JPS62215622A - Curable resin - Google Patents

Abstract

PURPOSE:The titled resin of novel structure which is suitable as coating compound, etc., readily synthesized and has improved heat resistance and mechanical strength, obtained by combining a specific epoxy resin-phenol adduct with an unsaturated monohydroxyl compound and a vinyl ester resin. CONSTITUTION:(A) An epoxy resin-phenol adduct containing two or more hydroxyl groups and two or more allyloxymethylene groups in one molecule is combined with (B) an unsaturated monohydroxyl compound containing two or more (meth)acryloyl groups and two or more hydroxyl groups in one molecule and (C) a vinyl ester resin containing two or more (meth)acryloyl groups and two or more hydroxyl groups in one molecule through (D) a diisocyanate to give the aimed resin having a structure shown by the formula. The component A is obtained by reacting an epoxy resin with a monohydric phenol, the component B by reacting a monoepoxy compound with (meth)acrylic acid and the component C by reacting the epoxy resin with (meth)acrylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a radically curable resin having a novel structure useful for various uses such as paints, adhesives, molding materials, and FRP.

[Conventional technology]

Currently, as radical-curing resins that can be cured at room temperature, unsaturated polyester resins and vinyl ester resins (
Epoxy acrylate (A) is a typical example, and each is used in a wide range of fields, taking advantage of its respective characteristics.

However, as the uses expand, the performance required of the resin becomes more detailed and sophisticated, and it may be difficult to satisfy these demands with conventional resins.

For example, if we take heat resistance as an example, the practical range in terms of heat distortion temperature of styrene as a crosslinking agent is about 120°C at most, and it cannot be used in applications that require higher temperatures. I can't.

Although there are special highly reactive, oil-saving, heat-resistant resins with a heat distortion temperature of 130 to 150°C, in many cases other physical properties, such as mechanical strength, are insufficient and pose problems for practical use. Sometimes it happened. 5 [Problems to be Solved by the Invention] In view of the above situation, the present inventors have conducted various studies in order to industrially easily produce a resin with high performance that exceeds the physical properties of these existing resins, particularly vinyl ester resins. discovered a radically curable resin having a novel structure with excellent heat resistance and mechanical strength, and arrived at the present invention.

[Means for solving problems]

That is, in the curable resin of the present invention, (A) monohydric phenols are added to epoxy horse chestnut resin having two or more epoxy groups in one molecule, and the epoxy groups and phenolic hydroxyl groups are substantially equimolar. (B) a nixy resin-phenol adduct that shares two or more hydroxyl groups and allyloxymethylene groups in each molecule, and (B) has one epoxy group in one molecule. A saturated or unsaturated monoepoxy compound is reacted with acrylic acid or methacrylic acid (hereinafter referred to as (meth)acrylic acid) in substantially equimolar amounts, each having at least one in each molecule. An unsaturated monohydroxyl compound that shares an acryloyl group or a methacryloyl group (hereinafter referred to as a (meth)acryloyl group) and one hydroxyl group; A vinyl product that shares two or more (meth)acryloyl groups and hydroxyl groups in each molecule, which is obtained by reacting (meth)acrylic acid in a ratio in which epoxy groups and carboxyl groups are substantially equivalent. It is characterized by being bonded to an ester resin via (b) diincyanate.

[For production]

First, in order to facilitate understanding of the present invention, the chemical structural formula of the curable resin of the present invention is shown using representative examples.63o1. Ekidef resin-phenol adduct (which shares two or more hydroxyl groups and allyloxymethylene groups in each molecule of otophenol)
6) (ii) Unsaturated monohydroxyl compound (B) (out) CH that shares one (meth)acryloyl group and one hydroxyl group in each molecule.

Engineering I xy resin CH5 + 2CH2-C-COOH Methacrylic acid 0-CH2-CH-CH2-0-C ■ Vinyl ester resin that shares two or more (meth)acryloyl groups and hydroxyfur groups in each molecule ( C
) By reacting vinyl ester resin with diisocyanate,
It is known to link vinyl esters together.

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

What) Resin synthesis can be performed safely.

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

However, according to the present invention, resins can be synthesized safely even with the same diisocyanate usage ratio.

(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, since the curable resin of the present invention has a hard and bulky group such as an allyloxymethylene group introduced into the side chain, physical properties such as heat resistance and hardness are significantly improved.

eC) The raw materials can be changed widely and the properties can be changed accordingly.

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

The epoxy resin-phenol adduct having two or more hydroxyl groups and allyloxymethylene groups in each molecule used as component (4) of the present invention is a phenol adduct having two or more epoxy groups in one molecule. It is produced by reacting monohydric phenols with a resin so that the epoxy groups and phenolic hydroxyl groups are substantially equimolar, converting the epoxy groups to alcoholic hydroxyl groups and introducing allyloxymethylene groups. Ru.

At this time, a quaternary ammonium salt is used as a reaction catalyst.

Aliphatic tertiary amine, trisdimethylaminophenol,
A necessary amount (generally 0.5%) of a substance that promotes the reaction between an epoxy group and a phenolic hydroxyl group, such as a secondary amine salt, sulfonium salt, phosphonium salt, or triphenylphosphine, is added.
1 to 1 phr) must be used together.

The reaction is smoothly carried out at 120-160°C. The end point of the reaction is determined by infrared analysis and the disappearance of the nixyl group.

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

For example, as a diglycidyl ether type of bisphenol A, Epiny) 827 from Yuka Shell Co., Ltd.

828, DIR-330, 331, and 332 from Dow, and GY-257 from Ciba.

Typical examples of Noblak's glycidyl ether type epoxy resins include DEN-431 and 438 from Dow.

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
Bij-tl+, which is called X-4000
ill M J M J $+l ml A diglycidyl ether type epoxy resin using bisphenol F instead of bisphenol A, ie, Epiny) 807 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 nyxylated with shrimp chlorohydrin.

The phenol to be reacted with the epoxy resin is not particularly limited, except that it is a monohydric phenol. An example is the following.

Phenol, 0-cresol, m-cresol, p-cresol, 2,3 xylenol, 2,4 xylenol,
2,5 xylenol, 2,6 xylenol, 3.4 xylenol, 3,5 xylenol, barisopropylphenol, bara tertiary butylphenol, bara octylphenol, i9 la/nylphenol, nographenylphenol, nografumylphenol, α -naphthol, β-naphthol, 2,5-dibromophenol, 2,6-di-t-butyl-1-hydroxytoluene, 2,6-di-t-butyl-1-hydroxyanisole.

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

The unsaturated monohydroxyl compound used as component (B) of the present invention, which shares at least one (meth)acryloyl group and one hydroxyl group in each molecule, has at least one (meth)acryloyl group and one hydroxyl group in each molecule. It is produced by reacting a saturated or unsaturated monoepoxy compound having an epoxy group with (meth)acrylic acid in a substantially equimolar ratio.

Examples of saturated monoepoxy compounds include, for example, phenyl glycidyl ether, cresyl glycidyl ether, 2
, 5-dibromucresyl glycidyl ether, styrene oxide, propylene oxide, ethylene oxide, butylene oxide, butyl glycidyl ether, and the like.

Examples of the unsaturated monoepoxy compound include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and the like.

For the reaction between monoepoxy compound and (meth)acrylic acid,
The reaction catalyst used in the reaction system of phenols and epoxy resin mentioned above is used as a catalyst.

At this time, it is necessary to use a polymerization inhibitor such as polyhydric phenols to prevent ketalization during the reaction.

Of course, commercial products such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, which are reaction products of a monoepoxy compound and (meth)acrylic acid, can also be used as component (B) of the present invention. C) A vinyl ester resin that shares two or more (meth)acryloyl groups and a hydroxyl group in one molecule, which is used as a component, is an epoxy resin that has two or more epoxy groups in one molecule. It is produced by reacting meth)acrylic acid such that epoxy groups and carboxyl groups are substantially equivalent.

The epoxy resins used in the production of vinyl ester resins are of course of the types mentioned above, but the types are expanded to include types having one or more hydroxyl groups, i.e., those having a molecular weight of 350 to 2.
Types in the range of 500 are also available.

For the reaction between epoxy resin and (meth)acrylic acid, reaction catalysts such as quaternary ammonium salts, tertiary amines, tertiary amine salts, secondary amine salts, sulfonium salts, phosphonium salts, )IJ phenylphosphine are used. .

Furthermore, it is necessary to use a polymerization inhibitor typified by polyhydric phenols in order to prevent dulling.

Note that the unsaturated monohydroxyl compound and the vinyl ester resin can also be produced simultaneously by reacting a mixture of a saturated monoepoxy compound and an epoxy resin with (meth)acrylic acid in substantially equivalent amounts ( The resin mixture obtained by this method is hereinafter abbreviated as unsaturated vinyl ester).

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

2.4 tolylene diisocyanate, 2,4 tolylene, ・
mixture with acrylic // ``? Nat, 1
, 6 hexamethylene diisocyanate, inphorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate.

The curable resin of the present invention is produced by combining component (4) with component (B) and component (Q). From the viewpoint of preventing dulling, the reaction is most preferably carried out by first adding component (4) to produce an incyanato adduct, and then reacting all components (B) and (C).

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

The epoxy resin-phenol adduct and the diisocyanate are reacted in a substantially equimolar ratio.

The blending ratio of the incyanato addition product and the unsaturated monohydroxyl compound and the vinyl ester is selected as necessary so that it is at least 1 equivalent of the hydroxyl group of the unsaturated monohydroxyl compound and the vinyl ester per 1 equivalent of the incyanato group.

A proportion of hydroxyl groups of 2 or more means that there may be free unsaturated monohydroxyl compounds and vinyl esters that do not participate in the reaction, but unless this remains is the main component, it is not included in the present invention. Can be put in.

The reaction of the incyanate adduct with the unsaturated monohydrokyfur compound and the vinyl ester can also be smoothly carried out in a solvent or a solvent.

It goes without saying that the curable resin according to the present invention may be used in combination with a filler, a reinforcing material, a coloring agent, a mold release agent, a 4-reamer, etc., as necessary.

〔Example〕

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

Example 1 Into a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 360II of Epicoat 827 from Yuka Shell Epoki 7 Co., Ltd. was added as an epoxy resin.

When phenol 188.9' and trimethylbenzylamsonium chloride 1.5I were charged and heated, 12
It rapidly generates heat when the temperature exceeds 0℃.

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 completely disappeared.

Epoxy resin-phenol adduct (1
) is shirarug-like and light yellowish brown in color.9.

Production of unsaturated vinyl ester […] 1 with a stirrer, reflux condenser, and temperature needle! In a Mitsuro flask, about 18 liters of palm resin was added.
5 bisphenol A diglyphyl ether 37ON
, glycidyl methacrylate) 14219. Methacrylic [
25B, 9, charged with 2.51 JT of benzyldimethylamine and 0.3 JT of hydroquinone, 125 in an air stream.
After reacting at ~130°C for 4 hours, the acid value became 8.1, so styrene 230I was added to obtain unsaturated vinyl ester (II) as a reddish brown liquid.

Preparation of isocyanate adduct [111) In a 317-paraple flask equipped with a stirrer, a reflux condenser, and a thermometer, adduct CI]t'540L styrene 260J, 0.01. Sl.

After weighing and making a homogeneous solution, 2.4-) lylene diiso7anate 35011 was added and reacted at 60°C for 5 hours. As a result of infrared analysis, it was estimated that the incyaner) M degree was almost halved. .

The nine isocyanate adduct (Iff) obtained was a yellowish brown liquid.

To this K, add the entire amount of unsaturated vinyl ester (It) (styrene solution), and then add diptyltin silacrate 511
and/added 0.311t of benzoquinone, 60
After reacting at ~65°C for 5 hours, infrared analysis showed that the free incyanato groups had completely disappeared.

Add 1170g of styrene and add curable resin (All
was obtained with a reddish brown color and a viscosity of 5.9 poise.

Resin CA) 100 parts by weight, Kayaku Nury Co., Ltd.'s 32
1 part of 8E and 0.2 part of cobalt naphthenate were added, and the round thread became rolyzed in 6 minutes, rapidly generating heat and reaching a maximum temperature of 166°C.
reached.

The physical properties of the cured resin were as follows.

Bending strength 15.9 Yu/■2 Heat deformation temperature 136°C Rockwell hardening M-1167 Yarby impact value 2.4/2 Example 2 Production of epoxy resin-xylenol adduct [■] Stirrer, reflux condenser, 2 with a thermometer attached! In the Mitsuro flask? As a rack-containing knee medium 7 resin, Dow Ch
@m1aa1 DEN-431e 360 i2.6
-Xylenol 270#, benzyldimethylamine 2I
i, and reacted at 150-160℃ for 3 hours,
As a result of infrared analysis, it was confirmed that 7 free epoxy groups had disappeared.

Additionally, styrene 37011 and hydroquinone 9.1
&Additionally, an epoxy resin-xylenol adduct [■] was obtained in the form of a pale reddish brown liquid.

1 with a stirrer, reflux condenser, and thermometer! 24 in a three-way flask? DotChemic as xy resin
A1 DEN-438 380#, Fznylglycidele ether/L/15011, methacrylic acid 258I
, dimethylbenzylamine 2.5I and norabenzoquinone 0.3.9. After all the preparations were reacted at 130-135℃ for 3 hours, the acid value was 6.4, so styrene 2
12IIt-added, t, unsaturated vinyl ester CV'l was obtained in the form of a reddish-brown liquid.

In a 21-cell Δrable flask equipped with a stirrer, a reflux condenser, and a thermometer, add the adduct CIVI (styrene solution 1) 5
00.9. Unsaturated vinyl ester CV: 1500g, diphenylmethane diisocyanate 2501i.

After charging styrene 420.1/f rapenzoquinone 0.1 J' and reacting at 60°C for 5 hours, digtyltin dilaurate 31 was added and reacting for another 3 hours at 60°C. As a result of infrared analysis, free incyanate groups were completely removed. It was confirmed that it had disappeared.

The obtained curable resin CB] has a reddish brown color and a viscosity of 9.4?
It was Is.

A system in which 100 parts of resin (B), 1 part of Su 328E from Kayaku Nuri Co., Ltd. and 0.2 parts of cobalt naphthenate were added, rapidly generated heat after being cured in 11 minutes, and the maximum exothermic temperature reached 169°C. Reached.

The physical properties of the cured resin were determined as follows.

Bending strength 13.7 kg/+w+2 Heat deformation temperature 131℃ Charpy impact value 2.2 kgcm
/ cm 20mm hardness M-118
Example 3 260 g of Union Carbide's ERL-4221 as an epoxy resin, α-naphthol 2801 and triphenylphosphine 2I were charged into a 21-three flask equipped with a stirrer, a reflux condenser, and a thermometer.
Increase temperature to 150-160℃, cool to 160℃ if necessary
After reacting for 8 hours, it was confirmed by infrared analysis that the free Epoxy group had disappeared.

Next, 460 g of p-methylstyrene was added at a temperature of around 120°C to obtain an epoxy resin-α naphthol adduct CM) in the form of a pale reddish brown liquid.

After adding 440 g of isophorone noisocyanate and 260.1 g of p-methylstyrene to the entire amount of epoxy resin-α-7tol adduct CVII and heating to 60°C,
Diptyltin zolaureate) 3JF was added and heated at 60″CK for 6 hours, and as a result of infrared analysis, it was found that the isocyanate groups were reduced by almost half.

The obtained incyanato adduct [■] was pale reddish brown and liquid.

1 with a stirrer, reflux condenser, and thermometer! In a Mitsuro flask, add 26 ON of ERL-4221, 2281 allyl glycidel ether, 288 g of acrylic acid, )+
After charging 2.5Ii of 77enylphosphine and 0.2Fk of hydroquinone and reacting at 120°C to 125°C for 5 hours, the acid value became 9.2, so p-methylstyrene 224II was processed and unsaturated vinyl ester [■] was obtained as a light reddish brown liquid.

Isocyanate adduct [■] Total: f into a 31-cell arm-rable flask equipped with a stirrer, reflux condenser, and thermometer.
itf, lower section n vinyl ester cvno c styrene solution) was added and reacted at 60°C for 3 hours, then butyltin diclay) 2Ii was added and reacted for a further 5 hours. As a result of infrared analysis, free It was observed that the isocyanate group of was disappeared.

Next, add 550 #t of p-methylstyrene, and the curable resin [C] is a reddish brown liquid with a viscosity of 3.1? Obtained with is.

Resin (c) i o In the o part, φ32 made by Kayaku Nouri Co., Ltd.
The system containing 1 part of 8E and 0.5 part of cobalt naphthenate is 3
After 3 minutes of thickening, it gradually heats up and the maximum temperature of heat generation is 14.
The temperature reached 9℃.

The physical properties of the cured resin were as follows.

Bending strength: 11.4 kg/■2 Kualpy Impact value: 1.9 kH/m' Explosive well hardness: M-116 Heat deformation temperature: 128°C Separately, painted to a thickness of 0.1 ■ on I-indellite treated steel plate. The resulting coating film became a tack-free coating film in about 1 hour after being cured for 35 minutes.

The hardness of the gold film after being left at room temperature for 3 days was 2H to 3H, and it could be polished. ) to 5
50II, hexamethylene diinocyanate 330jl
, styrene 420#, penzoquinone 0.2 g,
diptyltin silaclay) 4. ! After charging Ml to make a homogeneous solution, the mixture was reacted at 60° C. for 5 hours.

As a result of infrared analysis, it was estimated that the absorption of isocyanate was reduced by almost half.

The obtained isocyanate adduct (IX) was obtained in the form of a reddish brown liquid.

1 with stirrer, magnetic condenser, and temperature needle! seven'
In a 4'2 pull flask, add 1 phenyl glycidel ether.
50. ? , methacrylic acid 86.9, triphenylphosphine 0.51 and hydroquinone 0.05I were added and reacted at 120-130°C for 3 hours, the acid value was 8.1.
Therefore, 1,641 tons of styrene was added to obtain unsaturated monohydroxy compound [X] (styrene solution) in the form of a pale reddish brown liquid.

Into a 11 three-necked flask equipped with a stirrer, a reflux condenser, and a temperature needle, the above-mentioned Epicoat 82 was added as a resin.
7t-360&, methacrylic acid 1721, Hyde quinone 0.21, trimethylpensylammonium chloride 1.511t- and reacted at 120-130'G for 3 hours with slow stirring, the acid value became 5.9. .

Added 230 gu” of styrene, vinyl ester resin (1
113 was obtained as a reddish brown liquid.

3) Add the incyanato adduct (1) 0130ON to a three-meter flask equipped with a stirrer, reflux, a densifier, and a thermometer.
, vinyl ester resin αI] to 760II.

40ON of unsaturated monohydroxy compound (X) and 0.21 penzoquinone! , diptyltin silaclay)
After adding 5.9t and reacting at 60°C for 8 hours, it was confirmed by infrared analysis that the free isocyanate groups had completely disappeared.

Styrene 500j'? In addition, the curable resin (b) is reddish brown and has a viscosity of 7.1 f! Bayesian obtained.

A mixed system in which 100 parts of resin (D), 1.5 parts of Na328E, and 0.3 parts of cobalt naphthenate were added was glued in 14 minutes and rapidly generated heat, reaching a maximum exothermic temperature of 162°C.

The main uniformity of the cast product was that a hard and tough resin was obtained in the following pass.

Bending strength: 16.9 kg/1m2 Charpy impact value: 3.9 m/cm2 Heat deformation temperature: 119°C Rockwell hardness: M-113 [Effects of the invention] The curable resin having the novel structure of the present invention has a It is easy to synthesize, and by radical curing,
A cured product with better physical properties than vinyl ester resin, especially heat resistance and mechanical strength, can be obtained.
It is extremely useful for various applications such as paints, adhesives, molding materials, and FRP.

Claims (1)

[Claims] (A) An epoxy resin having two or more epoxy groups in one molecule is reacted with monohydric phenols so that the epoxy groups and phenolic hydroxyl groups are substantially equimolar. and (B) a saturated or unsaturated monomer having one epoxy group in one molecule. A compound obtained by reacting an epoxy compound with acrylic acid or methacrylic acid in substantially equimolar amounts, each having at least one acryloyl group or methacryloyl group and one hydroxyl group in one molecule. Obtained by reacting a saturated monohydroxyl compound and C) an epoxy resin having two or more epoxy groups in one molecule with acrylic acid or methacrylic acid in a proportion where the epoxy groups and carboxyl groups are substantially equivalent. , a vinyl ester resin each having two or more acryloyl or methacryloyl groups and a hydroxyl group in one molecule, and (D) a curable resin bonded via a diisocyanate.