JP2869753B2 - Polymerizable vinyl compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION << Field of Industrial Application >> The present invention relates to a polymerizable vinyl compound which is a raw material of an epoxy acrylate resin or the like having excellent flexibility.

<< Conventional Technology >> There are various epoxy (meth) acrylate resins obtained by ring-opening acrylic acid or methacrylic acid to the epoxy group of the epoxy resin, including bisphenol A type epoxy (meth) acrylate resin. It is used for various purposes by utilizing the excellent reaction name of the meth) acrylate group.

For example, epoxy (meth) acrylate resin dissolved in styrene is radically polymerized using an organic peroxide, and is used in applications related to corrosion-resistant FRP and resin concrete.

Further, by irradiating an epoxy (meth) acrylate resin dissolved in a reactive diluent such as styrene or acrylate ester with ultraviolet rays or the like in the presence of a sensitizer,
Alternatively, it can be cured in an extremely short time by irradiating an electron beam without a sensitizer, and can be used for coating, adhesive, vehicle for printing ink, solder resist ink, letterpress material,
It is used for applications such as mortar floor lining and PVC tile coating.

<< Problems to be Solved by the Invention >> However, epoxy (meth) acrylate resins are hard and brittle, have high viscosity, and are poor in workability or weather resistance despite being used in many applications. There are various disadvantages.

Conventionally, as a means of imparting flexibility to an epoxy acrylate resin, a method of mainly adding a plasticizer has been adopted, but there has been a drawback that the bleeding of the plasticizer and the physical properties such as water resistance and heat resistance are reduced.

<< Means for Solving the Problems >> Accordingly, the present inventors have intensively studied to improve the disadvantages of the epoxy (meth) acrylate resin and further expand the possibility of the epoxy (meth) acrylate resin.
It has been found that a polymerizable vinyl compound obtained by reacting an aliphatic cyclic epoxy resin represented by the general formula (I) with an unsaturated acid or an unsaturated acid anhydride can impart appropriate flexibility to these resins. The present invention has been completed.

That is, the present invention provides a polymerizable compound obtained by reacting an unsaturated acid or an unsaturated acid anhydride with all or a part of the epoxy groups in the aliphatic cyclic epoxy resin represented by the general formula (I). Is what you do.

The polymerizable vinyl compound of the present invention has a property of imparting flexibility to the aliphatic cyclic epoxy resin represented by the general formula (I) as A
Can be freely changed by the amount of.

In this respect, unlike the external plasticization method in which a plasticizer is added, there is no bleeding phenomenon of the plasticizer, and almost no deterioration in physical properties is observed.

In addition, since the compound of the present invention has both a cationically curable alicyclic epoxy group and a radically curable acrylic group, the compound may contain a photosensitizer for ultraviolet curing or a catalyst which decomposes with light to generate a cation. Can provide a new coating curable by both radicals and cations.

Further, unlike the conventional bisphenol A type epoxy acrylate, the compound of the present invention does not have a benzene nucleus, so that excellent weather resistance can be expected.

 Hereinafter, the present invention will be described in detail.

In the general formula (I), R is an alkyl group having 1 to 30 carbon atoms, and is an m-valent organic compound residue.

It may be alicyclic or linear and may have a double bond.

 Further, an aromatic compound may be used.

Ra and Rb are a hydrogen atom or an alkyl group generally containing 1 to 9 carbon atoms, which is derived from the raw material lactone.

For example, when ε-caprolactone is used as a raw material, RaRb
Are all hydrogen.

When β-methyl-δ valerolactone is used, R
a and Rb are an ethyl group and hydrogen, and when 3 ethyl-caprolactone is used, Ra and Rb are an ethyl group and hydrogen.

 Also, c is determined by the raw material lactone.

For example, c = 5 for ε-caprolactone, c = 4 for valerolactone, and c = 7 for cyclooctanone lactone.

 nm is the number of moles of the added lactone.

For example, when no lactone is added, nm =
When adding 0 and 5 moles, n ₁ + n ₂ +... + Nm = 5.

m is the number of polyfunctional alicyclic esters and corresponds to the number of functional groups of the starting carboxylic acid and acid anhydride used. Examples of the aliphatic cyclic epoxy resin represented by the general formula (I) include, when m is 1, a caprolactone-modified product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (III) or 3 Modified trimethylcaprolactone of 1,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (I
V), (IV) ′ and valerolactone-modified 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate (V),
(V) 'and the like.

Further, in the formula (I), when m is 2, the following formula [Where X ¹ is the following structure —O— (CH ₂ ) ₅ —CO— R ¹ is the following structure And n ₁ and n ₂ represent integers in which n ₁ + n ₂ is 1 or more.
(VI) [Where X ¹ is the following structure: —O— (CH ₂ ) ₅ —CO—; R ² is the following structure: And n ₁ and n ₂ represent integers in which n ₁ + n ₂ is 1 or more.
(VII) Further, in the formula (I), when m is 4, the following formula [However, in the formula (VIII), X ¹ represents the following structure —O— (CH ₂ ) ₅ —CO—, n1, n2, n3, and n4 represent n1 + n2 + n3 +
and represents an integer that satisfies n4 = 1] Also, in the formula (I), when m is 6, the following formula [However, in the formula (IX), X ¹ has the following structure: —O— (CH ₂ ) ₅ —CO—; R ² has the following structure: [Where, in the formulas (III) to (IX), Y ^e is And MY ^e is And n represents an integer of 1 or more].

Further, a method for synthesizing the aliphatic cyclic epoxy resin of the general formula (I) will be described below.

 First, it is produced by the following series of reactions.

[However, In the formula, X is the following structure Y ¹ has the following structure Y ² has the following structure Y ³ has the following structure Represents) or <Reaction-5> An aliphatic cyclic epoxy resin represented by the formula (I), which is a main substance in the curable resin composition of the present invention, is produced by the following oxidation reaction.

In the dehydration esterification reactions of <Reaction-2> and <Reaction-3>, a carboxylic acid and an alcohol can be collectively charged and reacted.

The reaction can be carried out at a temperature of 150 to 250 ° C. At the beginning of the temperature rise, a large amount of water is distilled off, and the temperature does not rise above a predetermined value even if heating is performed more than necessary.

The reaction proceeds, and as the amount of dehydrated water increases, the temperature of the reaction system also increases.

Since the acid value in the system decreases as the reaction proceeds, this can be used as a standard.

The molar ratio of carboxylic acid and alcohol to be charged is 1.0 mol or more of alcohol to 1 mol of carboxylic acid. This is because an excess of the alcohol causes a rapid decrease in the acid value in the system.

However, if the amount is more than the required amount, it takes much time for removal after the reaction is completed, which is not desirable.

Alternatively, when an acid anhydride is used in <Reaction-2> and <Reaction-3>, these reactions are an addition reaction of an acid anhydride and an alcohol and a dehydration esterification reaction of a carboxylic acid and an alcohol.

 The reaction proceeds even at relatively low temperatures.

 However, for industrial reaction, the temperature is 100-250 ° C.

The reaction between the acid anhydride and the alcohol proceeds at a relatively low temperature.

However, in the reaction between carboxylic acid and alcohol, it is advantageous to continuously remove water from the reaction system by a dehydration reaction. Therefore, it is desirable that the temperature be 100 ° C. or higher under normal pressure. Above 250 ° C., decomposition of the lactone oligomers and coloring of the product are extremely undesirable.

Next, <Reaction-1> and <Reaction-4> are lactone modification reactions.

In these reactions, a predetermined lactone is added to an ester or alcohol and a titanium catalyst or a tin catalyst is added in an amount of 0.1 to 10,000 pp.
m can be added and reacted at 150-250 ° C.

If the amount of the catalyst is less than 0.1 ppm, the reaction is slow, and even if it is added at 10,000 ppm or more, a large effect does not appear.

When the temperature is lower than 150 ° C., the speed is low.

Further, the thus obtained general formula By epoxidizing the compound of formula (I), an aliphatic cyclic epoxy resin of the general formula (I) is obtained <Reaction-5>.

This epoxidation is performed using a peracid or hydroperoxide.

As the epoxidizing agent for epoxidation, a peracid or various hydroperoxides can be used.

For example, the peracids include formic acid, peracid, perpropylene acid, perbenzoic acid, trifluoroperacetic acid and the like.

Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide, metachloroperbenzoic acid and the like. At the time of epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.

In the case of hydroperoxides, a catalyst effect is obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. Can be.

[Reaction Conditions] The epoxidation reaction is performed by adjusting the presence or absence of a solvent and the reaction temperature according to the apparatus and the physical properties of the raw materials.

The reaction temperature range that can be used is determined by the reactivity of the epoxidizing agent used.

Regarding peracetic acid, which is a preferred epoxidizing agent, 0
A range of -70 ° C is preferred.

If the temperature is lower than 0 ° C., the reaction is slow, and if the temperature is higher than 70 ° C., decomposition of peracetic acid occurs.

In the case of tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate, which is an example of hydroperoxide, the temperature is preferably from 20 to 150 ° C. for the same reason.

The solvent can be used for the purpose of lowering the viscosity of the raw material, stabilizing the epoxidizing agent by dilution, and the like.

In the case of peracetic acid, an aromatic compound, an ether compound, an ester compound or the like can be used.

In particular, ethyl acetate or xylene is a preferred solvent.

For example, in the case of a peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid may be used as a catalyst.

The charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed depending on the purpose such as how much the unsaturated bond is desired to remain.

When a compound having a large number of epoxy groups is intended, the epoxidizing agent is preferably added in an equimolar amount or more based on the unsaturated group.

However, due to economics and the side reactions described below,
It is usually disadvantageous to exceed 10 moles, and in the case of peracetic acid, 1 to 5 moles is preferable.

Depending on the conditions of the epoxidation reaction, the substituent in the raw material undergoes a side reaction with the epoxidizing agent at the same time as the epoxidation of the double bond, resulting in a modified substituent, which is contained in the target compound.

However, a small amount of by-products may be mixed in the obtained product, which may adversely affect the hue or the acid value. In order to prevent this, at least one of the following additives can be added.

Phosphoric acid, phosphoric acid-potassium, phosphoric acid-sodium, ammonium hydrogen phosphate, pyrophosphoric acid, potassium pyrophosphate, sodium pyrophosphate, sodium 2-ethylhexyl pyrophosphate, potassium 2-ethylhexyl pyrophosphate, sodium 2-ethylhexyl tripolyphosphate , Potassium 2-ethylhexyl tripolyphosphate, 2-
Sodium ethylhexyl tetrapolyphosphate and potassium 2-ethylhexyl tetrapolyphosphate.

The addition amount is 10 ppm to 10,000 ppm in the reaction crude liquid, preferably 50 p.
pm to 1000 ppm.

The effect of these additions is generally considered to be the action of chelating and inactivating metals mixed in from the reactor or raw materials.

[Purification] The product can be separated by various methods.

The crude reaction solution obtained can be directly used as a product by distilling off the solvent and the like.

The conditions for removing low boiling point are 50 to 200 ° C, preferably 80 to 160 ° C.

Further, the reaction can be performed by adjusting the degree of reduced pressure according to the boiling point of each solvent.

Also in this reaction, trace impurities are generated, and it is preferable to wash with water to remove these.

In washing with water, an aromatic compound such as benzene, toluene, or xylene, a hydrocarbon such as hexane, heptane, or octane, or an ester such as ethyl acetate or butyl acetate can be used as the reaction crude liquid.

The washing amount is 0.1 to 10 times, preferably 1 to 5 times the reaction crude liquid vol.
It is twice.

It is also an effective method to remove a trace amount of acid by washing with an aqueous alkali solution and further with water. Examples of the alkaline aqueous solution to be used include NaOH, KOH, K ₂ CO ₃ , Na ₂ C
Aqueous solutions of alkaline substances such as O ₃ , NaHCO ₃ , KHCO ₃ , NH ₃ and the like can be used.

The concentration at the time of use can be freely selected within a wide range.

Alkaline water washing and water washing are 10 to 90 ° C, preferably 10 to 90 ° C.
It is better to carry out in the temperature range of 50 ° C.

After separating the washed liquid into two layers, the organic layer is taken out,
The product can be cut out by low boiling.

The low boiling point removal is 50 to 200 ° C, preferably 80 to 160 ° C, and can be performed by adjusting the degree of reduced pressure according to the boiling point of each solvent.

The reaction can be carried out in any manner, continuous or batch.

In the case of a batch system, a method in which raw materials and additives are charged into a reactor and then an epoxidizing agent is added dropwise is preferable.

When this is washed with water, it is separated into two layers after washing with water, and the organic layer is evaporated with an evaporator to produce a product.

In the case of continuous operation, the raw material, the epoxidizing agent and the additive can be continuously charged into the reactor and continuously extracted. The reactor may be of any type, such as a complete mixing tank or a piston flow type.

The proportion of the aliphatic cyclic epoxy resin in the polymerizable vinyl compound used in the present invention is 97 to 5 parts by weight, preferably 95 to 30 parts by weight based on 100 parts by weight in total.

If the reason is too large, the desired sufficient flexibility can be obtained.

Conversely, if the amount is too small, the resin becomes too soft.

The polymerizable vinyl compound of the present invention can be obtained by subjecting the aliphatic cyclic epoxy resin and the unsaturated acid or unsaturated acid anhydride to a polymerization inhibitor, a solvent or a reactive agent as necessary in the presence or absence of a ring-opening catalyst for an epoxy group. It is obtained by a heat reaction in the presence of a diluent, and therefore, a hydroxyl group generated by ring opening of an epoxy group always exists.

[Effect] The polymerizable vinyl compound of the present invention is a raw material of an epoxy (meth) acrylate resin having excellent flexibility. By dissolving this polymerizable vinyl compound in styrene and subjecting it to radical polymerization using an organic peroxide, corrosion-resistant FRP
And resin concrete applications.

Alternatively, the lactone-modified epoxy (meth) acrylate resin dissolved in a reactive diluent such as styrene or acrylate is irradiated with ultraviolet rays or the like in the presence of a sensitizer, or an electron beam is emitted without a sensitizer. By irradiating, it can be cured in a very short time, and can be used for applications such as paints, adhesives, vehicles for printing inks, solder resist inks, letterpress materials, mortar floor linings, and PVC tile coatings.

[Examples] The polymerizable vinyl compound of the present invention will be described below with reference to examples, but the present invention is not limited thereto.

 In the examples, parts mean parts by weight.

Comparative Example 1 Araldite 6071 (trade name of epoxy resin manufactured by Ciba, epoxy equivalent 450-500) 930 in a five-necked flask equipped with an air inlet tube, a thermometer, a cooling tube, a dropping funnel, and a stirrer.
Parts, 0.54 parts of hydroquinone monomethyl ether as a polymerization inhibitor, and raise the reaction temperature to 85 ± 5 while flowing air.
While maintaining the temperature, 144 parts of acrylic acid and 1.07 parts of triethylamine as a catalyst were added dropwise over about 2 hours.

After the completion of the dropping, the mixture is allowed to react at about 90 ° C. for about 24 hours to obtain an acid value of 3.38 mgKOH / g, oxirane oxygen 0.09%, and a viscosity of about 2,000,000 cp.
/ 25 ° C resin was obtained.

Example 1 730 parts of an epoxy resin represented by the general formula (I) obtained by modifying 504 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate with 228 parts of caprolactone in the same apparatus as the comparative example, and hydroquinone 0.44 parts of monomethyl ether was charged, the reaction temperature was maintained at 85 ± 5 ° C. while flowing air, and 144 parts of acrylic acid and 0.96 parts of triethylamine were added dropwise over about 2 hours.

By reacting at about 90 ° C for about 24 hours after dropping,
Acid value 4.20mgKOH / g, oxirane oxygen 0.09%, viscosity about 50,000c
A resin at p / 25 ° C. was obtained.

Example 2 The same apparatus as in Example 1 was used. [Where X ¹ is the following structure: —O— (CH ₂ ) ₅ —CO—; R ² is the following structure: And Y ^e is the following structure Using the same reaction as above, acid value 1.20 mg KO
A resin having H / g, oxirane oxygen of 2.18%, and a viscosity of about 300,000 cp / 25 ° C. was obtained.

Example 4 The same apparatus as in Example 1 was used. [However, in the above formula, X ¹ represents the following structure: —O— (CH ₂ ) ₅ —CO—, n1, n2, n3, and n4 represent n1 + n2 + n3 +
n4 = 3 Y ^e has the following structure By reacting in the same manner, an acid value of 4.35 mgKOH /
g, oxirane oxygen 0.12%, and a resin having a viscosity of about 2 million cp / 25 ° C.

Application Examples 1 to 3 The epoxy acrylate resin obtained in Comparative Example 1 and the polymerizable vinyl compounds obtained in Examples 1, 2, and 3 were combined with a typical diluent monomer and sensitizer, and 15 μm on an iron substrate.
And applied UV irradiation to obtain a cured coating film.

 Table 1 shows the results.

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁶ identification code FI C08F 299/00 C08F 299/00 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 59/17 C07D 303/18 C07C 69/67 C07C 67/30 C08F 299/00-299/02

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I) [However, in the formula (I), X represents the following structure Y ¹ has the following structure Y ² has the following structure Y ³ has the following structure Represents R is alkyl having 1 to 30 carbon atoms, m-valent organic compound residue, R ^a and R ^b and R ¹¹ to R ^m9 are hydrogen, typically 1
Each group can be replaced simultaneously with an alkyl group containing up to 9 carbon atoms. c represents an integer of 4 to 8, nm represents an integer of 0 or more, and m represents an integer of 1 or more. A polymerizable vinyl compound obtained by reacting a product.