JPS6392632A - Curable resin - Google Patents

Abstract

PURPOSE:To provide the title resin having excellent hardness and strength and useful for paints, molding materials, etc., by bonding a specified polyhydroxyl compd. to a vinyl ester resin through a diisocyanate. CONSTITUTION:A polyhydric phenol (a) having at least two phenolic hydroxyl groups per molecule or a novolak is reacted with a monoepoxy compd. (b) having an epoxy group in an equimolar amount to the phenolic hydroxyl group of the component (a) at 160-180 deg.C to obtain a polyhydroxyl compd. (A) having at least two alcoholic hydroxyl groups per molecule. Separately, an epoxy resin (c) having at least two epoxy groups is reacted with (meth)acrylic acid (d) having a carboxyl group in an equimolar amount to the epoxy group of the component (c) at 100-140 deg.C to obtain a vinyl ester resin (B) having at least two (meth)acryloyl groups and at least two hydroxyl groups per molecule. A diisocyanate (C) is added to the component A and the resulting adduct is reacted with the component B.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a radical 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. It relates to curable resins.

[Conventional technology]

Currently, as radical-curing resins that can be cured at room temperature, unsaturated polyester resins and vinyl ester resins (
Epoxy acrylate resins are a typical example, and are widely used in various fields such as FRP, paints, and casting, taking advantage of their respective characteristics.

However, as the applications expanded, new demands arose.
Even in conventional applications, improving productivity and reducing costs are continuing challenges.

Therefore, the demands for improving the physical properties of resins are severe and there is no end in sight.

To give just one example, even if the surface layer of an FRP molded product is made of kerosene coat, it is harder and less prone to scratches.
There is always a demand for materials with excellent heat resistance and color stability.

Increased viscosity of vinyl ester resin, high performance SMC%B
There is also a desire to use it as a MC, and in this case diincyanate is reacted with the hydroxyl groups present in the vinyl ester resin.

However, although the reason is not clear, even when a small amount (5 or less) of diincyanate is added to the vinyl ester resin, gluing may occur during the reaction, and the resulting SMC, B
It is also known that the moldability of MC is not stable.

[Problem that the invention seeks to solve]

The present invention solves the above-mentioned problems, for example, by using diincyanate, to stably maintain the physical properties of the resin system, making it possible to manufacture modified resins, and also to improve the physical properties of FRP as much as possible. For example, in terms of hardness, even the most highly reactive hard type of unsaturated polyester resin has a Rockwell hardness of about 110 on the M scale and a pencil hardness of about 2H.

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. Met.

[Means for solving problems]

As a result of repeated studies to eliminate the drawbacks of existing radical-curing resins and expand their uses, the present inventors discovered (A) a polyhydric phenol or novolac containing two or more phenolic hydroxyl groups in one molecule. (hereinafter referred to as polyhydric phenols) with a monoepoxy compound so that the epoxy groups and phenolic hydroxyl groups are substantially equimolar. (hereinafter referred to as hydroxyl group); and (B) an epoxy resin containing two or more epoxy groups in one molecule, and acrylic, acid, or methacrylic acid, so that the epoxy group and the carboxyl group are substantially Vinyl ester resins each having two or more acryloyl or methacryloyl groups and a hydroxyl group in one molecule, which are obtained by reacting in equimolar proportions, are bonded via (C) diincyanate. The present invention was achieved by discovering that a curable resin is hard and has excellent strength.

[For production]

First, in order to help the understanding of the present invention, the chemical structural formula of the curable resin of the present invention using representative examples is shown.
It is known to link vinyl esters together.

Compared to this method, the advantages of the present invention can be summarized as follows.

(a) Resin synthesis can be performed safely.

When reacting a small amount (several coefficients) of diisocyanate with a vinyl ester, it is difficult to react, and when there is a large amount of diisocyanate as a whole, such as when reacting 0.5 to 1 molecule of diisocyanate with one molecule of vinyl ester. Although the reason is not clear, the resin cannot be successfully synthesized due to delification.

However, even if the proportion of diisocyanate used is the same, according to the present invention, since the positions of the two incyanate groups in the intermediate incyanate adduct are far apart, phenomena such as gluing or abnormal increase in viscosity can be prevented. You can safely synthesize resin without looking at it.

(b) Physical properties are improved.

Compared to the case where vinyl ester resin is directly reacted with diisocyanate, physical properties are improved in almost all respects. In particular, in the curable resin of the present invention, a hard and bulky group such as an allyloxymethylene group is introduced into the side chain, so physical properties such as heat resistance and hardness are significantly improved.

(c) The raw materials can be varied widely and the properties can be changed accordingly.

For example, the structure can be changed by changing the type of polyhydric phenol.

B) The molecular weight can be freely adjusted by changing the blending ratio of the polyhydroxyl compound, vinyl ester resin, and diisocyanate.

The polyhydroxyl compound having two or more hydroxyl groups in one molecule used as the captive component of the present invention is
A monoepoxy compound is reacted with a polyhydric phenol having two or more phenolic hydroxyl groups in the molecule so that the epoxy groups and phenolic hydroxyl groups become substantially equimolar, and the epoxy group is converted into an alcoholic compound. It is produced by converting it into a hydroxyl group.

At this time, as a reaction catalyst, quaternary ammonium salts, aliphatic tertiary amines, trisdimethylaminophenol, salts of secondary amines, sulfonium salts, phosphonium salts, and triphenylphosphine promote the reaction between epoxy groups and phenolic hydroxyl groups. the required amount (generally 0.1 to 1
phr) Must be used together.

The reaction is smoothly carried out at 180-160°C. The end point of the reaction is determined by infrared analysis based on the disappearance of epoxy groups.

Examples of the polyhydric phenols used in the present invention include the following types. Bisphenol A.

Bisphenol F1 Bisphenol 81 Catechol, resorcinol, hydroquinone, so-called novolac obtained by reacting phenol and formaldehyde with an acid catalyst. Phenols include phenol, 0-cresol, m-cresol, p-cresol, 3,5- Xylenol represented by xylenol, and cera-substituted phenolics such as bara tertiary butylphenol, bara octylphenol, bara phenylphenol, and bara mylphenol.

Examples of monoepoxy compounds that react with the above polyhydric phenols to convert phenolic hydroxyl groups into hydroxyl groups include ethylene oxide, propylene oxide, phenyl glycidyl ether, shrimp chlorohydrin,
Typical examples are styrene oxide and butyl glycidyl ether.

It is desirable that the reaction ratio between the epoxy group and the phenolic hydroxyl group is substantially 1:1.

The vinyl ester resin used as component (B) of the present invention, which shares two or more (meth)acryloyl groups and hydroxyl groups in one molecule, has two or more epoxy groups in one molecule. It is produced by reacting an epoxy resin with (meth)acrylic acid such that the epoxy group and the calf-xyl group are substantially equimolar.

As an example of the epoxy resin used in the production of vinyl ester resin, it is desirable to use a type that does not have many free hydroxyl groups.

Side light, as the noglycinolethyl type of bisphenol A, produced by Yuka Shell Co., Ltd. (Epicor) 827゜828,834
, 1001, Dow Company's DER-330, 331°332
, Ciba's GY-257, Dainippon Ink &Chemicals' Ebiclone #840, 850, 810, Tobu Kagasha's aX Poteau) VD-115, -127, Asahi Kasei's A, E.

Examples include R330 and 331.

A typical example of a novolac glycidyl ether type epoxy resin is DEN-431,438 manufactured by Dow Company.

There are many types of cycloaliphatic epoxy resins in the literature, but in reality, Union Carbide's ERL
-4221 is commercially available and can also be used in the present invention.

In addition, as a special epoxy resin, Yuka Shell Co., Ltd.'s Y
A biphenyl type called X-4000 is also available.

A diglycidyl ether type epoxy resin using bisphenol F and bisphenol S as a substitute for bisphenol A, such as Ebitsu 480 F type manufactured by Yuka Shell Co., Ltd., can also be used.

There is also a type in which alkylene oxide is added to bisphenol A and the terminal hydroxyl group is epoxidized with shrimp chlorohydrin.

The reaction between the epoxy resin and (meth)acrylic acid is carried out at a temperature of 100 to 140°C, using a catalyst such as a tertiary amine or a quaternary ammonium salt, and a stabilizer such as polyhydric phenols or quinones. carried out in the presence of

Examples of the diisocyanate used as component (C) of the present invention include the following types.

2.4 tolylene diisocyanate, mixture of 2,4 tolylene diisocyanate and 2,6 tolylene diisocyanate, tolydine diisocyanate, diphenylmethane diisocyanate, halapenylene diisocyanate, 1
, 5-naphthylene diisocyanate, 1,6 hexamethylene diisocyanate, inphorone diisocyanate,
Xylylene diisocyanate, hydrogenated xylylene diisocyanate.

The curable resin of the present invention is produced by combining the recovered portion and component (B) with component (C). In the reaction, from the viewpoint of preventing gluing, component (A) (
C) adding a component to leave an incyanato adduct;
The most preferred method is to then react component (B).

The synthesis of isocyanate adducts is safe, probably because the hydroxyl groups are located far apart. Since the resulting adduct has a high viscosity, it is advantageous to carry out the reaction as a solvent or monomer solution.

The blending ratio of the incyanato addition product and the vinyl ester is selected as necessary so that it is at least one amount of hydroxyl group in the vinyl ester per equivalent of incyanate group.

A ratio of 2 equivalents or more of hydroxyl groups means that there may be free novinyl esters that do not participate in the reaction, but as long as this amount does not constitute the main component, it is included in the present invention.

The reaction between the incyanate adduct and the vinyl ester can also be carried out smoothly in a solvent or monomer.

It goes without saying that the curable resin according to the present invention may be used in combination with fillers, reinforcing materials, colorants, mold release agents, polymers, etc., as necessary.

〔Example〕

Next, examples will be shown below to help understand the present invention.

Example 1 1! equipped with a stirrer, reflux condenser, and thermometer! In a Mitsuro flask, add bisphenol A1228I, phenyl glycidyl ether 300.9. To IJ methylbenzylammonium chloride 1.59 When the temperature is raised for all preparations,
It rapidly generates heat when the temperature exceeds 120℃.

Cool and keep at 150-160℃, then reheat for 15 minutes.
After reacting at 0 to 160°C for 5 hours, infrared analysis showed that free epoxy groups had completely disappeared.

The polyhydroxyl compound III) cooled to room temperature was semi-solid and pale yellowish brown in color.

In a similar apparatus, polyhydroxyl compound (:I) t-2
70,! i+, 130g of styrene, 0 rosebenzoquinone
．． After weighing 01,9 and dissolving it by heating at 60 to 70°C,
2.4-) Add 180g of lylene diinocyanate,
After reacting at 60℃ for 5 hours, as a result of infrared analysis, 2250
From the absorption area of benzoana-14 in clTt, it was estimated that about 54 of the incyanato groups had reacted. The incyanato adduct [111] was obtained in the form of a pale yellowish brown liquid.

In a Mitsuro flask equipped with a stirrer, a reflux condenser, and a thermometer, the above-mentioned Epikote 82 was added as a resin.
360I of 7, 172y of methacrylic acid, 0.2g of hydroquinone, and 1.5g of trimethylbenzylammonium chloride were charged and reacted for 3 hours with vigorous stirring at 120-130°C, resulting in an acid value of 5.9.

Styrene 230. When li+ was added, vinyl ester resin CI [[] was obtained in the form of a reddish-brown liquid.

Molding the curable resin [A] In two or three-necked flasks equipped with a stirrer, a reflux condenser, and a thermometer, add the above incyanate addition amount C]I)
Styrene m1) 400.1 vinyl ester resin [”1l
l) 530 g was charged, the temperature reached 60°C, and in the next step, 1. 'Add # and heat at 60℃ for 3
After reacting for a while, infrared analysis showed that the free isocyanate groups completely disappeared.

Styrene 3409 was added to obtain a curable resin (A) with a reddish brown color and a viscosity of 8.9 poise.

To 100 parts of resin (A), 1.5 parts of #328E from Kayaku Nouri Co., Ltd. as a curing agent and 0.5 parts of cobalt nanthenate were added, and the next system rapidly generated heat after being converted to a mole at room temperature in 24 minutes, reaching the maximum heat generation. The temperature reached 168°C.

As shown in Table 1, its properties were hard and highly tough.

Table 1 Bending modulus of elasticity 440 kg/rm" Charpy impact value 4.1 kg cm/crn" Tensile elongation rate 2.8 cm Heat deformation temperature 132°C Rockwell hardness M-115 (Note); Number in 0 is the average value of 5 measured values Comparative Example 1 In the same apparatus, 380 g of vinyl ester resin 1:IID (styrene solution) and 90 g of 2.4-) lylene diane dianate (inocyanate adduct []] and equimolar amount) When dibutyltin dilaurate 1.6.9 was added at 60°C, gluing occurred after about 7 minutes and no stable liquid resin was obtained. Example 2 Stirrer, thermometer, Product name B manufactured by Asahi Denka Co., Ltd., in which 1 mole of glopylene oxide was added to each bisphenol in a 27-four flask equipped with a reflux condenser and a gas inlet tube.
PX-11 for 350. ! ;I, styrene 250. p,
Rose benzoquinone 0.01. ! After homogeneously dissolving i', diphenylmethane diisocyaner) 500.9 was added and reacted at 60°C in dry air for 5 hours.As a result of infrared analysis, it was determined that the isocyanate group decreased by about 59 times. It was done.

The produced isocyanate adduct [■] was a slightly cloudy yellowish brown viscous liquid.

In a No. 11 three-meter flask equipped with a stirrer, a thermometer, and a reflux condenser, 350 y of DOW Ban Chemical Co.'s DEN-431 and 1721 y of methacrylic acid were added as Nordelac-type epoxy resin. Prepare benzyldimethylamine 71.5.9, rose benzoquinone 0.15.9, 120-130
When the reaction was carried out for 4 hours in an air stream at °C, the acid value reached 4.2, so the reaction was stopped and 378I of styrene was added to obtain vinyl ester resin [V] in the form of a reddish-brown liquid.

Preparation of curable resin [''B] In a 21 sepa 2 pull flask equipped with a stirrer, thermometer, gas inlet tube and reflux condenser, add isocier) --H0o
500g of body [IV], 5g of vinyl ester resin [■]
After adding 20g and reacting at 60°C for 3 hours under dry air,
After adding 2 g of dibutyl dilaurate and reacting for another 2 hours, infrared analysis showed that all free isocyanate groups had disappeared.

Add 300g of styrene to hardenable resin CB).
Reddish brown, viscosity 12. Obtained in 1 poise.

A system in which 100 parts of resin CB), 1.5 parts of 328E, and 0.3 parts of cobalt naphthenate were added was cured at room temperature in 12 minutes, and the maximum exothermic temperature reached 161°C.

As shown in Table 2, the physical properties of the cured resin are hard and strong.

Table 2 Bending modulus of elasticity 460 kliF/■2 Shalpy impact value 3.2 kgcm/cm" Tensile elongation rate
2.3 (H) Heat deformation temperature 156°C Rockwell hardness M-117 Example 3 Production of isocyanate adduct [■] Equipped with a stirrer, reflux condenser, thermometer, and dropping funnel. In a SENO-2 pull flask, add novolac (phenol 94ON, 40% formalin 750ji, oxalic acid 20
The product obtained by reacting g, with a melting point of 80° C., was steam distilled to give 0.4% free phenol.
The result of C analysis is that it seems to be about 2.1 to 2.5 nuclear bodies).
50.9, 190g of shrimp chlorohydrin, 1.5fi of trimethylbenzylammonium chloride 12
When heated to 0 to 130°C, it rapidly generates heat and reaches around 160°C, so cool it to prevent the temperature from rising any further.
After reacting at 150-160° C. for 5 hours, infrared analysis showed that free epoxy groups disappeared.

Styrene 460g, hydroquinone 0, 19 at 120℃
was added to form a solution, the temperature was lowered to 60°C, 444 g of isophorone diisocyanate and 156 g of styrene were added, and after reacting for 3 hours, diptyltin dilaurate 3I
was added, and the reaction was further continued for 3 hours. As a result of infrared analysis, it was estimated that the remaining incyanato group was the original 54(1).

The obtained isocyanate adduct [■] was a light brown liquid.

Add the isocyanate adduct [■] to two three-necked flasks equipped with a stirrer, a reflux condenser, and a thermometer.
% of the vinyl ester resin [v] described in Example 2.
After adding 0 g of butyl monolaurate and 0.111 of parabenzoquinone and reacting at 60° C. for 5 hours, it was determined that the free incyanato groups had completely disappeared as a result of infrared analysis.

The obtained curable resin [C] has a light brown color and a viscosity of 14.9.
It was Poise.

Curable resin [C], vinyl ester resin [111]
, vinyl ester resin [V], 100 parts each, 328
Add 1.5 parts of E and 0.5 parts of cobalt naphthenate to a thickness of 3
A casting plate of X, 15X100X (7) was prepared, immersed in methanol at 60°C, and changes in its physical properties were examined.

The results are shown in Table 3, and the superiority of the resin according to the present invention was recognized.

Table 3: Change in bending strength due to immersion time Blank 100 250 500 1000
Effects of the Invention The curable resin having the novel structure of the present invention is easy to synthesize, and by radical curing,
A cured product with better physical properties than vinyl ester resins, especially heat resistance and mechanical strength, can be obtained.
It is extremely useful for various uses such as paints, adhesives, coating agents, lining agents, molding materials, and FRP.

Claims (1)

[Scope of Claims] (A) A monoepoxy compound is added to a polyhydric phenol or novolak having two or more phenolic hydroxyl groups in one molecule so that the epoxy groups and phenolic hydroxyl groups are substantially equimolar. A polyhydroxyl compound having two or more alcoholic hydroxyl groups in one molecule obtained by reacting with (B) an epoxy resin having two or more epoxy groups in one molecule, and acrylic acid or methacrylic acid. , a vinyl ester resin that shares two or more acryloyl groups or methacryloyl groups and hydroxyl groups in each molecule, which is obtained by reacting an epoxy group and a carboxyl group in a substantially equimolar ratio, (C) A curable resin bonded via a diisocyanate.