JPS6392634A - Curable resin - Google Patents

Abstract

PURPOSE:To provide the title resin having excellent hardness and strength and useful for paints, adhesives, lining materials, molding materials, etc., by bonding a specified polyhydroxyl compd. to an unsaturated monohydroxyl compd. through a diisocyanate. CONSTITUTION:A novolak or polyhydric phenol (a) having at least two phenolic hydroxyl groups per molecule is reacted with a monoepoxy compd. (b) having an epoxy group in an equimolar amount to said hydroxy group in the presence of a catalyst at 80-160 deg.C to obtain a polyhydroxyl compd. (A) having at least two alcoholic hydroxyl groups per molecule. Separately, an unsaturated monoepoxy compd. (c) having one unsaturated group and one epoxy group per molecule is reacted with an equimolar amount of (meth)acrylic acid (d) in the presence of a catalyst and a polymn. inhibitor to obtain an unsaturated monohydroxyl compd. (B) having two unsaturated groups and one hydroxyl group per molecule, at least one of said unsaturated groups having a (meth) acryloyl group. A diisocyanate is added to the component A and the adduct is reacted with the component B.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention has 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. The present invention relates to radically 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 expand, new demands arise, and 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, there is always a demand for gel coats that form the surface layer of FRP molded products, which are harder, more scratch resistant, and have better heat resistance and color stability. There is.

High performance SMC,B by increasing the viscosity of vinyl ester resin
There is also a desire to use it as a MC, and in this case, it has been carried out to react the hydroxyl groups present in the vinyl ester resin with a diisocyanate.

However, although the reason is not clear, even when a small amount (less than 5%) of diisocyanate is added to vinyl ester resin, gluing may occur during the reaction, resulting in the formation of SMC and BM.
It is also known that the moldability of C is not stable.

[Problem that the invention seeks to solve]

The present invention solves 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 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 matahinyl ester resin ranks 105-106 on the Rockwell hardness M scale, which is far below the hardness of melamine resin, which is 115-12o1 on the Rockwell hardness M scale and 4H, which has a pencil hardness. Ta.

[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 found that (A) novolak or polyhydric phenol having two or more phenolic hydroxyl groups in one molecule ( (hereinafter referred to as polyhydric phenols),
Monoepoxy, polyhydroxyl having two or more alcoholic hydroxyl groups (hereinafter referred to as hydroxyl groups) in one molecule, obtained by reacting a compound so that the epoxy group and phenolic hydroxyl group are substantially equimolar. (B) Adding acrylic acid or methacrylic acid (hereinafter referred to as (meth)acrylic acid) substantially to an unsaturated monoepoxy compound that shares one unsaturated group and one epoxy group in each molecule. Two unsaturated groups in one molecule [at least one of which is an acryloyl group or a methacryloyl group (hereinafter referred to as (meth)acryloyl group)] obtained by reacting in equimolar proportions with (C) an unsaturated monohydroxyl compound that shares one hydroxyl group;
The inventors have discovered that a curable resin bonded via a diisocyanate is hard and has excellent strength, and have arrived at the present invention.

[Effect]

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.

(Left below) ＾ 40th grade S'Tatsumi ΦKyoQ Pekyo
-K Ro vinyl ester resin is reacted 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.

(a) Resin synthesis can be performed safely.

When reacting a small amount (several positions) of diisocyanate with vinyl ester, ・One molecule of vinyl ester・
When there is a large amount of diisocyanate as a whole, such as when 0.5 to 1 molecule of diisocyanate is added, the resin becomes calcified and cannot be synthesized successfully, although the reason is not clear.

However, even if the proportion of diisocyanate used is the same, according to the present invention, since the positions of the two isocyanate groups in the intermediate inocyanate adduct are far apart, phenomena such as dulling or an abnormal increase in viscosity may occur. Resins can be synthesized safely without having to look at them.

(mouth) Physical properties improve.

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

The polyhydroxyl compound having two or more hydroxyl groups in one molecule used as component (A) of the present invention is a polyhydric phenol having two or more phenolic hydroxyl groups in one molecule, and a monoepoxy compound. It is produced by reacting the epoxy group and the phenolic hydroxyl group so that the epoxy group and the phenolic hydroxyl group become substantially equimolar, and converting the epoxy group into an alcoholic 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 80-160°C. The end point of the reaction is determined by infrared analysis and the disappearance of epoxy groups.

Examples of the polyhydric phenols used in the present invention include the following types. Bisphenol A1 Bisphenol F1 Bisphenol 81 Catechol, resorcinol, hydroquinone, so-called novolac obtained by reacting phenol with formaldehyde using an acid catalyst. Phenols include phenol, o-cresol, m
- xylenol represented by cresol, p-cresol, 3,5-xylenol; nosola-substituted phenols such as paratertiary-butylphenol, paraoctylphenol, paraphenylphenol, nografumylphenol.

Examples of monoepoxy compounds for converting phenolic hydroxyl groups into hydroxyl groups by reacting with the above polyhydric phenols include ethylene oxide, propylene oxide, phenyl glycidyl ether, shrimp chlorohydrin, styrene oxide, butyl glycidyl ether, is typical.

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

Unsaturated which shares two unsaturated groups (at least one of which is a (meth)acryloyl group) and one hydroxyl group in one molecule used as component (B) of the present invention A monohydroxyl compound is produced by reacting an unsaturated monoepoxy compound that shares one unsaturated group and an epoxy group in each molecule with (meth)acrylic acid in a substantially equimolar ratio. Ru.

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

For the reaction between the unsaturated monoepoxy compound and (meth)acrylic acid, the reaction catalyst used in the reaction system of the polyhydric phenol and the monoepoxy compound described above is used as a catalyst.

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

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

2.4 tolylene diisocyanate, 2.4) mixture of lylene diiso7anate and 2,6 tolylene diisocyanate, trinon diisocyanate, sophenylmethanoisocyanate, paraphenylene diinocyanate,
1,5-naphthylene diisocyanate, 1.6-hexamethylene diisocyanate, isophorone diincyanate, quinolin diinocyanate, hydrogenated x7-lylene diisocyanate.

The curable resin of the present invention is produced by combining the (A) component and (B) component with the (C) component. The reaction can be carried out by adding the three components simultaneously, but after adding component C) to the recovered portion or one of component (B),
A method in which the remaining component (B) or component (C) is reacted is preferred from the viewpoint of preventing gluing.

The addition reaction between the recovered fraction and component (C), that is, the reaction between the polyhydroxyl compound and diisocyanate, is carried out safely, probably because the hydroxyl groups are located far apart.

The blending ratio of the polyhydroxyl compound, unsaturated monohydroxyl compound, and noiso/anate, that is, the molecular weight, can be selected as necessary, but it is practically preferable to blend the repeating units so that the number is 5 or less.

It is practically convenient to carry out the reaction in a monomer or in a solvent.

It goes without saying that the curable resin according to the present invention can be used in combination with fillers, reinforcing materials, mold release agents, colorants, thermoplastic polymers, etc. when put into practical use.

〔Example〕

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

Example 16 Production of polyhydroxyl compound (1) Bisphenol A was added to a 1J three-way flask equipped with a stirrer, a reflux condenser, and a thermometer. When warmed,
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 (1) cooled to room temperature was a pale yellowish brown semi-solid.

Production of Isocyanate Addition 6 [■] In a similar apparatus, 550% of the polyhydroxyl compound CI) was added.
．． 9. Styrene 250.9. /# Labenzoquinone 0.0
After weighing IN and dissolving it by heating at 60 to 70°C, 2.4
-Tolylene diisocyaner) 35011 was added, and 60°C
After reacting for 5 hours, infrared analysis showed that the incyanato group-containing system had decreased by almost half to 53%.

Add styrene 25ON and incyanate adduct [■
] was obtained in the form of a pale yellowish brown liquid.

Preparation of unsaturated monohydroxyl compound [I[1] Into a 11-three flask equipped with a stirrer, a reflux condenser, and a thermometer, 284 N of glycidyl methacrylate, 172 g of methacrylic acid, 2 J of triphenylphosphine, and 0.2 Fli of hydroquinone were added. When heated and stirred at ℃ for 5 hours, the acid value became 11, so styrene 24
41 was added to produce an unsaturated monohydroxyl compound [■] (glycerin dimethacrylate styrene solution).

Preparation of curable resin CA) 700 J of the isocyanate adduct [■] all-needle, unsaturated monoalcohol compound [■] (styrene solution) is transferred to a 31-meter flask equipped with a stirrer, a reflux condenser, and a thermometer.

After raising the temperature to 60°C, dibutyltin dilaurate4. l
After adding il and reacting at 60° C. for 3 hours, infrared analysis confirmed that the incyanato group had disappeared.

Furthermore, styrene 600I is added to make a curable resin [A]
was obtained with a reddish brown color and a viscosity of 3 poise.

A system in which 100 parts of resin (A) was mixed with 1.5 parts of ≠328E from Kayaku Nouri Co., Ltd. as a hardening agent and 0.3 parts of cobalt naphthenate was cured in 12 minutes, rapidly exothermic, and reached a maximum. The temperature reached 168°C.

The physical properties of the molded resin are: bending strength 13.9 t2 heat distortion temperature
143°C Rockwell hardness M-117 Shalpy impact value 2.3 kg / 2,
Although it is hard, it has been found to be highly heat resistant and strong.

Example 2 1 mole of propylene oxide was added to each bisphenol in a 21-four flask equipped with a stirrer, a thermometer, a reflux condenser, and a gas inlet tube.Product name B manufactured by Asahi Denka Co., Ltd.
PX-11 to 35011. After uniformly dissolving 250 g of styrene and 0.01 g of parabenzoquinone, diphenylmethane diisocyanate soo,p was added and reacted at 60°C for 5 hours in dry air. As a result of infrared analysis, incyanate groups were approximately 59 (% ) was judged to have decreased.

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

Production of curable resin CB'l Unsaturated monohydroxyl compound produced in Example 1 [
■] (Styrene solution of glycerin dimethacrylate) 6
00F'i - Weighed the mixture into a 31-meter flask equipped with a stirrer, a reflux condenser, and a thermometer, added 1100 g of incyanato adduct and 300 I of styrene, reacted at 60°C for 5 hours, added 3.4 g of diptyltin dilaurate, and added 2. After reacting for a period of time, infrared analysis showed that the free incyanato groups had completely disappeared.

Styrene 750011 was added to obtain a curable resin CB) having a viscosity of 2.1 poise and a pale reddish brown color with a slightly cloudy appearance.

A system prepared by adding 1.5 parts of 328E and 0.2 parts of cobalt naphthenate to 100 parts of resin CB) glued at room temperature in 13 minutes and rapidly generated heat, reaching a maximum exothermic temperature of 161°C.

The physical properties of the cured resin are shown in Table 2, and it was hard and had high toughness.

Bending strength: 15.7 Li 2 Flexural modulus: 490 Yu/l 1 II 2 Heat deformation temperature
154℃ Rockwell hardness M-118 Shalpy impact value 2.6 cyn/accuracy 2 Example 3
° Into a 11 separable flask equipped with a stirrer, reflux condenser, and thermometer, 228 g of allyl glycidyl ether!
! , acrylic acid 1749, benzyldimethylamine 1.
2F, hydroquinone monomethyl ether 0.2
II, and reacted at 90-95°C for 12 hours, the acid value became 14.3, so styrene 1289 was added, and the unsaturated monohydroxyl compound [''V] became pale yellow,
Obtained in liquid form.

Production of inocyanate adduct [■] Equipped with a stirrer, reflux condenser, and thermometer 2! In a separable flask, unsaturated monohydroxyl compound [■]
(styrene solution) at 5301. 444 g of isophoro/diisocythi) and 356 I of styrene were added, and 0.2 N of hydroquinone monomethyl ether and 42 of sibutyltin dilaurate were added and reacted at 60°C for 5 hours.
As a result of infrared analysis, the free isocyanate groups are approximately 44 (I
It was recognized that N remained.

The obtained isocyanate adduct [■] was a pale yellow liquid.

Synthesis of curable resin [C] In a 31 separable flask equipped with a stirrer, reflux condenser, rm meter, and dropping funnel, add novolac (phenol 940 #, 40% formalin 750 g, oxalic acid 201
The product obtained by reacting 1 was steam distilled to give 0.4% free phenol, melting point about 80°C, GPC
The result of the analysis is that it seems to be about 2.1 to 2.5 nuclear bodies).
0.9. Phenylgucidyl ether 300.9. Trimethylbenzylammonium chloride 2.5 F,
When heated to 120-130℃, it rapidly generates heat and reaches around 160℃, so it is cooled to prevent further temperature rise and reacted at 150-160℃ for 5 hours. Infrared analysis shows that free epoxy It was observed that the group had disappeared.

450 ml of styrene was added to obtain a Novosic-monoepoxy adduct in the form of a pale yellowish brown liquid.

To this, 1,300 g of isocyanate adduct [■] was added, and further 2ji of dibutyltin tholaurate, 0.2.9 of hydroquinone monomethyl ether. After reacting at 60° C. for 5 hours, infrared analysis showed that free isocyanate groups had completely disappeared.

250 g of styrene was added to obtain a curable resin [C] having a light reddish brown color (Gardner color number: 2) and a viscosity of 3.4 poise.

2 parts of methyl ethyl ketone peroxide and 0.5 parts of naphthenic cobalt were added to 100 parts of resin [''C], and the mixture was coated onto a sonderite-treated steel plate using a bar coater to a thickness of 0.2%.

The coating film glued in about 23 minutes and became tack-free after 1 hour.

The hardness of the coating film after one week was 48.

〔Effect 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 novolac or polyhydric phenol 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 unsaturated monoepoxy having one unsaturated group and one epoxy group in each molecule; Two unsaturated groups in one molecule (at least one of which is an acryloyl group or a methacryloyl group) obtained by reacting a compound with acrylic acid or methacrylic acid in substantially equimolar proportions. ) and an unsaturated monohydroxyl compound sharing one hydroxyl group through (C) a diisocyanate.