JPH0132828B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing cyanurate group-containing (meth)acrylates. More specifically, the (meth) which does not substantially contain acid chloride chlorine atoms
An improved method for producing acrylates. Cyanurate group-containing (meth)acrylate is
It is a polyfunctional (meth)acrylate useful as a photosensitive resin. For example, by laminating a cured product of the (meth)acrylate on a thermoplastic resin film, the surface performance of the film, especially the abrasion resistance, is significantly improved, and the film has high elongation. It has excellent performance that cannot be obtained with laminated materials that have been used for the purpose of improving wear resistance. Such a cyanurate group-containing (meth)acrylate can be obtained in principle by reacting cyanuric chloride with a hydroxyl group-containing (meth)acrylate in the presence of a deoxidizing agent. However, the cyanurate group-containing (meth)acrylates that can be preferably used for the above-mentioned purposes are susceptible to the acid chloride activity of cyanuric chloride, which has a significant negative effect on the durability of the cured product, especially on performance such as weather resistance and moisture resistance. It is important that it does not substantially contain chlorine atoms. In the substitution reaction between a hydroxyl group and an active chlorine atom of cyanuric chloride, the present inventor has found that by reacting the hydroxyl group with at least 1.5 times the equivalent of the active chlorine atom under specific conditions, the hydroxyl group can be substantially It has already been proposed that (meth)acrylates containing cyanurate groups can be obtained which do not contain active chlorine atoms. However, in the above method, the hydroxyl group is at least
Since a large excess of 1.5 times equivalent or more is required,
The process of removing the hydroxyl group-containing compound, which is a raw material, from the product becomes complicated, and the manufacturing cost increases. Moreover, since such excessive use and relatively high reaction temperature of 60 to 150°C, preferably 80 to 120°C are adopted, transesterification by the hydroxyl group-containing (meth)acrylate itself as shown in the following formula (1) is possible. A large amount of alkylene di(meth)acrylate is produced as a by-product, and the resulting cyanurate group-containing (meth)acrylate may cause a bad odor or skin injury, or may have poor curing properties. This sometimes caused the wear resistance of the product to be low and cause it to become slippery. [However, in the formula, R is a hydrogen atom or a methyl group,
R ¹ is an alkylene group having 2 to 4 carbon atoms. ] On the other hand, in this reaction, aliphatic 3 is used as a deoxidizing agent.
If a class amine is used from the beginning of the reaction, the reaction can proceed in a homogeneous system, so the hydroxyl group-containing (meth)acrylate is
Using only ~1.5 equivalents often results in a product substantially free of active chlorine atoms. However, at the same time, the reaction represented by the following formula (2) occurs at a high rate, and as a result, a large amount of structures unrelated to the curing reaction, such as the cyanuramide structure in product (a), are introduced, resulting in the The drawback was that the hardenability and abrasion resistance of the cured product were significantly inferior. [However, in the formula, R ² , R ³ and R ⁴ are the same or different alkyl groups, and R ¹ , R ² and R ³ may be partially or completely bonded to each other to form a ring structure. m represents an integer of 1 to 3, n represents an integer of 1 to 2, and m+n=3. ] The present inventors have conducted intensive research on a method to eliminate the adverse effects caused by excessive use of hydroxyl group-containing (meth)acrylates, and also overcome the drawback of deterioration in the performance of cured products due to the introduction of a large amount of cyanuramide structure, as described above. As a result, when reacting hydroxyl group-containing (meth)acrylate with cyanuric chloride, we first used a strong inorganic base as a deoxidizing agent to advance the reaction to a certain stage, and then used a homogeneous deoxidizing agent, such as a fat. Hydroxyl group-containing (meth)
acrylate to the chlorine atom of cyanuric chloride
A cyanurate group-containing (meth) with favorable performance, including substantially no active chlorine atoms and substantially less by-products and by-produced heterochemical structures even when used at 1.05 to 1.5 equivalents. They discovered that acrylate can be obtained and arrived at the present invention. That is, the present invention provides a chlorinated chloride method, characterized in that cyanuric chloride and a hydroxyl group-containing (meth)acrylate are first reacted in the presence of a strong inorganic base, and then an aliphatic tertiary monoamine is added and the reaction is continued. Cyanuric acid chloride chlorine atom is 1.5
This is a method for producing cyanurate group-containing (meth)acrylate containing only 0.3 units or less of cyanuramide structure at less than 0.3% by weight. The characteristics of the reaction of the present invention are as follows when compared with the reaction represented by the above formula (2). In the present invention, in the first step, cyanuric chloride is reacted in the presence of a strong inorganic base under mild conditions as described below, so that cyanuric chloride is not completely converted into a triester form, but some diester form remains. state. [However, R and R ¹ are as described above, and R'' is a group

Represents [formula]. ] Thereafter, the reaction is continued by adding an aliphatic tertiary monoamine to substantially eliminate -Cl remaining in the diester. The product thus obtained is substantially free of -Cl and contains cyanurate groups (meth) which, when cured, provides a cured product with excellent performance.
It is acrylate. The hydroxyl group-containing (meth)acrylate which is the reactant of the present invention has the following general formula (3). It is indicated by. In the formula, R is a hydrogen atom or a methyl group, and in particular, a hydrogen atom is preferred from the viewpoint of curability of the cyanurate group-containing (meth)acrylate obtained. Further, R ¹ is an alkylene group having 2 to 4 carbon atoms. When the number of carbon atoms in R ¹ is 5 or more, the abrasion resistance, which is a characteristic of the cured product of the cyanurate group-containing (meth)acrylate, decreases. Specific R ¹ is −CH ₂・CH ₂ −,

[Formula] −CH ₂・CH ₂・CH ₂・CH ₂ −,

[Formula] etc., but from the viewpoint of obtaining raw materials -CH ₂ · CH ₂ -,

[Formula] is preferred, and among these, -CH ₂ .CH ₂ - has the best polymerizability of the resulting (meth)acrylate and the best abrasion resistance of the cured product. In addition, the above-mentioned hydroxyl group-containing (meth)acrylate is selected from the viewpoint of suppressing the side reaction represented by the above formula (1), and from the performance and economic viewpoint of the obtained cyanurate group-containing (meth)acrylate, with respect to the chlorine atom of cyanuric chloride. 1.05-1.5 times equivalent, preferably 1.1-1.3
Double equivalent, i.e. 3.15 to 1 mole of cyanuric chloride
It is used in a proportion of 4.5 mol, preferably 3.3 to 3.9 mol. One of the features of the cyanurate group-containing (meth)acrylate obtained by the method of the present invention is that the acidity of unsubstituted cyanuric chloride greatly affects the durability of the cured product, especially the moisture resistance, water resistance, weather resistance, etc. It is substantially free of chloridic chlorine atoms.
Here, "substantially not containing" means that the (meth)
This means that the residual amount of chlorine atoms is sufficiently small to the extent necessary for the cured acrylate to exhibit sufficient durability, specifically, 1.5% by weight or less, preferably 1% by weight or less, and This means that it preferably contains no more than 0.7% by weight of acid chloride chlorine atoms. Furthermore, the cyanurate group-containing (meth)acrylate obtained by the method of the present invention has the following characteristics:
Although the aliphatic tertiary amine is used as a deoxidizing agent, the above formula (2) significantly affects the curability of the (meth)acrylate and the abrasion resistance of the cured product.
One example is that the cyanuramide structure-containing compound represented by is contained only in a substantially small amount. Here, "containing only a substantially small amount" means containing the (meth)acrylate only to the extent that the curability of the (meth)acrylate and the abrasion resistance of the cured product obtained by curing maintain sufficient performance. This means that the acrylate does not contain the compound as a by-product, and specifically, it means that it contains on average no more than 0.3 units, preferably no more than 0.23 units of cyanuramide structure per unit of cyanurate bone core. The feature of the method of the present invention is that the reaction between the hydroxyl group-containing (meth)acrylate and cyanuric chloride is divided into two stages.In other words, in the first stage, a strong inorganic base compound is used as a deoxidizer to convert the chloride into Most of the cyanuric acid is reacted with the (meth)acrylate to produce most of the desired cyanurate group-containing (meth)acrylate in the reaction system, and then in the second stage, aliphatic 3 is further added as a deoxidizing agent. By adding the class monoamine, the main purpose is to substantially eliminate the acid chloride chlorine atoms remaining in the system. Naturally, the first stage and second stage reactions are usually carried out consecutively in the same reaction system. The deoxidizing agent used in the first stage reaction is a strong inorganic basic compound, and hydroxides and carbonates of alkali metals and alkaline earth metals are usually used. Specific examples include sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, etc. In terms of reactivity and prevention of side reactions, sodium carbonate, potassium carbonate, etc. Alkali metal carbonates are preferred. Note that hydrogen carbonates of the above metals are not preferred because they have poor activity and the reaction does not proceed completely, giving a product with a high chlorine content. The inorganic base is preferably in the form of fine particles to powder. Further, the inorganic base is usually used in a ratio of 3 to 4.5 mol, preferably 3 to 4 mol, per 1 mol of cyanuric chloride. The first reaction is carried out at a reaction temperature of 60-150°C, preferably 80-120°C. If the temperature is out of this range, the reaction may not progress incompletely, the amount of chlorine remaining in the reaction system may become too large, or the hydroxyl group-containing (meth)acrylate as a reactant, the products and intermediate products may be exposed to high temperatures. In many cases, polymerization occurs, resulting in gelation of the reaction system or an increase in the amount of alkylene di(meth)acrylate by-produced due to the side reaction shown in formula (1) above. The reaction time cannot be determined unconditionally because it depends on the charging ratio of the reactants, the type and amount of the deoxidizing agent used, the reaction temperature, etc., but it is usually 1 to 10 hours, preferably 2 to 6 hours. The cyanurate group-containing (meth)acrylate obtained by the first-stage reaction contains triester in an amount of 50 mol% to 85 mol%, preferably 60 mol% to
The chlorine content is 75 mol%, and the remainder is mostly diester, and the chlorine content is 4.8% to 1.0% by weight, preferably 3.6% to 1.7% by weight. By performing the second stage reaction using the first stage reaction product, the cyanuramide structure in the cyanurate group-containing (meth)acrylate finally obtained is reduced to 0.3 units or less per cyanuric ring unit.
Preferably, it can be made 0.23 units or less, and the chlorine content can also be made 1.5% by weight or less, preferably 1% by weight or less, particularly preferably 0.7% by weight or less. If the chlorine concentration in the first stage reaction product is increased above the above range, the required amount of aliphatic tertiary monoamine used in the second stage reaction will increase, resulting in a cyanurate group-containing (meth) ) The cyanuramide structure increases in the acrylate due to the side reaction based on the above formula (2), and the content exceeds 0.3 units,
The performance of the (meth)acrylate is reduced. The deoxidizing agent used in the second stage reaction is an aliphatic tertiary monoamine. 2 amino groups in 1 molecule
Polyamines having more than 100% of polyamines may form a crosslinked structure during the reaction of formula (2) above, giving rise to insoluble materials, or abnormally increasing the viscosity of the resulting product.Also, aromatic amines often It is undesirable because it has drawbacks such as causing coloring. The aliphatic 3
Specifically, class monoamines include trimethylamine,
Triethylamine, tri-n-propylamine, triisobutylamine, tri-sec-butylamine,
Examples include tri-tert-amylamine, N-methylmorpholine, N-methylpyrrolidine, N-methylpiperidine, etc., and triethylamine is particularly preferred from the viewpoint of reactivity, ease of removing excess amine used from the product, and economical viewpoint. . The preferred amount of the above tertiary monoamine to be added depends on the remaining amount of acid chloride chlorine atoms in the reaction system after the first stage reaction, but it is usually 0.1 to 0.5 mol, preferably 0.1 to 0.5 mol per mol of cyanuric chloride. It is used in a proportion of 0.15 to 0.3 mole. The second stage reaction is carried out at a reaction temperature of 0 to 100°C, preferably 30 to 80°C. If the temperature is out of this range, the reaction may not progress incompletely, the amount of chlorine remaining in the product may increase, the cyanuramide structure may increase due to the side reaction shown by the above formula (2), or the above formula (2) may increase.
Alkylene di(meth) due to the side reaction shown in (1)
The amount of acrylate by-product may increase. In addition, the reaction time cannot be generalized because it depends on the reactant charging ratio, the type and amount of the deoxidizing agent used in the first stage reaction, the type and amount of the amine used, and the reaction temperature. Usually within 5 hours, preferably within 2 hours. In both the first and second stage reactions, polymerization inhibitors are usually used, such as hydroquinone, 2,6-di-tert-butyl-p-cresol, and N-nitrosodifluoride, in order to prevent the formation of gels. enylamine, p-methoxyphenol, phenokiazine,
It is preferable to carry out the process in the presence of 50 to 5000 ppm of copper powder or the like. Usually, the polymerization inhibitor is added at the time of preparing the first stage reaction. Further, in the method of the present invention, it is preferable not to use a solvent. By not using a solvent, the concentration of the reactant becomes substantially high, especially in the first stage reaction, and because the reaction system is an alcohol system that has good affinity with inorganic salts, the concentration of the added inorganic base is reduced. The activity is further increased, and the desired condensation reaction proceeds rapidly. A more detailed explanation of the reaction according to the method of the present invention is as follows. (First Stage Reaction) Cyanuric chloride and hydroxyl group-containing (meth)acrylate are mixed at a predetermined charging ratio to form a slurry. At this stage, there is almost no heat generation and the reaction does not substantially proceed. When a finely divided inorganic base is added to the slurry, the reaction system begins to proceed with intense heat generation. Although the reaction apparently proceeds as a heterogeneous reaction in the initial stage, in reality, a small amount of cyanuric chloride is dissolved in the hydroxyl group-containing compound as a reactant, and the reaction occurs in this solution. Therefore, when the reaction does not use a solvent, a large excess of hydroxyl groups per chlorine atom of cyanuric chloride participates, and the reaction proceeds rapidly. When the reaction is carried out for a predetermined period of time, the residual amount of acid chloride chlorine in the reaction system becomes 4.8% by weight or less based on the compound derived from cyanuric chloride. (Second Stage Reaction) After the first stage reaction, an aliphatic tertiary amine is added to the reaction system at the reaction temperature used in the second stage reaction. Upon addition, the reaction begins to proceed with some exotherm. Since the deoxidizing agent dissolves in the reaction system, the small amount of remaining acid chloride chlorine atoms are quickly replaced by the hydroxyl group-containing (meth)acrylate or by the added amine as shown in formula (2) above, resulting in substantial disappear. The reaction mixture thus obtained contains relatively little excess hydroxyl group-containing (meth)acrylate and is well soluble in water. Therefore, there is no need for recovery by vacuum distillation, which often causes gelation, and the reaction product is directly poured into water in an amount necessary to dissolve unreacted or by-product inorganic salts (meth). The acrylate compound can be precipitated and separated as an organic layer. Next, if necessary, it is diluted with a solvent, washed with water, the organic layer is separated, and the solvent used is distilled off to obtain a cyanuramide structure that does not substantially contain acid chloride chlorine atoms. A cyanurate group-containing (meth)acrylate is obtained which contains only a substantially small amount of. Moreover, the content of undesirable alkylene di(meth)acrylate in the (meth)acrylate is substantially low. Cyanurate group-containing (meth) obtained by the present invention
Acrylate has high abrasion resistance and high elongation when made into a thin film laminated material, and has excellent durability, especially moisture resistance, water resistance, and weather resistance, so it is particularly resistant to thermoplastic resin films. It is widely used as a laminated material for the purpose of imparting wear resistance, solvent resistance, etc. Other photosensitive resins include printing materials, adhesives, paints, and inks. EXAMPLES Hereinafter, the present invention will be explained with reference to Examples, but the present invention is not limited thereto in any way. In addition, all parts in the examples mean parts by weight. In addition, the oxygen flask method was used for chlorine analysis. Example 1 To a slurry mixture obtained by adding 92.2 parts of cyanuric chloride to a solution consisting of 209 parts of 2-hydroxyethyl acrylate and 0.04 parts of N-nitrosodiphenylamine, fine granules of soda carbonate ( (100 mesh or less) 175 parts were added.
Although the system immediately generated heat, it was stirred for 1 hour while being cooled to below 80°C. Next, the reaction temperature was raised to 90°C, and stirring was continued at that temperature for 4 hours. After taking a small sample of the reaction system and thoroughly washing it with water, the residual amount of acid chloride chlorine was measured to be 2.8% by weight based on the compound derived from cyanuric chloride. The reaction system was cooled to 60°C, and then 10.1 parts of triethylamine was added. The reaction system was stirred for 1 hour while being maintained at 60-70°C. The resulting reaction mixture was poured into 1500 parts of water with vigorous stirring, and the lower organic layer was separated. After washing three times with 200 parts of water and then diluting with 100 parts of toluene 20 parts of magnesium sulfate
After addition and dehydration, toluene was distilled off under reduced pressure to obtain 176 parts of cyanurate group-containing acrylate. This thing is
It has a structure mainly of tris(2-acryloyloxyethyl)acrylate, and its infrared absorption spectrum includes absorption based on carbonyl groups at 1725 cm ^-1 ,
Absorption based on vinyl groups at 1620 and 1640 cm ^-1 , 1335
Characteristic absorptions such as absorptions based on cyanurate rings were observed at 1560cm ^-1 and 1560cm -1 . The acrylate contained 0.15 units of cyanuramide structure based on the peak area ratio of the nuclear magnetic resonance absorption spectrum. In addition, the acrylate contains 0.35% of chlorine.
It contained 5% by weight of ethylene glycol diacrylate which was produced as a by-product from the reaction of formula (2) above. A coating solution consisting of 10 parts of the obtained cyanurate group-containing acrylate (hereinafter referred to as compound A), 0.15 parts of benzyl dimethyl ketal, and 10 parts of methyl isobutyl ketone was biaxially stretched to a thickness of 75 μm (3 times
3 times) It was coated on a polyethylene terephthalate film using a bar coater, and after removing the solvent at 120°C, it was irradiated in the air for 2 minutes under a 20cm 2kW high-pressure mercury lamp. The coating film thickness after curing was 3 μm and was hardly scratched by steel wool (#0000). The coating film was subjected to the Taber abrasion test based on ASTM-D1044-56 (CS-10F wear wheel, load 500g x 2,
As a result, the haze value of the polyethylene terephthalate surface was 47%, while the haze value of the coated surface was 3.8%, indicating a significant improvement in abrasion resistance. In addition, strips of width 1 cm and length 14 cm were cut from the coated film, and tested using an Instron tensile tester at sample length (gauge length) of 10 cm and tensile speed of 2 cm/min, 5 cm/min, and 10 cm/min. As a result of operating under various conditions and measuring the elongation until cracks appeared in the coating layer, the elongation was 31% under all conditions. The above-mentioned coated film was left for 4 weeks at 50° C. and 100% relative humidity, but no change in appearance was observed. Examples 2 to 4, Comparative Examples 1 to 3 Cyanurate group-containing acrylates were synthesized in the same manner as in Example 1, except that the amount of 2-hydroxylethyl acrylate and the amount of triethylamine added were changed. However, since triethylamine was not added in Comparative Example 3, the reaction system was immediately poured into water after the completion of the first stage reaction, and treated in the same manner as in Example 1. Table 1 below shows the acid chloride chlorine content immediately before adding triethylamine, the chlorine content of the product, the cyanuramide structure content, the by-produced ethylene glycol diacrylate content, and the results obtained using a 2kW high-pressure mercury lamp.
The ultraviolet curability under 20 cm (finger touch test), the abrasion resistance (steel wool test) and moisture resistance of the cured product obtained by irradiating ultraviolet light for 2 minutes under these conditions were recorded.

【table】

[Table] Example 5 2 instead of 2-hydroxyethyl acrylate
185 parts of cyanurate group-containing methacrylate was obtained as a pale yellow liquid in the same manner as in Example 1 except that 234.2 parts of -hydroxylethyl methacrylate was used. During this reaction, the amount of acid chloride chlorine remaining at the end of the first stage reaction was 2.9% by weight.
Moreover, the chlorine content of the obtained methacrylate was 0.43
In weight percent, the cyanuramide structure content was 0.16 units. 10 parts of the above cyanurate group-containing methacrylate,
A coating solution consisting of 0.2 parts of benzoyl peroxide, 4 parts of ethanol, and 6 parts of ethylene glycol monoethyl ether was applied onto a 100 μ thick polycarbonate film (obtained by condensation polymerization of bisphenol A and phosgene) and placed in a nitrogen atmosphere. It was cured at 140° C. for 5 minutes. The cured film thickness was 3μ, and the result of the taper abrasion test was a haze value of 6.4%, which was a marked improvement in abrasion resistance compared to the haze value of polycarbonate film, which was 45%. The elongation was 41%. Further, the results of the moisture resistance test did not show any change even after 4 weeks.

Claims (1)

[Claims] 1 Cyanuric chloride and hydroxyl group-containing (meth)
Acrylate is first reacted in the presence of a strong inorganic base, then an aliphatic tertiary monoamine is added and the reaction is further continued. A method for producing cyanurate group-containing (meth)acrylates containing no more than 0.3 units of structure.