JPH0133469B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing cyanurate group-containing (meth)acrylates. More specifically, by reacting a hydroxyl group-containing (meth)acrylate and cyanuric chloride under specific conditions,
This is a method for producing the (meth)acrylate substantially free of acid chloride active chlorine atoms. 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. The method for producing such cyanurate group-containing (meth)acrylates is disclosed in principle in JP-A-49-125380. According to this method, basically, cyanuric chloride and a hydroxyl group-containing (meth)acrylate are condensed in the presence of a deoxidizing agent,
At this time, a solvent (for example, chloroform, benzene, etc.) is used, and the reaction conditions are such that the charging ratio of the reactant is 1.0 to 1.5 equivalents of hydroxyl group per acid chloride chlorine atom of cyanuric chloride. There is a problem with this reaction condition; in the cyanurate group-containing (meth)acrylate produced, at least 2 to 3% by weight of the acid chloride active chlorine atoms of cyanuric chloride remain unsubstituted.
Only cyanurate group-containing (meth)acrylates that give cured products with poor durability such as moisture resistance, water resistance, and weather resistance can be obtained. As a result of intensive research to obtain a cyanurate group-containing (meth)acrylate that does not substantially contain unreacted and residual acid chloride chlorine atoms that adversely affect the durability of cured products, the present inventor has discovered a specific By reacting cyanuric chloride and hydroxyl group-containing (meth)acrylate under the following conditions,
The inventors have discovered that the above object can be achieved and have arrived at the present invention. That is, the present invention provides a mol of cyanuric chloride, represented by the following general formula (1). [However, in the formula, R is a hydrogen atom or a methyl group,
R ¹⁰ is an alkylene group having 2 to 4 carbon atoms. ] b mol of hydroxyl group-containing (meth)acrylate represented by and the following general formula (2) R ²⁰ (-OH) _y ... (2) [However, in the formula, R ²⁰ is a divalent to tetravalent carbon atom number of 2 to 6
is a saturated hydrocarbon group, which can have an ether bond in which some of the carbon atoms are replaced with oxygen atoms, and y is an integer from 2 to 4. ] When carrying out a condensation reaction of c moles of polyhydric alcohol represented by in the presence of a deoxidizing agent, the charging ratio of the reactant satisfies the following conditions (a) and (b), and b+2c≧4.5a...( b) o≦c≦0.5a...(b) The following general formula (3), characterized in that no solvent is used. [However, in the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a methyl group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴
and R ¹⁵ are each an alkylene group having 2 to 4 carbon atoms, and R ²¹ and R ²² are each a divalent to tetravalent saturated hydrocarbon group having 2 to 6 carbon atoms. This saturated hydrocarbon group can have an ether bond in which some of the carbon atoms are replaced with oxygen atoms. M is-
OH and/or

A group of [Formula] (where R is a hydrogen atom or a methyl group, and ^R10 is an alkylene group having 2 to 4 carbon atoms),
When l or p is 2, both groups can be used. l is an integer of 0, 1, or 2, and (l+2) is
R is an integer from 2 to 4, which is equal to the valence of ²¹ . n is 0
or an integer from 1 to 3. p is 0 or an integer of 1 or 2, and (p+2) is an integer of 2 to 4, which is equal to the valence of ^R22 . r is 0 or an integer of 1-3. ] This is a method for producing a cyanurate ring-containing (meth)acrylate represented by: The hydroxyl group-containing (meth)acrylate which is the reactant of the present invention is a compound of the above formula (1),
In the formula, R is a hydrogen atom or a methyl group, especially,
A hydrogen atom is preferred from the viewpoint of curability of the resulting cyanurate group-containing (meth)acrylate represented by the general formula (3). This R corresponds to R ¹ to ^{R 5} and R in the general formula (3). Further, R ¹⁰ is an alkylene group having 2 to 4 carbon atoms. In the general formula (3), this R ¹⁰ is R ¹¹ -
Equivalent to R ¹⁵ and R ¹⁰ . When the number of carbon atoms in R ¹⁰ is 5 or more, the abrasion resistance, which is a characteristic of the cured product of the cyanurate group-containing (meth)acrylate represented by the above general formula (3), decreases. Specific R ¹⁰ 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 preferable, and especially -CH ₂ · CH ₂ - is obtained from the above general formula
The compound (3) has the best polymerizability and the wear resistance of the cured product. Furthermore, R ²⁰ in the compound R ²⁰ (-OH) _y of formula (2), which is a polyhydric alcohol component, is a divalent to tetravalent saturated hydrocarbon group having 2 to 6 carbon atoms. It may have an ether bond in which some of the atoms are substituted with oxygen atoms. This R ²⁰ corresponds to R ²¹ and R ²² in the general formula (3). Also y
As becomes clear by comparing with equation (3),
Corresponds to (l+2) or (p+2). The case of R ²⁰ is also not preferable because if the number of carbon atoms is too large, the abrasion resistance of the resulting cured product of the compound of the general formula (3) decreases. A specific example of R ²⁰ (−OH) _y is
ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol, neopentyl glycol, diethylene glycol, glycerin, trimethylolpropane,
Examples include pentaerythritol. Such polyhydric alcohols may be halogen-substituted,
Flame retardancy is improved when a halogen substituted product is used. The cyanurate group-containing (meth)acrylate obtained by the method of the present invention is represented by the above general formula (3). In the formula, R ¹ to ^{R 5} are each a hydrogen atom or a methyl group, R ¹¹ to ^{R 15} are each an alkylene group having 2 to 4 carbon atoms, and R ²¹ and R ²² are each a divalent to tetravalent, A saturated hydrocarbon group having 2 to 6 carbon atoms,
As described above, this saturated hydrocarbon group can have an ether bond in which some of the carbon atoms are replaced with oxygen atoms. M is a hydroxyl group and/or the following formula (4) [However, in the formula, R is a hydrogen atom or a methyl group,
R ¹⁰ is an alkylene group having 2 to 4 carbon atoms,
As mentioned above. ] It is a group represented by the following, and when l or p is 2, both groups can be used. Alternatively, l and p are integers of 0 or 1 and 2, respectively, and (l+2) is equal to the valence of R ²¹ and (p+2) is equal to the valence of R ²² . n and r are each 0 or an integer of 1 to 3, preferably 0 or 1. More specifically, the compound of the general formula (3) is: [Here, R, R ¹⁰ and R ²⁰ in the above formula are as defined above]. However, cyanurate group-containing (meth)acrylates that are actually obtained have various structures depending on reaction conditions such as charging ratio, charging order, temperature, etc., either singly or as a mixture. In addition, the cyanurate group-containing (meth)acrylate obtained by the method of the present invention is characterized by the fact that unsubstituted cyanuric chloride acid chloride greatly affects the durability of the cured product, especially the moisture resistance, water resistance, weather resistance, etc. chlorine atoms. Here, the term "substantially free" means that the residual amount of chlorine atoms is sufficiently small to the extent necessary for the cured product of the (meth)acrylate to exhibit sufficient durability. is 1.5% by weight or less, preferably 1% by weight or less, more preferably 0.7% by weight
This means that it contains only the following acid chloride chlorine atoms. Such cyanurate group-containing (meth)
Acrylate can only be achieved by reacting cyanuric chloride with a hydroxyl group-containing compound under the reaction conditions described below. The charging ratio in the present invention is cyanuric chloride a
b moles of the hydroxyl group-containing (meth)acrylate of the formula (1) and c moles of the polyhydric alcohol of the formula (2) satisfy the following relational expressions (a) and (b) relative to the mole, and b+2c≧ 4.5a...(a) o≦c≦0.5a...(b) Preferably, the following conditions satisfy the relational expressions (c) and (b). b + 2c ≧ 6a ... (c) o ≦ c ≦ 0.5a ... (b) By adding polyhydric alcohol in the above ratio, as is clear from formula (3), the functional group (meth)acrylate in one molecule The number of bases increases, thereby improving photopolymerizability and abrasion resistance of the cured film. On the other hand, since cyanuric chloride is trifunctional, if the amount of polyhydric alcohol added is too large, crosslinking and gelation will occur due to the reaction, which is not preferable. To specifically explain the above relational expression, cyanuric chloride and the hydroxyl group-containing compound are prepared in a ratio of 1.5 times or more equivalents, preferably 2 times or more equivalents of hydroxyl groups per acid chloride chlorine atom of cyanuric chloride. . Further, it is not necessary to use a polyhydric alcohol; for example, the cyanurate group-containing (meth)acrylate of the present invention, which is obtained without using a polyhydric alcohol, is one of the most preferred compounds. When using a polyhydric alcohol, from the viewpoint of curability and wear resistance of the cyanurate group-containing (meth)acrylate obtained according to the method of the present invention, an average of 3 or more (meth)acryloyl groups per molecule should be bonded. Also, from this point of view and for the purpose of preventing the formation of a gel, the polyhydric alcohol component should be contained in an average amount of 0.5 per mole of cyanuric chloride.
Used in moles or less. Further, in this polyhydric alcohol, two or more -OH groups in one molecule do not react with one cyanuric acid to form a ring. The deoxidizing agent used in the present invention 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. When a tertiary amine, such as an organic base compound such as triethylamine or pyridine, is used for such purposes, the reaction may not proceed sufficiently, resulting in a product with a large amount of chlorine remaining, or side reactions may occur, such as when the added amine is used as a deoxidizing agent. In many cases, the target compound cannot be obtained or the product becomes colored due to involvement in the reaction. The method of the present invention is characterized in that it does not use any solvent that does not participate in the reaction. Therefore, as the substantial concentration of the reactant increases, the reaction system becomes only alcohol-based, which has good affinity with inorganic salts.
The activity of the added inorganic base is further increased, so that the desired condensation reaction proceeds rapidly. Further, the method of the present invention is carried out at a reaction temperature of 60° to 150°C, preferably 80° to 120°C. If the temperature is outside of this range, the reaction may not progress incompletely and the amount of chlorine remaining in the product may increase, or the hydroxyl group-containing (meth)acrylate as a reactant, the product, and intermediate products may be exposed to high temperatures. Polymerization occurs, often resulting in gelation of the reaction system. A more detailed explanation of the reaction according to the method of the present invention is as follows. Cyanuric chloride, hydroxyl group-containing (meth)acrylate, and polyhydric alcohol if necessary are mixed at the above-described mixing 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, the reaction substantially involves a large excess of hydroxyl groups per one chlorine atom of cyanuric chloride, and when two or more hydroxyl group-containing compounds are used, the reaction proceeds quickly depending on the charging ratio. Also, near the end of the reaction,
Since the hydroxyl group-containing compound is used in a stoichiometric amount of more than 1.5 times the stoichiometric amount of the cyanuric chloride charged and is solvent-free, the reaction is carried out in a large excess per chlorine atom of unsubstituted cyanuric chloride. In addition, under high reaction temperature conditions and a strong deoxidizing agent, the substitution reaction is almost completely completed, and unreacted acid chloride chlorine atoms are substantially eliminated. The reaction is usually carried out using a polymerization inhibitor such as hydroquinone, 2,6-di-
Preferably, tert-butyl-p-cresol, N-nitrosodiphenylamine, p-methoxyphenol, phenokiazine, copper powder, etc. are present in an amount of 50 to 5000 ppm. The reaction time depends on the charging ratio of the reactants, the type of deoxidizing agent, the reaction temperature, etc., so it cannot be stated unconditionally, but it is usually 1 to 20 hours, preferably 2 to 10 hours. The reaction mixture thus obtained is usually distilled off under reduced pressure to remove excess hydroxyl group-containing compounds, and if necessary, especially if the system is viscous, it is diluted with a solvent and washed with water, and the organic layer is separated and used. By simply distilling off the solvent, unreacted raw materials and by-product inorganic salts are removed, and a cyanurate group-containing (meth)acrylate containing substantially no acid chloride chlorine atoms is obtained. In the above operation, the excess hydroxyl group-containing compound is often dissolved well in water, and in that case, the reaction mixture may be directly washed with water without performing this operation. 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. Example 1 To a slurry mixture obtained by adding 55.3 parts of cyanuric chloride to a solution consisting of 209 parts of 2-hydroxyethyl acrylate and 0.04 part of N-nitrosodiphenylamine, fine granules of soda carbonate ( (100 mesh or less) 95.4 g was 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 100°C, and stirring was continued at that temperature for 5 hours. A vacuum distillation device is attached to the reaction system, and the temperature is 70 to 75 at 5 mmHg.
The residue was distilled off at a temperature of 0.degree. C. to recover 83 parts of 2-hydroxyethyl acrylate. The remainder was poured into about 1 part of water with stirring. The lower organic layer was separated, diluted with 200 ml of ethyl acetate, washed three times with 200 ml of water, then dried over 20 g of magnesium sulfate, and the ethyl acetate was distilled off to obtain acrylate 113 having a cyanurate ring.
I got the department. This substance has the structure of tris(2-acryloyloxyethyl) cyanurate, 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 , and absorption based on vinyl groups at 1335 and 1560 cm -1. ^-1 , characteristic absorptions such as those based on cyanurate rings were observed. Chlorine content of the cyanurate group-containing acrylate
It was 0.47% by weight. A coating solution consisting of 10 parts of the obtained cyanurate ring-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) was coated on a polyethylene terephthalate film using a bar coater, and after removing the solvent at 120°C, it was irradiated for 2 minutes in the air under a 20 cm 2K.W. high pressure mercury lamp. The coating film thickness after curing was 3μ, and it was hardly scratched by steel wool (#0000). The coating film was subjected to a taper wear test based on ASTM-D1044-56 (CS-10F wear wheels, load 500g x 2,
As a result, the haze value of the polyethylene terephthalate surface was 55%, while the haze value of the coated surface was 5.0%, indicating a significant improvement in abrasion resistance. Also, a strip of 1 cm width and 14 cm length was cut out from the coated film, and tested using an Instron tensile tester at a sample length (gauge length) of 10 cm and a 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 35% 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. Example 2 69.7 parts of 2-hydroxyethyl acrylate, 15.9 parts of diethylene glycol and 2,6-di-tert
To a slurry mixture obtained by adding 55.3 parts of cyanuric chloride to a solution consisting of 0.02 parts of -butyl-p-cresol, 95.4 g of fine particles of soda carbonate (100 mesh or less) were added with stirring at room temperature. Although the system immediately generates heat, it was stirred for 1 hour while being cooled to below 50°C, and then stirred for 3 hours at 90-95°C, and then 104.5 parts of 2-hydroxyethyl acrylate and 2,6-di- A solution consisting of 0.02 part of tert-butyl-p-cresol was added and the reaction was continued at 95°C for an additional 3 hours. A vacuum distillation device was installed in the reaction system and distilled off at 5 mmHg in a temperature range of 70 to 75°C.
90 parts of 2-hydroxyethyl acrylate were recovered. The remainder was poured into about 1 part of water with stirring. Separate the lower organic layer and dilute with 200ml of ethyl acetate.
The mixture was washed three times with 200 ml of water, then dried over 20 g of magnesium sulfate, and ethyl acetate was distilled off to obtain 104 parts of a pale yellow viscous liquid. The infrared absorption spectrum of the obtained acrylate having a cyanurate ring was similar to that of the compound of Synthesizer 1. In addition, from the nuclear magnetic resonance absorption spectrum (deuterated chloroform solution), the characteristic absorption (δ: 3.6 to 4.0 ppm) based on -O-C-CH ₂ -O-CH ₂ -C-O- derived from diethylene glycol and 2- Characteristic absorption based on -CH ₂ -CH ₂ - derived from hydroxyethyl acrylate and -O-CH ₂ -C-O-C-CH ₂ derived from diethylene glycol which overlaps with it.
The peak area with the characteristic absorption based on -O- (δ: 4.1 to 4.8 ppm) is about 1:5, and the characteristic absorption based on hydroxyl group was not confirmed, and the average acryloyloxy It was confirmed that the compound was composed of two ethyl groups and 0.5 oxydiethylene groups. From the above, this compound is a compound represented by the following formula. 〔however,

[Formula]] is a compound whose main component is The chlorine content of the cyanurate group-containing acrylate was 0.49% by weight. Using the above cyanurate group-containing acrylate,
A polyethylene terephthalate film having a coating layer having a coating thickness of 3 μm was obtained in the same manner as in Example 1.
The elongation of this material was 40%, and the result of the taper wear test was 5.7%. A moisture resistance test similar to that in Example 1 was conducted, and no change in appearance was observed even after 4 weeks. Example 3 69.7 parts of 2-hydroxyethyl acrylate, 13.4 parts of trimethylolpropane, 2,6-di-tert
To a slurry mixture consisting of 0.02 parts of -butyl-p-cresol and 55.3 parts of cyanuric chloride, 136.8 parts of finely divided potassium carbonate, which had been ground and sieved through a 150 mesh, was added with stirring at room temperature. Hereinafter, the same operation as in Example 2 was carried out to obtain a compound represented by the following formula. 〔however,

98 parts of a compound containing [Formula]] as a main component was obtained. The chlorine content of the cyanurate group-containing acrylate was 0.48% by weight. A cured coated film was obtained in the same manner as in Example 1 using the above cyanurate group-containing acrylate. No changes were observed during the 4-week humidity test. Example 4 In the same manner as in Example 1, 55.3 parts of cyanuric chloride,
2-hydroxyethyl methacrylate 195.2 parts (1st stage 78.1 parts, 2nd stage 117.1 parts), 2,6-
0.05 parts of di-tert-butyl-p-cresol and 1 part,
Using 13.5 parts of 4-butanediol, 107 parts of cyanurate ring-containing methacrylate having a structure having an average of 2 methacryloxyethyl groups and 0.5 tetramethylene groups per cyanurate ring was obtained as a viscous liquid. . The chlorine content of the cyanurate group-containing methacrylate was 0.48% by weight. 10 parts of the above cyanurate ring-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 4 minutes. The cured film thickness was 4μ, and the result of the taper abrasion test was a haze value of 7.5%, which was a marked improvement in abrasion resistance compared to the haze value of polycarbonate film, which was 53%. The elongation was 35%. Further, the results of the moisture resistance test did not show any change even after 4 weeks. Examples 5-6, Comparative Examples 1-2 Cyanurate group-containing acrylates were synthesized in the same manner as in Example 1, except that the amount of 2-hydroxylethyl acrylate added was changed. Table 1 below shows the chlorine content of the product and the moisture resistance of the cured product.

[Table] Comparative Examples 3 to 4 Cyanurate group-containing acrylates were synthesized in the same manner as in Example 1, except that 200 parts of the solvents listed in Table 2 below were added to the reaction system from the beginning. The chlorine content in the obtained product was as follows.

【table】

Claims (1)

[Claims] 1 a mol of cyanuric chloride, the following general formula (1) [However, in the formula, R is a hydrogen atom or a methyl group,
R ¹⁰ is an alkylene group having 2 to 4 carbon atoms. ] b mol of hydroxyl group-containing (meth)acrylate represented by and the following general formula (2) R ²⁰ (-OH) _y ... (2) [However, in the formula, R ²⁰ is a divalent to tetravalent carbon atom number of 2 to 6
is a saturated hydrocarbon group, which can have an ether bond in which some of the carbon atoms are replaced with oxygen atoms, and y is an integer from 2 to 4. ] When carrying out a condensation reaction of c moles of polyhydric alcohol represented by in the presence of a deoxidizing agent, the charging ratio of the reactant satisfies the following conditions (a) and (b), and b+2c≧4.5a...( (a) o≦c≦0.5a... (b) The following general formula (3) characterized in that no solvent is used. [However, in the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each a hydrogen atom or a methyl group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴
and R ¹⁵ are each an alkylene group having 2 to 4 carbon atoms, and R ²¹ and R ²² are each a divalent to tetravalent saturated hydrocarbon group having 2 to 6 carbon atoms. This saturated hydrocarbon group can have an ether bond in which some of the carbon atoms are replaced with oxygen atoms. M is-
OH and/or [Formula] (where R is a hydrogen atom or a methyl group, and ^R10 is an alkylene group having 2 to 4 carbon atoms), and when l or p is 2, both It can be based on
l is an integer of 0, 1, or 2, and (l+2)
is an integer from 2 to 4, which is equal to the valence of ^R21 . n is 0 or an integer of 1-3. p is 0 or an integer of 1 or 2, and (p+2) is an integer of 2 to 4, which is equal to the valence of ^R22 . r is 0 or an integer of 1-3. ] A method for producing a cyanurate group-containing (meth)acrylate represented by: