As a result of infrared analysis, it was confirmed that the free isocyanate groups had completely disappeared. The obtained curable resin [B] has a yellowish brown color and a viscosity of
It was 3.9 poise. A system in which 100 parts of resin [B], 2 parts of 328E, and 0.5 parts of cobalt naphthenate were added gelled at room temperature for 27 minutes.
The patient rapidly developed a fever, reaching a maximum temperature of 164°C. The physical properties of the cured resin were as follows. Bending strength 16.8Kg/mm ^2Bending modulus of elasticity 420Kg/mm ^2Heat distortion temperature 118℃ Rockwell hardness M-115 Sharpie impact value 3.2Kgcm/cm ^2Example 3 Production of isocyanate adduct [] Stirrer, reflux condenser, Add styrene to a 3-separable flask equipped with a thermometer and gas inlet tube.
300g, 2-hydroxyethyl methacrylate 260
g and 444 g of isophorone diisocyanate were added and heated in dry air at 70-75°C for 8 hours. As a result of infrared analysis, the free isocyanate group was 48 (%).
The isocyanate adduct [] was obtained in a pale yellow liquid state. Production of novolac-epoxy compound adduct [] Into two separable flasks equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, add novolac (940 g of phenol, 750 g of 40% formalin,
The product obtained by reacting 20 g of oxalic acid was steam distilled to contain 0.4% free phenol, with a melting point of approx.
At 80°C, 250 g of 2.1-2.5 nuclear bodies (according to GPC analysis), 300 g of phenyl glycidyl ether
g, trimethylbenzylammonium chloride
When 2.5g of 2.5g was prepared and heated to 120-130℃, it rapidly generated heat and reached around 160℃, so it was cooled to prevent the temperature from rising any further and reacted at 150-160℃ for 5 hours.The result of infrared analysis was It was observed that free epoxy groups disappeared. 450 g of styrene was added to obtain a novolac-monoepoxy adduct in the form of a pale yellowish brown liquid. Production of curable resin [C] Add 1000 g of novolak-epoxy compound adduct [] to the isocyanate adduct [] equipped with the above-mentioned equipment, and add 0.1 g of parabenzoquinone.
g, 5 g of dibutyltin dilaurate, and 5 g at 70℃.
After the time reaction, it was determined that free isocyanate groups disappeared as a result of infrared analysis. 400 g of styrene was added, and the resulting curable resin [C] had a yellowish brown viscosity of 4.4 poise. A system containing 100 parts of resin [C], 1.5 parts of 328E, and 0.5 parts of cobalt naphthenate rapidly generated heat after gelling at room temperature for 27 minutes, reaching a maximum exothermic temperature of 167°C. The physical properties of the cured resin were as shown in the table below. Bending strength 15.9Kg/mm ² Bending modulus of elasticity 470Kg/mm ² Heat distortion temperature 124℃ Rockwell hardness M-114 Sharpie impact value 2.3Kgcm/cm ² [Effects of the invention] The novel structure obtained by the method of the present invention This curable resin is easy to synthesize, and by radical curing, a cured product with better physical properties than vinyl ester resins, especially in heat resistance and mechanical strength, can be obtained. ,
Paints, adhesives, coating agents, lining agents,
Extremely useful for various applications such as molding materials and FRP.

Claims (1)

[Scope of Claims] 1 (A) A polyhydric phenol or novolak having two or more phenolic hydroxyl groups in one molecule,
A polyhydroxyl compound having two or more alcoholic hydroxyl groups in one molecule, which is obtained by reacting a monoepoxy compound so that the epoxy group and the phenolic hydroxyl group are substantially equimolar; (B) 1 One acryloyl group or methacryloyl group in each molecule obtained by reacting acrylic acid or methacrylic acid in substantially equimolar amounts with a saturated monoepoxy compound having one epoxy group in the molecule. An unsaturated monohydroxyl compound that shares a hydroxyl group is reacted with (C) a diisocyanate to form components (A) and (B) with component (C) through at least four urethane bonds. A method for producing a curable resin characterized by bonding with a resin.