JPH0687916A - Production of epoxy resin - Google Patents

Abstract

PURPOSE:To produce an epoxy resin having extremely low acidity concentration. CONSTITUTION:In a process for producing an epoxy resin by reacting (a) a compound containing one or more vinyl groups and one epoxy group in one molecule with (b) at least one selected from a polybasic acid anhydride, a polybasic acid, an acid ended polymer and a carboxylic acid group-containing polymer and (c) at least one selected from compounds containing one or more active atoms hydrogen to give a vinyl group-containing resin and reacting the resin with peracetic acid, 0.01-1.0% polyphosphoric acid or its metal salt based on peracetic acid is added to peracetic acid to produce an epoxy resin. An epoxy resin having extremely low acidity concentration is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy resin having excellent heat resistance, water resistance and weather resistance.

Since the polymer of the present invention has an epoxy group, it can be used as an initiator or an acid anhydride which produces a cation when exposed to light or heat.
It is a substance that can be used by reacting with epoxy curing agents such as phenol and amine, and is useful as a resin for paints and resin for adhesives. It has excellent heat resistance, weather resistance, water resistance, and blocking resistance. Is an improved epoxy resin.

[0003]

The most widely used epoxy resin in the industry today is the so-called epibis type epoxy resin produced by the reaction of bisphenol A and epichlorohydrin.

This resin has a wide range of products from liquid to solid, and has the advantage that the reactivity of the epoxy group is high and it can be cured at room temperature with polyamine.

However, even though the cured product has excellent water resistance and is tough, it has poor weather resistance and poor electrical properties such as tracking resistance.
There are drawbacks such as low heat distortion temperature. Especially recently
Epoxy resin made to react with phenol or novolac resin and epichlorohydrin is used as the sealing resin for VLSI, etc., but the resin contains several hundred ppm of chlorine, which deteriorates the electrical characteristics of electrical parts. There is a problem. An alicyclic epoxy resin is an epoxy resin that does not contain chlorine and has excellent electric characteristics and heat resistance.

The epoxy resin proposed in Japanese Patent Application Laid-Open No. 04-083739 has excellent heat resistance, water resistance and weather resistance, has a higher reactivity than conventional epoxy resins, and has an acid anhydride,
Can cure phenolamine.

JP-A-04-083739 proposes that an epoxy resin is produced by reacting a resin having a vinyl group with an epoxidizing agent. Considering industrial production, peracetic acid, which is relatively stable and highly reactive as an epoxidizing agent and is industrially available at low cost, is advantageous.

[0008]

However, as a result of investigations by the present inventors, an acidic substance other than acetic acid is by-produced at the same time as a target product in the reaction between a resin having a vinyl group and peracetic acid. It was found that the higher the temperature during the reaction, and the higher the concentration of peracetic acid, the larger the amount produced, and that once produced, it is extremely difficult to remove it by a usual method such as distillation or washing with water. This acidic substance present in the epoxy resin not only reduces the stability of the epoxy,
It is considered that the physical properties of the cured product are also affected. For example,
When it is used for sealing a semiconductor, it may lower the insulating property and cause metal corrosion. Therefore, it is desirable to suppress the production of acidic substances as much as possible. In fact, it is possible to suppress the production of acidic substances to some extent by lowering the reaction temperature, the amount of charged peracetic acid, and the concentration of peracetic acid, but the reaction rate is slow and the epoxidation rate is low, which is economical It wasn't practical at all.

The present invention solves the above problems and provides a method for producing an alicyclic epoxy resin which is excellent in heat resistance, water resistance and weather resistance and has an extremely small content of acidic substances. .

As a result of the present inventors' investigations under these circumstances, as a result of the reaction of a resin having a vinyl group with peracetic acid, 0.01% to 1.0% of polyphosphoric acid or its It was found that an epoxy resin having an extremely low acid concentration can be produced by adding a metal salt, and the present invention has been completed.

Further, it has been clarified that the characteristics of the epoxy resin can be changed and various characteristics can be given by combining various kinds of (a), (b) and (c) to be used.

[0012]

The present invention comprises (a) a compound having at least one vinyl group and one epoxy group in one molecule, (b) a polybasic acid anhydride, a polybasic acid, A vinyl group obtained by reacting at least one selected from an acid-terminated polymer and a polymer containing a carboxylic acid group with (c) at least one selected from compounds having one or more active hydrogens. Of the epoxy resin, wherein 0.01 to 1.0% of polyphosphoric acid or a metal salt thereof is added to peracetic acid in the step of producing an epoxy resin obtained by reacting a resin having It relates to the manufacturing method.

Next, the present invention will be described in more detail.

The compound having one epoxy group and one or more vinyl groups in one molecule used in the present invention is represented by the general formula (I
V) << i is an integer of 1 to 5, R ¹ and R ⁴ are hydrogen atoms or an alkyl group having 1 to 50 carbon atoms or a substituted phenyl group,
R ² and R ³ are a hydrogen atom or an alkyl group having 1 to 50 carbon atoms, and R ² and R ³ may be wound around a ring. 》
It is represented by.

Examples of the compound represented by (IV) are the compounds shown below.

4-vinylcyclohexene-1-oxide, 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide, limonene monoxide, trivinylcyclohexane monoxide, divinylbenzene monoxide, butadiene mono Oxide and 1,2-epoxy-
Examples thereof include compounds represented by (Formula 1) such as 9-decene, compounds represented by (Formula 2) such as allyl glycidyl ether, and compounds such as glycidyl styryl ether.

Further, the following compounds can also be used.

[0018]

[Chemical 1]

[Chemical 2]

[Chemical 3]

[Chemical 4] These may be used alone or in combination of two or more.

If necessary, ethylene oxide,
Propylene oxide, cyclohexene oxide, styrene oxide, monoepoxides such as α-olefin epoxide, vinyl cyclohexene dioxide, 3,4-
A diepoxide such as epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate may be used at the same time as the compound having one epoxy group and one or more vinyl groups in one molecule.

The polybasic acid anhydrides or polybasic acids (b) used in the present invention include aromatic polybasic acids and acid anhydrides thereof, and aliphatic polybasic acids and acid anhydrides thereof. Examples of aromatic polybasic acids and acid anhydrides thereof include:
Examples include phthalic anhydride, isophthalic acid, terephthalic acid and trimellitic anhydride. Examples of the aliphatic polybasic acid and its acid anhydride include tetrahydrophthalic acid, 4-methylhexahydrophthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, and their acid anhydrides, fumaric acid and sebacic acid. , Dodecane diacid, etc.

The acid-terminated polymer used in the present invention is an acid-terminated polymer obtained by reacting a polybasic acid with polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol, polyvinyl cyclohexene glycol or the like. Examples include ethers, acid-terminated polyesters, acid-terminated polybutadienes and acid-terminated polycaprolactones.

Further, an acrylic copolymer having a carboxylic acid group can be used instead of the acid terminal polymer, and it contains a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and a carboxylic acid group. These polymers may be used alone or in combination of two or more.

Next, as the compound (c) having active hydrogen used in the present invention, alcohols, phenols, carboxylic acids, amines, thiols, hydroxyl group-terminated polymers, polymers having a hydroxyl group and the like are listed. can give.

Alcohols are monovalent, divalent, trivalent or higher, such as methanol, ethanol,
Examples thereof include benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol and triglycerol. In addition, neopentyl glycol, neopentyl glycol ester of hydroxyhyvalic acid, dipentaerythritol,
1,4-cyclohexanedimethanol, trimethylpentanediol, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide addition of hydrogenated bisphenol A A thing etc. can also be used.

The phenols include phenol, cresol, catechol, pyrogallol, hydroquinone,
Hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, phenol resin, cresol novolac resin and the like.

Examples of the hydroxyl group-terminated polymer used in the present invention include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol and polyvinyl cyclohexene glycol, hydroxyl group-terminated polyesters, hydroxyl group-terminated polybutadiene, Examples include hydroxyl-terminated polycaprolactone and polycarbonate diol. Further, an acrylic copolymer having a hydroxyl group or the like can be used instead of the hydroxyl group-terminated polymer.

The carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane diacid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid. Acid, terephthalic acid, etc.

Further, compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid and oxycaproic acid, can also be mentioned.

The amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine,
Octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine and the like.

As the thiols, methyl mercaptan,
Mercapto such as ethyl mercaptan, propyl mercaptan, phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol ester of mercaptopropionic acid, for example, ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, pentaerythritol pentamercaptopropionic acid, etc. Can be given.

Further, as the compound having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, Styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin,
Examples include polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, polytetramethylene glycol, and the like.

The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, acrylic acid, methacrylic acid,
There are 2-hydroxyethyl methacrylate, 3-cyclohexenemethanol, tetrahydrophthalic acid and the like.

Any compound can be used as long as it is a compound having these active hydrogens, and two or more kinds thereof may be mixed.

The epoxy resin used in the present invention includes the compound (a) having at least one vinyl group and one epoxy group in the above molecule, a polybasic acid anhydride, a polybasic acid, and an acid terminal polymer. , And a resin having a vinyl group obtained by reacting at least one selected from the polymer (b) containing a carboxylic acid group and at least one selected from the compound (c) having active hydrogen. Further, it is obtained by epoxidizing with an epoxidizing agent.

The starting materials (a), (b), and (c) are charged at a ratio of 1 to 99 parts by weight of (a), preferably 30 to 80 parts, and 99 to 1 parts by weight of (b). Parts, preferably 20 to 70 parts, and 0 to 99 parts by weight of (c), preferably 0 to 30 parts. The component (c) may not be used depending on the case. When the component (c) is not used,
It is necessary to control the molecular weight while detecting the dehydration amount by controlling the reaction time, the degree of reduced pressure, the reaction temperature, and the like.

When the amount of component (a) used is relatively small, the epoxy group content in the target epoxy resin is small. The molar ratio of component (a) / component (b) is 0.
It is 4 to 5.0, preferably 0.5 to 3.0.

When the ratio of the component (a) is high, the ratio of terminal hydroxyl groups is high, and when the terminal of hydroxyl group and the terminal of carboxyl group are present, all terminals become hydroxyl groups as the dehydration reaction proceeds.

On the contrary, when the ratio of the component (b) is increased, the ratio of the terminal to be the carboxyl group is increased, and in the case where the hydroxyl group terminal and the carboxyl group terminal are present, all the terminals become the carboxyl group as the dehydration reaction proceeds. Become. However,
When the ratio of the component (a) increases, a part of the component (a) remains unreacted and remains. Further, when the ratio of the component (b) becomes unnecessarily large, the component (b) remains without reacting.

In the reaction for synthesizing the resin having a vinyl group, a catalyst for promoting the ring-opening reaction of the epoxy group by the carboxyl group and, if necessary, a catalyst for promoting the (dehydration) esterification reaction may be used in combination. Good.

As the catalyst for promoting the ring-opening reaction of an epoxy group with a carboxyl group which can be used in the present invention, a tertiary amine such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, tri-n-octylamine, or tetramethylammonium chloride is used. , Quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide, alkylureas such as tetramethylurea, and alkylguanidines such as tetramethylguanidine.

The catalyst for promoting the ring-opening reaction that can be used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0.1 to 5.0 relative to the epoxy compound.
%, Preferably 0.5 to 3.0% by weight. The ring-opening reaction is 50 to 200 degrees, preferably 1
Perform at 00 to 180 degrees.

Examples of the catalyst for promoting the (dehydration) esterification reaction that can be used in the present invention include Sn compounds such as tin octylate and dibutyltin laurate, and Ti compounds such as tetrabutyl titanate.

The catalyst for promoting the (dehydration) esterification reaction used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0-100 with respect to the reaction system.
It is recommended to use 0 ppm, preferably 50 to 500 ppm. This (dehydration) esterification reaction is 180 to 240 ° C.
Done in.

The ring-opening reaction of the epoxy group with the carboxyl group and the (dehydration) esterification reaction may be carried out sequentially, but after the raw materials and the catalyst are charged in a batch, the reaction temperature is raised stepwise according to the progress of the reaction. Method is preferred. If necessary, after the component (c) and the catalyst are charged at once,
The components (a) and (b) may be dropped.

When the resin thus synthesized having a cyclic olefin or vinyl group is epoxidized with peracetic acid, 0.01 to 1.0% of polyphosphoric acid or a metal salt thereof is added to peracetic acid. Added.

As the polyphosphoric acid, phosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, hexametaphosphoric acid, tetrapolyphosphoric acid and the like can be used. In addition, the alkali metals such as Na and K,
Salts of alkaline earth metals such as Ca and Mg and transition metals such as Zn can be used. As the polyphosphoric acid and its metal salt, those in which some or all of them are organic esters such as alkyl esters and phenyl esters can also be used.

The polyphosphoric acid and its metal salt can be used alone or in combination of two or more.

When the addition amount of polyphosphoric acid and its metal salt is less than 0.01% with respect to peracetic acid, no remarkable effect of suppressing the production of acidic substances other than acetic acid is observed, and 1.
Even if it is added in an amount of 0% or more, no further effect can be expected, and the manufacturing cost only increases. Therefore, the amount of the additive is 0.01-1.0%, preferably 0.05-1.0% with respect to peracetic acid.
It is 0.5%.

The polyphosphoric acid and its metal salt can be added directly to the resin solution or gradually added dropwise. Also,
It can be used by dissolving it in peracetic acid.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the physical properties of the equipment and raw materials.

The reaction temperature is preferably 0 to 70 ° C.

At 0 ° C. or lower, the reaction is slow, and at 70 ° C., decomposition of peracetic acid occurs.

As the solvent, aromatic compounds, ethers, esters and the like can be used for the purpose of reducing the viscosity of the raw material and stabilizing by diluting peracetic acid.

The charged molar ratio of peracetic acid to the unsaturated bond can be changed according to the purpose such as how much unsaturated bond is desired to remain.

When the charged molar ratio of peracetic acid to the unsaturated bond is large, a compound having many epoxy groups is produced, but at the same time, many side reactions occur. On the other hand, when the molar ratio is reduced, side reactions are reduced but epoxy groups are reduced. Therefore, the charged amount of peracetic acid is preferably 0.6 to 1.5 times mol.

The epoxidation reaction is carried out continuously or batchwise, but in the case of continuous reaction, the piston flow type is preferred.
At this time, each of the polymerization inhibitors may be charged individually, but it is preferable that the powdery one is dissolved in a solvent and then charged. further,
The same applies to the batch method, but it is desirable to use the semi-batch method in which the epoxidizing agent is sequentially charged.

The composition of interest can be taken out from the reaction crude liquid by chemical engineering means such as concentration. However, for the purpose of removing the added polyphosphoric acid and metal salt from the system, the reaction crude liquid is washed with water before concentration. Alternatively, it is preferable to perform adsorption treatment or the like.

[0058]

Since the epoxy resin produced by the production method of the present invention has an epoxy group in the side chain, it cures an initiator such as an acid anhydride, phenol, amine or the like which produces a cation by light or heat. It is a substance that can be used by reacting with an agent and is useful in various fields. further,
The epoxy resin of the present invention has an epoxy group having a reactivity different from that of the glycidyl group, and is a useful substance as a resin for paints and a resin for adhesives. In particular, a substance having a high Tg and hardly blocking is a substance useful as a resin and a curing agent for powder coatings.

Further, the epoxy resin produced by the production method of the present invention is crosslinked using a phenol novolac resin or other curing agent, so that it is excellent in LSI encapsulation due to the low concentration of halogen impurities and acidic substances. It can also be used as a stopper.

Next, the present invention will be described with reference to examples.

Claims (11)

[Claims] 1. (a) A compound having one or more vinyl groups and one epoxy group in one molecule, and (b) a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and a carboxylic acid. At least one selected from the group-containing polymers, (c)
In the step of producing an epoxy resin obtained by reacting a resin having a vinyl group, which is obtained by reacting at least one selected from compounds having one or more active hydrogens, with peracetic acid, the amount of the resin having a vinyl group of 0. A method for producing an epoxy resin, which comprises adding 01 to 1.0% of polyphosphoric acid or a metal salt thereof. 2. The method for producing an epoxy resin according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is 4-vinylcyclohexene-1-oxide. 3. The compound having one or more vinyl groups and one epoxy group in one molecule is 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide. 1. Epoxy resin manufacturing method of 1. 4. The method for producing an epoxy resin according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is limonene monoxide. 5. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (I): The method for producing an epoxy resin according to claim 1, wherein the compound is represented by << n is an integer of 0 to 30 >>. 6. A compound having one or more vinyl groups and one epoxy group in one molecule is represented by the following general formula (II): The method for producing an epoxy resin according to claim 1, wherein the compound is represented by << n1 and n2 are integers from 0 to 30 >>. 7. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (III): The method for producing an epoxy resin according to claim 1, wherein the compound is represented by "Ph is a substituted phenyl group and n is an integer of 0 to 30". 8. A compound having one or more active hydrogens,
The method for producing an epoxy resin according to claim 1, which is an alcohol, a hydroxyl group-terminated polymer, or a polymer containing a hydroxyl group. 9. The method for producing an epoxy resin according to claim 1, wherein the acid-terminated polymer is an acid-terminated polyester. 10. The method for producing an epoxy resin according to claim 8, wherein the hydroxyl group terminated polymer is a hydroxyl group terminated polyester. 11. The method for producing an epoxy resin according to claim 8, wherein the hydroxyl group-terminated polymer is a hydroxyl group-terminated polyether.