JP2000103815A - Trimethylolpropane tri(meth)acrylate and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide trimethylolpropane tri(meth)acrylate suitable for curable compositions such as a resist ink, etc., a preparation process thereof and a curable composition containing trimethylolpropane tri(meth)acrylate. SOLUTION: Trimethylolpropane tri(meth)acrylate is obtained by allowing (meth)acrylic acid to react with trimethylolpropane in the presence of a copper compound. The viscosity of a slurry form composition, obtained under a predetermined condition wherein 80.0 g trimethylolpropane tri(meth)acrylate and 20.0 g talc are mixed and stirred for 5 minutes at 5,000 rpm using a homodisper, is 1,020 cps or smaller at 25 deg.C. A curable composition exerting a performance superior to that of the conventional composition is obtained using this.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to trimethylolpropane tri (meth) acrylate, a process for producing the same, and the trimethylolpropane tri (meth) acrylate, which is used for paints, inks, adhesives, polymer concretes, etc. In particular, the present invention relates to a curable composition which is preferably used in a resist ink and is curable by ultraviolet light or heat.

[0002]

2. Description of the Related Art Generally, a curable composition comprises a reactive prepolymer, an inorganic substance such as an inorganic filler and a pigment, a reactive diluent, a polymerization initiator and the like.

[0003] The above-mentioned inorganic substances are blended for the purpose of improving physical properties such as low shrinkage, adhesion, heat resistance and corrosion resistance and reducing costs, and it is usually preferable to add as much as possible. However, the addition of a large amount of an inorganic substance causes an increase in the viscosity of the curable composition, and its handling becomes extremely difficult. Therefore, in order to reduce the viscosity of the curable composition, the molecular structure of the resin (reactive prepolymer, reactive diluent) and the shape, particle size and particle size distribution of the inorganic substance have been studied. In any case, satisfactory results have not been obtained.

[0004] The viscosity of the curable composition is adjusted by the reactive diluent so as to have an optimum viscosity according to a predetermined application. Usually, (meth) acrylate is used as a reactive diluent for the curable composition.

[0005] In order to increase the amount of the inorganic substance in the curable composition, a low-viscosity reactive diluent or a highly dilutable reactive diluent is desired. However, in general, a low-viscosity material has a small number of functional groups and is inferior in reactivity, so that the curing rate of the curable composition is reduced.Thus, a highly reactive material having a large number of functional groups has a large molecular weight and a high viscosity, The effect as a diluent is reduced. Therefore, conventionally, the viscosity of the curable composition has been adjusted by using a combination of a low-viscosity resin having a small number of functional groups and a compound having a large number of functional groups and high reactivity.

[0006]

Therefore, although a (meth) acrylate having high reactivity, low viscosity or high dilutability is demanded, such a (meth) acrylate has not yet been obtained. It is.

The present invention has been made in view of the above, and an object of the present invention is to use trimethylolpropane tri (meth) acrylate as a highly dilutable (meth) acrylate capable of realizing a low viscosity. An object of the present invention is to provide a method for producing methylolpropane tri (meth) acrylate and a curable composition containing the trimethylolpropane tri (meth) acrylate.

[0008]

As a result of various investigations to solve the above-mentioned problems, the viscosity of the curable composition is not limited to the type of the reactive diluent contained therein,
Found that it is greatly influenced by its manufacturing method,
The present invention has been completed.

That is, the trimethylolpropane tri (meth) acrylate according to the present invention has a viscosity of 25.degree.
Under the temperature conditions of 1020 cps or less.
The method for producing trimethylolpropane tri (meth) acrylate is a method in which (meth) acrylic acid and trimethylolpropane are reacted in the presence of a copper compound. The product comprises the above-mentioned trimethylolpropane tri (meth) acrylate and an inorganic substance as essential components.

More specifically, the above-mentioned trimethylolpropane tri (meth) acrylate is prepared by reacting acrylic acid or methacrylic acid (hereinafter referred to as (meth) acrylic acid) with trimethylolpropane in the presence of a catalyst and a polymerization inhibitor. It is produced by dehydration esterification. In the case of purification if necessary, the object of the present invention may not be achieved by distillation, so that purification by extraction or adsorption is preferred.

Examples of the esterification catalyst include commonly used sulfuric acid, sulfonic acids, phosphoric acid, boron trifluoride, and cationic ion exchange resin.

As the polymerization inhibitor of the present invention, a copper compound is used. Examples of the copper compound include metallic copper, copper oxide, sulfide, hydroxide, ammonia complex, sulfate, halide, carbonate, phosphate, and carboxylate. Cuprous oxide, cupric oxide, cuprous sulfide, cupric sulfide, cuprous sulfate, cupric sulfate, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide Copper, cupric hydroxide, basic copper chloride, basic copper carbonate, cupric phosphate, cuprous cyanide, copper thiocyanate, copper acetate, basic copper acetate,
Copper formate, copper oxalate, copper citrate, copper tartrate, copper acrylate, copper methacrylate, copper naphthenate, copper phthalate, cupric ammonium chloride, copper phthalocyanine, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, etc. For example, two or more of these may be used in combination. Hydroquinone, phenolic compounds such as hydroquinone monomethyl ether, phenylenediamine, amine compounds such as phenothiazine, nitro compounds,
And commonly used polymerization inhibitors such as sulfur compounds.

The preferred amount of the copper compound is from 0.1 to (meth) acrylic acid or (meth) acrylate.
It is from 0.01 to 5% by weight, more preferably from 0.05 to 0.5% by weight.

In the present invention, the prescribed conditions for mixing and stirring trimethylolpropane tri (meth) acrylate with talc to obtain a slurry-like composition are as follows: 80.0 g of trimethylolpropane tri (meth) acrylate and talc 20 And 0.05 g, and mixed with a homodisper.
It is a condition of stirring at 000 rpm for 5 minutes. The viscosity of the resulting slurry composition is 1020 cps or less under a temperature condition of 25 ° C. In the measurement of the viscosity, in order to make the whole slurry-like composition substantially constant at 25 ° C.,
It is preferable to leave the mixture in a thermostat at 5 ° C. for 1 hour.

The preferred range of the amount of trimethylolpropane tri (meth) acrylate used is 5 to 95% by weight based on the curable composition.

Examples of the inorganic substance include inorganic fillers and pigments, and can be widely used such as talc, clay, silica, calcium carbonate, barium sulfate, calcium sulfate, mica, glass beads, cement, asbestos, kaolin, and carbon black. . The shape may be any shape that can be dispersed in (meth) acrylate, and may be any shape such as powder or fibrous. The amount of the inorganic substance used is preferably in the range of 5 to 90% by weight based on the curable composition.

In addition, if necessary, various polymers,
Prepolymers, oligomers, polymerization initiators, stabilizers, surfactants, leveling agents, antistatic agents, pigments, dyes, and the like can be added to the curable composition. 90% by weight or less based on the weight of the product.

[0018]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 In a 1-liter four-necked flask equipped with a stirrer, a water separator with a cooling tube, a thermometer and an air blowing tube, 201.3 g of trimethylolpropane and 389.1 g of acrylic acid were used as a solvent. Toluene 265.
5 g, 36.2 g of p-toluenesulfonic acid as a catalyst,
0.4 g of cuprous oxide was weighed out as a polymerization inhibitor, and the water / toluene produced was distilled off at a pressure of 230 Torr under air blowing, and the separated toluene was refluxed and reacted for 8 hours. The reaction temperature at this time was 70 to 85 ° C.

Next, the above reaction solution was transferred to a separatory funnel, and 623.5 g of toluene was added. Then, 500 g of water and then 4%
Washing was performed with 1100 g of NaOH water and 500 g of water. Thereafter, the toluene layer was passed through a strongly acidic ion exchange resin (Dowex HCR-W2H), and then hydroquinone monomethyl ether was adjusted to 100 ppm as a polymerization inhibitor. Toluene was removed under reduced pressure to obtain a yield of 417.8 g and a viscosity of 84 cps. A pale yellow transparent liquid of trimethylolpropane triacrylate (hereinafter referred to as TMPTA) at / 25 ° C was obtained (94% yield). The Cu content in the obtained TMPTA was 0.1 ppm or less.

Thereafter, 80.0 g of the obtained TMPTA and 20.0 g of talc as an inorganic substance were mixed and stirred under the above-mentioned predetermined conditions. Then, after the slurry-like composition comprising TMPTA and talc was allowed to stand for 1 hour in a thermostat at 25 ° C., the viscosity was measured.
/ 25 ° C.

"Examples 2 to 10" The same operation as in Example 1 was carried out except that the copper compounds shown in Table 1 below were used as polymerization inhibitors, and all other conditions were the same. Table 1 shows the physical properties (viscosity and residual polymerization inhibitor content) of the obtained TMPTA and the viscosity of the slurry-like composition comprising TMPTA and talc.

"Comparative Examples 1 to 3"
The same operation as in Example 1 was performed under the same conditions except for using the substance shown in Table 1. Thereby, the physical properties (viscosity and residual polymerization inhibitor content) of the obtained TMPTA,
Table 1 shows the viscosity of the slurry composition composed of TMPTA and talc.

[0024]

[Table 1]

Example 11 In Example 11, 402.9 g of methacrylic acid and 174.5 g of trimethylolpropane were used.
And the same operation as in Example 1 was performed under the same other conditions. The Cu content in the obtained trimethylolpropane trimethacrylate (hereinafter referred to as TMPTMA) was 0.1 ppm or less.

Table 2 shows the viscosity of the obtained TMPTMA and the viscosity of the slurry composition comprising the TMPTMA and talc.

Comparative Example 4 Hydroquinone was used as a polymerization inhibitor in an amount of 0.4 g, and all other conditions were the same as those in Example 11.
The same operation was performed in the same manner as described above. In addition, the obtained TMP
The hydroquinone content in TMA was 1 ppm or less.

Table 2 shows the viscosity of the obtained TMPTMA and the viscosity of the slurry composition comprising the TMPTMA and talc.

Reference Example 345.9 g of acrylic acid and 1,
236.4 g of 6-hexanediol was charged, 0.4 g of hydroquinone was used as a polymerization inhibitor, and all other conditions were the same as in Example 11, and the same operation was performed.
The hydroquinone content in the obtained 1,6 hexanediol diacrylate (hereinafter referred to as HDDA) is 1%.
ppm or less.

The viscosity of the obtained HDDA and the H
Table 2 shows the viscosity of the slurry composition comprising DDA and talc.

[0031]

[Table 2]

As can be seen from the above Examples 1 to 11 and Comparative Examples 1 to 4, the TMPTA and TM
When PTMA is mixed and stirred with talc under predetermined conditions to prepare a slurry-like composition, its viscosity is 600 to 1020 cps or less under a temperature condition of 25 ° C.

Further, the above TMPTA and TMPTMA
According to the method of the present invention, the comparison between the case where a copper compound is used as a polymerization inhibitor for dehydration esterification and the reaction and the case where a compound other than the copper compound is used shows that the obtained TMPTA or TMPTA
No difference in the appearance and physical properties of MPTMA itself was observed (both are pale yellow transparent liquids, show almost the same viscosity, and the content of residual polymerization inhibitor in TMPTA or TMPTMA is 1 ppm or less). However, it is clear from the comparison of the viscosity of the slurry-like composition comprising the obtained TMPTA or TMPTMA and the inorganic substance that the TMPTA or TMPTMA produced using the copper compound is apparent.
PTMA shows higher dilutability. Thus, when a slurry-like composition with talc is prepared under predetermined conditions, TMPTA or TMPTMA whose viscosity becomes 1020 cps is particularly produced by a dehydration esterification reaction using a copper compound as a polymerization inhibitor. Then, it can be seen that it has excellent dilutability for inorganic substances.

Here, one synthesis method of the reactive prepolymer used in the photocurable composition is shown in Synthesis Example 1 below.

"Synthesis Example 1" Epoxy equivalent 180 to 200
Bisphenol A type epoxy resin (ARALDIT
E GY250 CIBA-GEIGY) 173 g,
Acrylic acid (70 g) and diethylaminoethyl methacrylate (1.2 g) were charged into a flask equipped with a stirrer and a thermometer, reacted at 80 to 100 ° C., cooled when the acid value reached 1.9. Liquid (15000ps /
25 ° C.).

"Example 12" and "Comparative Examples 5 to 7" were kneaded with three rolls according to the mixing ratio shown in Table 3 below.
A resist ink of 250 to 300 ps / 25 ° C. was obtained.
In Example 12, the TMPTA obtained in Example 1 was
In Comparative Examples 5 to 7, the TMPTA obtained in Comparative Example 1 is used, and in Comparative Example 5, the HDDA obtained in Reference Example is further used. Then, this ink was applied to a glass-epoxy printed circuit board on which a circuit pattern was formed in a thickness of about 20 μm by a screen printing method. Thereafter, a negative mask is applied to the film, and the film is irradiated with a high-pressure mercury lamp of 80 W / cm and cured until the surface hardness of the film becomes 3H or more (JIS D-0202). The test was performed. The results are shown in the same table.

[Comparative Example 8] Kneading with three rolls according to the compounding ratio shown in Table 3 below (Irgacure 651 in the table is a trade name of CIBA-GEIGY), 500 ps /
A resist ink at 25 ° C. was obtained. This ink was applied to a glass-epoxy printed circuit board on which a circuit pattern was formed in the same manner as in Example 12 above. The film thickness at this time was approximately 30 μm. Thereafter, various performance tests were performed in the same manner as in Example 12.

The results are shown in the same table.

[0039]

[Table 3]

The various performance tests shown in the table are as follows.
The test was performed according to the following test method.

"Curable" 80 W / cm high pressure mercury lamp
It is installed at a position 10 cm above a belt conveyor that moves at a speed of 10 m / min, and the belt conveyor is irradiated with ultraviolet rays. A substrate on which the respective resist inks are printed is placed on the belt conveyor, and the substrate is passed through an ultraviolet irradiation position, and the surface hardness of the coating film is measured. At this time, if the surface hardness of the coating film is 3H or less, the substrate is passed through the ultraviolet irradiation position repeatedly until the surface hardness becomes 3H or more. The test results are shown by the minimum number of passes until the surface hardness becomes 3H or more.

"Solder resistance" The substrate after the cured
The state of the coating film when immersed in molten solder at 30 ° C. for 30 seconds was determined as follows (JIS C-648).
1).

：: No abnormality in appearance of coating film ×: Blistering, melting, and peeling are observed “Pressure Cooker Test (PCT)” The cured substrate was treated in an autoclave at 121 ° C. and 98% HR for 24 hours. The adhesion of the subsequent coating film was judged.
In addition, the judgment of the adhesion follows the adhesion test shown below.

Adhesion test (JIS-0202): 1 m
In the cross-cut cellophane adhesive tape peel test at m intervals,
It is expressed as follows by the ratio of the remaining area of the coating film after the cellophane pressure-sensitive adhesive tape is removed.

：: 100/100 Δ: 10-99 /
100 ×: 0 to 9/100 “Solvent resistance” The adhesion of the coating film was determined when the cured substrate was immersed in trichlorethylene at 25 ° C. for 1 hr. The determination of adhesion is based on the adhesion test described above.

As can be seen from the above Example 12, the resist ink obtained by using the TMPTA and TMPTMA according to the present invention, that is, the curable composition is excellent in all of curability, solder resistance, PCT and solvent resistance. It shows the properties.

Comparative Example 5 is different from TMPTA in that the proportion of the reactive prepolymer (resin of Synthesis Example 1) and talc, which is an inorganic substance, and the viscosity of the resist ink are the same as those in Example 12. This is an example using HDDA having a low viscosity. In the above, since the HDDA having a lower reactivity than the TMPTA is used as the reactive diluent, the curing speed of the resist ink is slow and the solder resistance is poor.

Comparative Example 7 is an example in which the amount of talc, an inorganic substance, was reduced in order to make the viscosity of the resist ink the same as in Example 12. In the above, it is considered that since the amount of the inorganic substance is small, the shrinkage ratio at the time of curing becomes large, and sufficient adhesion is not obtained.

Comparative Example 8 is an example in which the amount of the reactive prepolymer (the resin of Synthesis Example 1) was reduced in order to make the viscosity of the resist ink the same as in Example 12. In the above, since the reactive resin component is small, the curing speed of the resist ink is low and the adhesiveness is poor.

In Comparative Example 9, since the composition was the same as that of Example 12, the viscosity of the resist ink was higher than that of Example.

[0051]

As described above, the trimethylolpropane tri (meth) acrylate according to the present invention comprises 80.0 g of the trimethylolpropane tri (meth) acrylate.
And 20.0 g of talc as an inorganic substance, and the viscosity of a slurry composition obtained under predetermined conditions of stirring at 5000 rpm for 5 minutes using a homodisper is 1020 cps or less at a temperature of 25 ° C. It becomes.

The above trimethylolpropane tri (meth)
Since the acrylate has a high diluting property with respect to the inorganic substance, the viscosity of the curable composition can be reduced. In other words, if the composition is the same as the conventional one, the viscosity of the curable composition can be reduced.If the viscosity is the same as the conventional one, the amount of the inorganic substance or the reactive prepolymer in the curable composition can be reduced. Or more reactive trimethylolpropane tri (meth) acrylate can be used.

Accordingly, the curable composition obtained according to the present invention has the same performance as the conventional one and has a low viscosity (the same performance is exhibited if the composition is the same as the conventional one). , Very good workability.

Further, the curable composition of the present invention can increase the amount of the inorganic substance as long as it has the same viscosity as the conventional one, so that the physical properties such as low shrinkage, adhesion, heat resistance and corrosion resistance can be improved. , And cost reduction.

Claims (3)

[Claims] 1. A slurry composition obtained by mixing and stirring with talc under predetermined conditions has a viscosity of 10 ° C. at a temperature of 25 ° C.
Trimethylolpropane tri (meth) acrylate characterized by being 20 cps or less. 2. The process for producing trimethylolpropane tri (meth) acrylate according to claim 1, wherein (meth) acrylic acid and trimethylolpropane are reacted in the presence of a copper compound. 3. A curable composition comprising the trimethylolpropane tri (meth) acrylate according to claim 1 and an inorganic substance as essential components.