JPS5812896B2 - Epoxy ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing unsaturated epoxy esters with improved curability, more specifically (A epoxy compounds having two or more epoxy groups in the molecule; Reacting a monoglycidyl compound, (C) an unsaturated dibasic acid or an unsaturated alkoxydide having carboxyl groups at both ends, and (D) a saturated or unsaturated monobasic acid or a half-esterified product of a saturated or unsaturated dicarboxylic acid anhydride. This is a method for producing unsaturated epoxy esters with good curability, allowing the molecular weight and resin liquid viscosity to be freely adjusted.

Photopolymerizable compositions, especially reaction products of epoxy resin prepolymers with ethylenically unsaturated acids such as acrylic acid or methacrylic acid (β-hydroxy esters) as vehicles that polymerize rapidly when exposed to ultraviolet light and certain photosensitizers. Agent (
A composition consisting of a photopolymerization initiator was published in Japanese Patent Publication No. 44-1903.
It is described in Publication No. 8.

However, such β-hydroxy ester has very poor fluidity, and since carboxyl groups are bonded to both ends of the epoxy compound, it cannot be expected to have a high molecular weight. It also has the disadvantage of poor curability because it does not have any unsaturated groups with properties.

In order to improve these drawbacks, β, which is composed of polyepoxide and α/β-monoethylenically unsaturated monocarboxylic acid, has been proposed.
- A photopolymerizable composition consisting of a small amount of a mixture of a hydroxy ester, a polyitaconate consisting of a polyepoxide and an itaconic acid (Japanese Unexamined Patent Publication No. 18989/1989), or a part or most of a polymerizable unsaturated monobasic acid. An unsaturated epoxy ester (Japanese Patent Publication No. 4.5-40069) is known, which is obtained by reacting an acid component obtained by substituting a polybasic acid with a saturated or unsaturated polybasic acid and an epoxy compound.

These unsaturated epoxy esters can be used to adjust the degree of crosslinking, increase the molecular weight to a certain extent, and improve curing properties to some extent, but it is still not sufficient, and the reaction product has a very high viscosity. In some cases, there is a risk of gelation occurring during the synthesis reaction, so it is necessary to add an organic solvent or polymerizable monomer as a diluent during synthesis, or add a solvent or polymerizable monomer to the resin liquid that is the reaction product. Monomers had to be added to adjust the required viscosity.

The use of this solvent not only significantly reduces workability during synthesis reactions or curing, but also causes so-called so-called problems such as crystallization of the monomer in the photosensitive layer, generation of bad odors due to volatilization of the solvent, and deterioration of the working environment. It also causes solvent pollution.

In addition to these, polyepoxy compounds, reaction products of polyepoxy compounds and acrylic acid or methacrylic acid, which are obtained by simultaneously reacting a monoepoxy compound and acrylic acid or methacrylic acid, and reaction products of a monoepoxy compound and acrylic acid or methacrylic acid, Unsaturated epoxy ester resin composition consisting of a mixture of reaction products (
JP-A-50-33279) is also known.

This resin composition can be synthesized in a one-step reaction, and does not necessarily require solvents or monomer components during the synthesis reaction or curing.Although this resin composition has excellent workability, it does not have a high molecular weight and cannot be cured. Furthermore, since the resin composition contains low-molecular-weight volatile components, there were problems such as a bad odor being produced during curing.

On the other hand, in recent years, due to the demands of the times such as environmental protection, improvement of workability, and energy saving, resins that exhibit fluidity at room temperature, have high molecular weight, high reactivity (excellent curability), and low volatility, and can be adjusted to meet the needs of resin viscosity. This is an unsaturated epoxy ester (photosensitive oligomer) that can control the properties of the cured product. Saturated epoxy esters are in high demand.

The present inventors conducted intensive studies to produce an unsaturated epoxy ester that fully satisfies these requirements, and as a result, completed the present invention.

That is, the present invention provides (A) an epoxy compound having two or more epoxy groups in the molecule, (a a saturated or unsaturated monoglycidyl compound, and (q an unsaturated dibasic acid or an unsaturated alkoxy compound having carboxyl groups at both ends). Half-esterified products of saturated or unsaturated monobasic acids or saturated or unsaturated dicarboxylic acid anhydrides in molar ratio -C
-(A:(F3)=90~10: 10~90, (Q:
(Il1=90-10: 10-(B+(I)90, -> 0.25, and the total number of (Al+(Q poquin groups/carboxyl groups-0.8-1) in all reaction components.

This is a method for producing an unsaturated epoxy ester with improved curability, which is characterized in that the reaction is carried out within a range such that 2.

The method of the present invention does not necessarily require organic solvents or polymerizable monomers during the synthesis reaction or curing, so it has excellent workability, and the molecular weight and viscosity of the resin obtained can be freely adjusted. In addition, because it has a highly reactive polymerizable group in its main chain, it has excellent photocurability with ultraviolet rays and peroxide catalysts, and furthermore, because the resin itself has a high molecular weight. It has very excellent properties such as very little volatile component contamination and almost no odor.

The present invention will be explained in detail below.

In the present invention, the epoxy compound having two or more epoxy groups in the molecule refers to saturated or unsaturated aliphatic, cycloaliphatic, aromatic, or heterocyclic polyepoxides, such as bisphenol A and shrimp. Sumiepoxy ELA-1.28, -11.5 (synthesized by reaction with chlorohydrin or methyl epichlorohydrin)
Sumitomo Chemical Co., Ltd. (product name), Epicote-827, -8 2
Sumiepoxy ELR-130, ELP-160, ESCN-22 obtained by reacting bisphenol-A type epoxy compounds such as 8 (Shell Co., Ltd. trade name), phenol, cresol, resorcinol, or their analogues with epichloro, ruhydrin, or methylepichlorohydrin.
Epoxy compound DEN-4 such as 0 (product name of Sumitomo Chemical Co., Ltd.)
31 (trade name of Dow Chemical Company), or Sumie epoxy ELN-125, ELM-120, which is made by reacting aniline or meta-aminophenol with shrimp chlorohydrin.
Di- or triglycidyl-type epoxy compounds such as (trade name of Sumitomo Chemical Co., Ltd.), and epoxy compounds synthesized from the reaction of glycols with epichlorohydrin or methylepichlorohydrin, halogenated phenols and shrimp chlorohydrin or methylepichlorohydrin. Epoxy compounds are synthesized by oxidizing double bonds in the molecule, and epoxy compounds are synthesized by reacting phenols with ethylene oxide, propylene oxide, etc., with shrimp chlorohydrin or methyl epichlorohydrin. Any compound having two or more epoxy groups in its molecule can be used, such as epoxy compounds obtained by reacting carboxylic acid with epichlorohydrin or methyl epichlorohydrin, and these epoxy compounds may be used alone or in combination. Used as a mixture of more than one species.

Unsaturated dibasic acids are common α/β monounsaturated dibasic acids,
Examples include maleic acid, halogenated maleic acid, fumaric acid, citraconic acid, itaconic acid, halogenated itaconic acid, etc., and unsaturated monoalcohols of polycarboxylic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride. It also includes a compound that is a partially esterified product and contains two one-COOH groups in the molecule and acts substantially as an unsaturated dibasic acid in the reaction.

The unsaturated alkyd having carboxyl groups at both ends is, for example, a normal unsaturated polyester obtained by heating and reacting a polyhydric alcohol and an unsaturated polycarboxylic acid in an excess of acid components.

Saturated or unsaturated monoglycidyl compounds are monoepoxy compounds such as butylchrycidyl monoter, phenylglycidyl ether, glycidyl acrylate, glycidyl methacrylate, styrene oxide, and other glycidyl esters of higher fatty acids.

Examples of saturated or unsaturated monobasic acids include acetic acid, propionic acid, acrylic acid, methacrylic acid, crotonic acid, etc. Among unsaturated monobasic acids, unsaturated dibasic acids such as methyl maleate, methyl fumarate, etc. Also included are monoesterified products.

Half esters of saturated or unsaturated dicarboxylic acid anhydrides are 2-hydroxyethyl anhydrides of saturated or unsaturated dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid. It is made into a half ester with acrylate or polyhydric alcohol.

In the present invention, each of the above components may be used alone or in combination.
Used as a mixture of more than one species.

The present invention provides such (epoxy compounds having two or more epoxy groups in the AI molecule, (uniformly saturated or unsaturated monoglycidyl compounds, (C) unsaturated dibasic acids or unsaturated alkyds having carboxyl groups at both ends, (D
Saturated or unsaturated monobase? Alternatively, an unsaturated epoxy ester is produced by reacting a half-esterified product of a saturated or unsaturated dicarboxylic acid anhydride, and the molar ratio of these components is (A):(B=9
0-10:10-90(%), (C):(D)=90-
If (A) is 90% or more, the viscosity will increase too much, causing problems in workability, and if it is less than 10%, the molecular weight will increase. can no longer be expected, and there is a similar tendency in the relationship between (C) and (D).

Furthermore, (B) relative to the total number of moles of component (A) and component (C)
The ratio of the total number of moles of component (B) + (D) and component (D), that is, (Al + (
Q It is necessary that it is 0.25 or more, preferably 1.0 or more.

If this molar ratio is less than 0.25, the polyfunctional component will be in excess, making it difficult to control the molecular weight during the reaction or causing a risk of gelation during the reaction.

Also, the ratio of total carboxyl groups to total epoxy groups is 0.
．． It needs to be in the range of 8 to 1.2.

If it is less than 0.8, unreacted epoxy residues will be produced, which will adversely affect the stability and toxicity of the product.

Moreover, if it is 1.2 or more, unreacted carboxylic acid residues will have an adverse effect on toxicity and the like.

The production of unsaturated epoxy esters by the method of the present invention is extremely easy, and each raw material is charged into a reactor in the proportions specified in the present invention, and if necessary, a tertiary amine such as triethylamine, hydroxide, etc. Catalysts of quaternary salts such as quaternary ammonium and tetramethylammonium chloride, and polymerization inhibitors such as phenols such as para-methoxyphenol and para-cresol, hydroquinones, amines such as naphthylamine, and quinones such as penzoquinone. Using any amount of
The reaction is carried out by heating the reaction in the range of 0 to 150°C.

It is sufficient to monitor the reaction based on the acid value, and it is possible to stop the reaction at a desired reaction rate.

By arbitrarily selecting the raw material composition ratio and the composition molar ratio under the reaction conditions, it is not only possible to freely adjust the molecular weight, but also to obtain a liquid with any viscosity depending on the purpose of use. .

The resin obtained by this method can be used as a vehicle for printing, for paint, for molding, etc. Depending on the purpose, if necessary, the resin can be used in ordinary general solvents, or in styrene, vinyltoluene, divinylbenzene, acrylonitrile, methacrylate, etc. Polymerizable monomers such as methyl acid, methyl acrylate, and trimethylolpropane acrylate may be added,
This is optional depending on the purpose.

However, the most important feature of the present invention is that it can be cured without the need for these solvents and polymerizable monomers.

In recent years, countermeasures against organic solvents have become a major issue from the viewpoint of environmental conservation and pollution prevention, and resins that do not use organic solvents or polymerizable monomers and have good fluidity at room temperature are available as products that do not cause such solvent pollution. It is strongly required for printing, paint, and general molding, and in particular, high-speed curing in the air by ultraviolet irradiation is strongly required to shorten and simplify the work process and prevent air pollution. , the unsaturated epoxy esters produced by the present invention are suitable for such purposes.

The unsaturated epoxy ester of the present invention is not particularly limited in its curing method, and can be cured, for example, by the following method.

(1) Photocuring: Usually carried out by adding a photopolymerization initiator such as penzophenone, acetophenone, triphenylphosphine, benzoin, bensoin methyl ether, Michler's ketone, and mixtures thereof.

The amount of photopolymerization initiator used is about 2 to 5% by weight.

Further, when a coloring agent or the like is added, the amount is increased as appropriate.

(2) Peroxide curing: Room temperature curing or heat curing is possible with methyl ether ketone peroxide and cobalt naphthenate, and other commonly used penzoyl peroxide, ditertiary butyl peroxide, dicumyl peroxy toner Any peroxide can be used, and curing properties can be further improved if an accelerator such as dimethylaniline is used in combination.

Examples will be described in detail below.

Example 1 Sumiepoxy ELA-128 (manufactured by Sumitomo Chemical Co., Ltd., bisphenol epoxy resin) 0.24 mol, glycidyl acrylate 1.12 mol, itaconic acid 0.24 mol and acrylic acid 1.12 mol were mixed in a stirrer, a reflux condenser and The mixture was charged into a 500 ml flask equipped with a thermometer, heated on an oil bath, and reacted at 60 to 120°C.

Tetramethylammonium chloride was used as a catalyst at a weight ratio of 0.3% based on the total reaction raw materials, and methylhydroquinone was used at 500 ppm as a polymerization inhibitor.

The reaction time reached 92.8% in about 6.0 hours.

The obtained resin liquid (sample 1a) was 3~
4, and the viscosity was about 100 stox (temperature 25°C).

The resulting resin liquid was applied onto a glass plate and heated using a high-pressure mercury lamp (
Ushio Inc. <Hi-AVK> 250W used) Nite irradiation surface intensity: DV-3 6 5 n-m-7 0 0
When irradiated with ultraviolet rays using W, it hardened in about 15 seconds (benzoin methyl ether: 3%).

Furthermore, when a penzophenone-Michel's ketone system was used as a sensitizer, it cured in about 1.0 seconds under the same conditions, and a cured film with good chemical resistance and adhesion was obtained.

Example 2 A reaction was carried out in exactly the same manner as in Example 1 except that fumaric acid was used in place of itaconic acid in Example 1, and the reaction rate reached 94.1% in about 11 hours.

The hue of the obtained resin liquid (sample = b) was 3 to 4 according to the Gardner color number, and the viscosity was about 250 Stokes (temperature: 25°C).
)Met.

When this resin liquid was subjected to an ultraviolet irradiation test under the same conditions as in Example 1, it was cured in about 20 seconds using benzoin methyl ether as a sensitizer.

In addition, in the penzophenone-Michel's ketone mixed system, approximately 3
It cured in seconds and a good film was obtained.

Example 3-(a) Sumiepoxy ELA-128 and Sumiepoxy ESCN-H (manufactured by Sumitomo Chemical Co., Ltd.: cresol novolank type polyfunctional epoxy resin (epoxy equivalent: 220
)) in a mixed system, 0.7 mole of glycidyl acrylate, 0.05 mole of itaconic acid, and 0.9 mole of acrylic acid were charged, and a reaction was carried out under the same conditions as in Example 1.

The reaction rate reached 92.5% in about 9 hours.

The resulting resin liquid (Sample 10) had a hue of 3 to 4 on a Gardner colorimeter, and a viscosity of about 100 Stokes (temperature 25°C).

When this resin liquid was subjected to an ultraviolet irradiation test under the same conditions as in Example 1, it was found that when benzoin methyl ether was used as a sensitizer, it
The penzophenone-Michael's ketone system cured in about 0.5 seconds, and a good film was obtained.

Example 3-(b) Trimethylolpropane triacrylate was selected as a polymerizable monomer to the resin liquid obtained in Example 3-(a),
When 20% by weight was added to the resin, the Gardner Issei Color Counter showed a viscosity of 3 to 4 and a viscosity of approximately 22.7 Stokes (temperature 25°C).
) resin liquid (sample 1d) was obtained.

When this product was photocured under the same conditions, it took about 21 seconds for benzoin methyl ether.

Example 3-(c) 40 parts of styrene as a polymerizable monomer was dissolved in 60 parts of the resin (sample-c) obtained in Example 3-(a), and 1 wt% of methyl ethyl ketone peroxide and naphthenic acid were added as catalysts. When cured at room temperature using 0.5 wt% of cobalt (6% cobalt content product) and 0.1 wt% of dimethylaniline, the gel time was 13 minutes, the minimum curing time was 19 minutes, and the maximum exothermic temperature was 223°C.

Comparative Example 1 When 0.9 mol of Sumiepoxy ELA-1 28, 0.2 mol of crissicicil acrylate, 09 mol of itaconic acid, and 0.2 mol of acrylic acid were reacted, gelation (sample-
e) Did.

Comparative Example 2 0.3 mol of Sumieboxy ELA-128, 1.4 mol of glycicyl acrylate, 0.3 mol of itaconic acid, and 19 mol of acrylic acid [epoxy group/carboxyl group (equivalent ratio) - 0.77] were reacted. However, the obtained resin liquid (sample 1f) had a low resin viscosity and good workability, but a strong acrylic odor remained.

Comparative Example 3 An epoxy acrylate resin (sample-g) was synthesized by reacting 1.0 mol of Sumie epoxy ELA-128 with 20 mol of acrylic acid in the presence of a tertiary amine catalyst.

It exhibits high viscosity at the end of the reaction and loses almost all fluidity when stored at room temperature.

Requires diluent monomer for handling.

When the epoxy acrylate resin obtained by the above method was diluted with trimethylolpropane triacrylate as a polymerizable monomer and cured with ultraviolet light, the curing time was proportional to the dilution rate of trimethylolpropane triacrylate, and as the dilution rate increased, Therefore, as the viscosity decreased, the curing time increased.

It took 30 seconds when the resin liquid viscosity was about 400 stokes to 60 seconds when the resin liquid viscosity was about 50 stokes.

30% (by weight) of benzoin methyl ether was used as a sensitizer.

Comparative Example 4 When 1.0 mol of Sumiepokin ELA-128, 1.4 mol of acrylic acid, and 0.3 mol of fumaric acid were used as catalysts to esterify the reaction using triethylamine, the viscosity in the system was high. Therefore, it had to be diluted with a diluent monomer (trimethylolpropane triacrylate).

This sample (h) was mixed with 3.0wt of benzoin methyl ether.
When the curing time was measured using %, it required 60 seconds.

Comparative Example 5 0.6 mol of Sumiepokin ELA-1-28, 0.8 mol of glycidyl acrylate and 2.0 mol of acrylic acid, and 0.06 mol of catalytic triethylamine. Epoxy acrylate was synthesized using 3 wt%.

Although the obtained product had a low resin viscosity and good workability, it had a strong odor during handling and was considered impractical for practical use.

This sample was designated as (i), and benzoin methyl ether 3.

When cured using Owt%, it took 140 seconds.

Comparative Example 6 A common iso-based monounsaturated polyester resin (sample-j) was irradiated with ultraviolet light in the same manner as in Example 1.
When benzoin methyl ether was used as a sensitizer, curing took about 250 seconds.

Comparative Example 7 Eboxy acrylate resin obtained in Comparative Example 3 (sample-
g) Mixing 60 parts of styrene with 40 parts of styrene and methyl ethyl ketone peroxide (MEKPO) as a catalyst]. wt
%, cobalt naphthenate (Na-Co) 0.5
wt%, dimethylaniline (DMA) O. I. JIS method room temperature curing characteristics (K-6901-1968
), the gel time was 24 minutes, the minimum curing time was 41 minutes, and the maximum exothermic temperature was 134°C.

Table 1 summarizes the charging composition ratios of the above examples and comparative examples, the physical properties of the obtained resin liquids, and the results of curability with ultraviolet rays and peroxide.

Claims (1)

[Claims] 1 (A) A compound having two or more epoxy groups in the molecule.”
Poquin compounds, (8 saturated or unsaturated monoglycidyl compounds, (Q unsaturated dibasic acids or unsaturated alkyds having carboxyl groups at both ends) and (D saturated or unsaturated monobasic acids or saturated or unsaturated dicarboxylic acid anhydrides) The half-esterified compound 2 of (A):(
B) = 90-10: 10-90, 0.25, and epoxy group/carboxyl group in all reaction components -0.8-12
A method for producing an unsaturated epoxy ester with improved curability, characterized by carrying out the reaction within a range such that: