JPS611642A - Acrylate compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is H or CH3; R2 is CH3 or C2H5). EXAMPLE:Ditrimethylolpropane tetraacrylate. USE:Raw material of paint, adhesive, printing ink, etc. curable with ultraviolet radiation or electron ray. PREPARATION:The compound of formula I can be produced by reacting 4.2- 6mol of (meth)acrylic acid with 1mol of the alcohol component of formula II in the presence of an acidic catalyst (e.g. sulfuric acid, phosphoric acid, etc.) at 75-120 deg.C. The use of a solvent is not necessarily required; however, in the case of using a solvent, it is preferable to use a solvent having low solubility in water, exhibiting a boiling point of 60-140 deg.C under normal pressure, and capable of forming an azeotropic mixture with water (e.g. n-hexane). A polymerization inhibitor such as hydroquinone may be added to the system in the reaction.

Description

[Detailed description of the invention] The present invention relates to novel acrylate compounds.

[Prior art]

In recent years, in the fields of paints, adhesives, printing inks, etc., ultraviolet curable or electron beam curable inks have been on the rise from the viewpoint of pollution-free, resource saving, and energy saving.

For example, in the case of ultraviolet □ ray-curable or electron beam-curable paints, ■ a paint base consisting of a polymer or oligomer such as polyester acrylate, urethane acrylate, or epoxy acrylate; acrylate monomer or methacrylate monomer,
゛■ Multifunctional acrylate monomer or methacrylate monomer added to improve the crosslinking density of the polymer or oligomer, and ■ Sensitizer for accelerating curing such as benzophenone, acetophenone, benzoin alkyl ether, etc. It is composed of the following ingredients.

[Summary of the Invention] As a result of extensive research into new acrylate compounds that can be used in ultraviolet curable or electron beam curable paints, adhesives, printing inks, etc., the present inventors have developed the present invention. Completed the invention.

That is, the present invention relates to an acrylate compound represented by the general formula (1): % (11 (wherein R1 is a hydrogen atom or a methyl group, and R2 is a methyl group or an ethyl group).

[Embodiments of the invention]

The acrylate compound of the present invention has acrylic acid, methacrylic acid, or a derivative thereof that forms an ester (hereinafter referred to as an acid component), and the general formula (2): % formula % (wherein R2 is the same as above). It can be obtained by reacting the alcohol component shown (hereinafter referred to as alcohol component).

For example, in the case of an esterification reaction between acrylic acid or methacrylic acid and an alcohol component, the amount of acrylic acid or methacrylic acid used is 4 to 4 to 1 mole of alcohol component.
8 mol, preferably 4.2 to 6 mol.

As a catalyst for the esterification reaction, acidic catalysts such as sulfuric acid, p-toluenesulfonic acid, phosphoric acid, and hydrochloric acid are preferably used, and the amount used is 1 % based on the alcohol component charged.
~20% (weight%, the same applies hereinafter), preferably 1 to 10%
It is.

When carrying out the esterification reaction, a solvent is not necessarily required, but if used, it has low solubility in water,
It is advantageous to use a solvent that has a boiling point of about 60 DEG to 140 DEG C. at normal pressure and is azeotropic with water. Examples of such solvents include aliphatic hydrocarbons such as n-hexane and n-hebutane, benzene, aromatic hydrocarbons such as toluene and xylene, and alicyclic hydrocarbons such as cyclohexane. When using a solvent, the amount used is 30 to 500%, especially 50% to the amount of ester produced.
About 200% is preferable.

The temperature at which the esterification reaction is carried out is preferably about 60 to 140°C, but from the viewpoint of shortening the reaction time and preventing polymerization, it is advantageous to carry out the esterification reaction at about 75 to 120'C.

Usually, a polymerization inhibitor is already added to acrylic acid or methacrylic acid, but the polymerization inhibitor may be added again during the reaction.

Such polymerization inhibitors include hydroquinone, p-
Methoxyphenol, t-butylcatechol, 2,4-
Dimethyl-6-t-butylphenol, α-nitroso-
Examples include β-naphthol and copper salts, which are usually added in an amount of about 0.01 to 1% to the reaction mixture. Polymerization can also be prevented by blowing air into the reaction solution.

For example, the esterification reaction involves alcohol components, acid components,
This can be carried out by charging a mixed solution consisting of a catalyst, a polymerization inhibitor, and a solvent into a reactor equipped with a water separator, and allowing the reaction to occur while removing the water produced when the solvent boils by azeotroping with the solvent. can.

When the reaction to obtain the acrylate compound of the present invention is a transesterification reaction between an alcohol component and an alkyl ester of acrylic acid or methacrylic acid, the alcohol constituting the alkyl ester of acrylic acid or methacrylic acid may be Lower alcohols such as methanol and ethanol are generally used because the alcohol produced can be easily distilled off.

When carrying out the transesterification reaction, the appropriate amount of the alkyl ester to be charged is 4 to 6 moles per mole of the alcohol component. When the alkyl ester is used in excess, it is not necessary to use a reaction solvent, but a solvent such as benzene, toluene, n-hexane, or cyclohexane may be used. Further, an ester conversion reaction catalyst such as an acid such as sulfuric acid or paratoluenesulfonic acid, or an alcoholade such as an alkali metal alcoholade, an aluminum alcoholade, or a titanium alcoholade may be used.

When the 7-acrylate compound of the present invention is obtained by the transesterification reaction, the same amount of polymerization inhibitor as in the case of the esterification reaction may be added to the reaction, or the polymerization inhibitor may be added. Alternatively, air may be blown into the reaction solution to prevent polymerization.

In the transesterification reaction, for example, a mixed solution consisting of an alcohol component, an alkyl ester of acrylic acid or methacrylic acid, a solvent, a polymerization inhibitor, and a catalyst is charged into a reactor equipped with a fractionator, and the alcohol produced by reaction with the alkyl ester is charged. This can be carried out by distilling off the alcohol produced under boiling with water and refluxing the alkyl ester.

Regardless of the reaction format, the method for removing the acrylate compound of the present invention from the reaction solution is to wash the reaction solution with water, neutralize it with alkaline water, etc., and then remove the layer containing the acrylate compound. Collect the liquid,
It is desirable to collect the solvent after purification using activated carbon or the like if necessary, and obtain the residue as the target product. Since the acrylate compound of the present invention produced in this way has four acrylic acid or methacrylic groups in its molecule, it can be polymerized by irradiation with ultraviolet rays or electron beams, or by organic peroxides. By adding agents, homopolymers or copolymers can be produced. Therefore, the acrylate compound of the present invention is extremely useful as a raw material for resins, reactive plasticizers, adhesives, inks, paints, and the like.

When the acrylate compound of the present invention is used, for example, as a polyfunctional acrylate monomer or methacrylate monomer, which is the component (1) of the above-mentioned ultraviolet curable or electron beam curable coating, It can lower the viscosity of the resin, increase the crosslinking density, and accelerate curing.

Therefore, the resin composition containing the 7-acrylate compound of the present invention is useful not only as a paint as described above, but also as an ultraviolet curable or electron beam curable adhesive, a vehicle for printing ink, etc. .
Since the acrylate compound of the present invention is easily polymerized by radicals other than ultraviolet rays or electron beams, it is also useful as a crosslinking agent for vinyl ester resins, polyester resins, and the like. Furthermore, the acrylate compound of the present invention showed a PII of 0.9 in a temporary skin irritation test (see reference side), and a similar product, trimethylolpropane triacrylate (PII 2.2-3.
75 >, pentaerythritol tetraacrylate (
Skin irritation is lower than PII 2.5-4,3).
This is extremely rare.

Next, the acrylate compound of the present invention will be explained based on Examples.

Example 1 In a 1a glass flask equipped with a stirrer, reflux condenser, water separator, thermometer, and air inlet, 10 g of ditrimethylolpropane, 173 CI of acrylic acid, and 10 g of sulfuric acid were added.
, 0.4Q of copper sulfate, 0.4g of hydroquinone and 180g of benzene, and 20d of air was added while stirring.
The solution was blown into the solution at a flow rate of 1/min and heated under reflux for 5 hours. During heating to reflux, water was separated from the distilled benzene-water distillation valve through a water separator, and the benzene was continuously returned to the reaction flask.

The amount of distilled water separated by the water separator was 30 g.

After the reaction, the reaction solution was cooled, washed with water, neutralized with a 10% aqueous sodium hydroxide solution, and further washed with a 10% aqueous NaCl solution, and then benzene was distilled off from the upper layer under reduced pressure at 50° C. or lower. After treating the residue with 1 g of activated carbon and filtering it,
150Q of product (liquid) was obtained.

The obtained product was confirmed to be ditrimethylolpropane tetraacrylate from elemental analysis, ester value, and NOR spectrum analysis according to conventional methods.

Elemental analysis value theoretical value (%): H7,35C61,79 analysis value (%)
: H7,4I C61,74 ester value theoretical value = 482 Analysis value = 480 1) 1-NOR spectrum (δ value: ppn+)5.
72-6.48 (12HSm, C 曵=岨-), 4.0
8 (8H1s, -CHz-0-CO-), 0.
775-0.925 (6H,,t, -CH2-C city), Example 2 Into the same apparatus as in Example 1, ditrimethylolpropane 1
00i; 11 methacrylic acid 206 (], sulfuric acid 1 og, copper sulfate 0.4 g, hydroquinone 0.2 g and benzene 1
00 g was charged, and the reaction was carried out in the same manner as in Example 1 while blowing air at a flow rate of 20 d 7 min.
0 was distilled out.

After the reaction, purification was carried out in the same manner as in Example 1 to obtain 169 g of product.

The obtained product was subjected to elemental analysis and ester value, NOR
From the results of each spectrum analysis, it was confirmed that it was ditrimethylolpropane tetramethacrylate.

Elemental analysis value theory 1i! (%) :) -18,05C64,37 Analysis value (%) : H8,07C64,33 Works ester value: 430 Analysis value: 428 1 H-NOR spectrum (δ value: ppm) 6,02
5 (4H,S, CH2=C-), 5.525
(4H1S, CH2=C-), 4.07
5 (8H,S, -CHz-0-CO-), 1.91
(12H,,S, CH2=C-), 1
．． 375-1.625 (4H1Q, -C1h
-CH3), 0.78 to 0.94 (6H,t
, -CH2-C Town), Example 3 Into the same apparatus as in Example 1, ditrimethylolethane 89
Q, acrylic acid 173g, sulfuric acid 9g, copper sulfate 0.369
, 18 g of hydroquinone monomethyl ether O, and 100 Q of benzene were charged, and while blowing air at a flow rate of 20-7 minutes, the reaction was carried out in the same manner as in Example 1, and 2 eQ of water was distilled out.

After the reaction, the product was purified in the same manner as in Example 1 to obtain 140 g of product.

The obtained product was subjected to elemental analysis and ester value, NOR
From the results of each spectrum analysis, it was confirmed that it was dimethylolethane tetraacrylate.

Elemental analysis value theoretical value (%): H6,85C60,27 analysis value (%)
:H6,89C60,25 ester number theory @: 512.4 Analysis value: 507.4 1 H-NOR spectrum (δ value: ppi+) 5.8
2-6.57 (12H,m, CH,=CH-)
, 4.08 (8H1s, -CH, -0-CO-
), 0.84 (6H,S, -?-CH1) Example 4 In the same apparatus as in Example 1, ditrimethylolethane 89
g, methacrylic acid 206g, sulfuric acid 9g, copper sulfate 0.36
Q, hydroquinone 0.18g and benzene 100Q
was charged, and the reaction was carried out in the same manner as in Example 1 while blowing air with 20 d/7 min of flowing hot water, and 29 g of water was distilled out.

After the reaction, the product was purified in the same manner as in Example 1 to obtain 158 g of product.

The obtained product was subjected to elemental analysis and ester value, NOR
From the results of each spectrum analysis, it was confirmed that it was dimethylolethane tetraacrylate.

Elemental analysis value theoretical value (%'): H7,69G 63.16 Analysis value (%): H7,75G 63.19 ester value theory @: 454.3 Analysis value: 450 1 H-NHR spectrum (δ value: ppm) 6.05
(4H1S, -C=CHX), 5.55 (
4H,s, -1-ring), 4.08 (8H,s 1
-Chiki-0-CO->, 3.33 (4H1s, -
C Hiki-0-CHi-), reference example weight 2.0~. Using 6 healthy white rabbits with a size of 3.0 and 9, four 2-inch test sites were placed on their backs, and a ditrimethylolpropane tetraacrylate patch test was conducted. Irritation has characteristic values of erythema and edema, and is 4.2
When the characteristic values were scored after 4.48 hours, the total average pH of the six animals was 0.7.

Application Example A photopolymerizable composition consisting of 95 parts of ditrimethylolpropane tetraacrylate obtained in Example 1, 3 parts of benzophenone, and 2 parts of dimethylaminoethanol was prepared.

After the photopolymerizable composition was uniformly applied to the plastic plate shown in Table 1 whose surface had been wiped with alcohol using a bar coater of 8, immediately a 50-lα high-pressure mercury lamp (manufactured by Ushio Inc.) was applied. The coating film was cured by irradiating it with light for 20 seconds in the air using MiniCure 450).

The hardness, adhesion, and abrasion resistance of the resulting cured coating film were measured by the following methods. The results are shown in Table 1.

(hardness) Evaluated by pencil hardness according to JIS 5401-1969.

(Adhesion) Evaluated by cross-cut cellotape peeling test according to JIS K 540G-1979.

(Abrasion resistance) Rub the coating surface once with NoOOOO steel wool,
Evaluated according to the following criteria.

A: Even if you rub it hard, it will probably get scratched (1 B: Slight scratches will occur if rubbed too hard. C: Slight scratches occur when rubbed lightly. D: Significant damage occurs even if rubbed lightly. [Margin below]

Claims (1)

[Claims] 1 General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, R_1 is a hydrogen atom or a methyl group, and R_2 is a methyl group or an ethyl group.) acrylate compounds.