JPH03296514A - Preparation of polyester (meth)acrylate - Google Patents

Abstract

PURPOSE:To prepare the title compd. having a high lipophilicity, quickly curing properties, and a low viscosity and useful for a coating material and a lithographic printing ink by reacting a specific branched aliph. satd. dibasic acid, a specific polyhydric alcohol, a specific fatty acid, and (meth)acrylic acid in a specified ratio. CONSTITUTION:A polyester (meth)acrylate is prepd. by the esterification of Amol of a 9C or higher branched aliph. satd. dibasic acid and/or an anhydride thereof, (e.g. dodecylsuccinic anhydride), Bmol of a polyhydric alcohol having N primary hydroxyl groups in the molecule (e.g. pentaerithritol), Cmol of a 10-20C fatty acid (e.g. oleic acid), and Dmol of (meth)acrylic acid in such a ratio that A, B, C, and D simultaneously satisfy the conditions: 3<=N; 0.9<=NXB /(2XA+C+D)<=1.1; and 2<=D/C<=5. The polyester (meth)acrylate has a high lipophilicity, quickly curing properties, and a low viscosity and is esp. useful for a coating material and a lithographic printing ink.

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention provides a method for curing by irradiation with ultraviolet rays or electron beams, or by curing means such as heating or the like in the presence of a radical polymerization catalyst at room temperature. The present invention relates to a method for producing curable compounds that can be used in various industrial fields such as paints or lithographic printing inks.

In this specification, acrylate and methacrylate are referred to as (meth)acrylate, acryloyl group and methacryloyl group are referred to as (meth)acryloyl group, and acrylic acid and methacrylic acid are referred to as (meth)acrylic acid.

[Conventional technology]

When (meth)acrylate-based active energy ray-curable compounds are used as vehicles for paints or lithographic printing inks, 2XA+C+D, which requires various properties, is particularly lipophilic, that is, soluble in natural oils and fats. In such cases, the balance between curability and lipophilicity is often an issue. In other words, in order to improve the curability, it is effective to increase the content of (meth)acryloyl groups per molecule in the compound, but in this case, the amount of ester bonded gold also increases, so the polarity of the compound increases. increases and lipophilicity decreases.

Various techniques have been proposed in the past for the purpose of obtaining high lipophilicity without reducing curability. For example, in the invention described in Japanese Patent Publication No. 5B-5949, a polyhydric alcohol having a terminal hydroxyl group (meth)
The invention contains urethane (meth)acrylate obtained by the reaction of acrylic acid ester and polyvalent incyanate as the main component, contains castor oil or castor oil fatty acid alkyl ester as a subcomponent, and is also described in Japanese Patent Publication No. 54-22128. In, epoxy resin and (meth)
In the epoxy acrylate obtained by reaction with acrylic acid, an epoxidized product of drying oil such as soybean oil or linseed oil is used as the epoxy resin.

However, urethane (meth)acrylate is expensive, and epoxy (meth)acrylate has residual secondary hydroxyl groups generated during esterification, so it can be used as a lipophilic liquid, such as in paints. There is a problem of emulsification during mixing.

Also, epoxy (meth)acrylate and urethane (meth)
Acrylates generally have extremely high viscosity, and there is a problem in that it is difficult to handle them alone as paints, lithographic printing inks, or the like.

A polyester obtained by esterifying a fatty acid-modified alkyd resin and (meth)acrylic acid, which has residual hydroxyl groups, is a cheaper and lower viscosity compound than the above two types of (meth)acrylic acid ester compounds. There is poly(meth)acrylate (Special Publication No. 52-2323
).

However, in order to obtain sufficient lipophilicity in the polyester poly(meth)acrylate, it is necessary to increase the molecular weight of the fatty acid to be added or to increase its addition equivalent. When the molecular weight of the fatty acid is increased, the melting point of the fatty acid itself becomes higher, so the resulting resin solidifies.
The resin becomes very difficult to handle. Additionally, when modifying alkyd resins, increasing the amount of fatty acids added will reduce the amount of residual hydroxyl groups, resulting in a decrease in the amount of (meth)acryloyl groups introduced into polyester poly(meth)acrylate, resulting in a marked deterioration of curability. . Therefore, it has been extremely difficult to obtain a low-viscosity, liquid activated Lugie wire-curable compound that has sufficient lipophilicity and good curability.

[Problem to be solved by the invention]

An object of the present invention is to solve the above-mentioned problems and provide a method for producing a low-viscosity polyester poly(meth)acrylate that has fast curing properties and excellent lipophilicity.

(11) Structure of the Invention [Means for Solving the Problems] As a result of intensive studies to provide a method for producing a compound that can achieve both the contradictory properties of fast curing and high lipophilicity, the present inventors discovered that A polyhydric alcohol having three or more primary hydroxyl groups in one molecule, using a branched aliphatic saturated dibasic acid having a number of 9 or more and/or the dibasic acid anhydride as one component of the raw material. By reacting with a fatty acid having 10 to 20 carbon atoms and (meth)acrylic acid in a specific range of ratios, it is possible to obtain a low-viscosity polyester poly(meth)acrylate that has fast curing properties and excellent lipophilicity. We have discovered that this can be done, and have completed the present invention.

That is, the present invention provides: (a) A mole of a branched aliphatic saturated dibasic acid and/or the dibasic acid anhydride having a total carbon number of 9 or more; (b) N primary primary acids in the molecule; A method for producing polyester polyacrylate and/or polyester polymethacrylate by esterifying 8 mol of polyhydric alcohol having a hydroxyl group, (c) C mol of fatty acid having 10 to 20 carbon atoms, and (d) 0 mol of acrylic acid and/or methacrylic acid. It is.

However, the above A, B, C, and D are numerical values that simultaneously satisfy the following conditions.

(1) 3≦N (3) 2≦□≦5 The components and manufacturing method used in the present invention will be described in detail below.

(Component) O Aliphatic saturated dibasic acid or dibasic acid anhydride The aliphatic saturated dibasic acid or dibasic acid anhydride used in the present invention [hereinafter referred to as component (a)] has a total carbon number of 9 It is above and branched. If the total number of carbon atoms is less than 9, the resulting polyester poly(meth)acrylate will have low lipophilicity, and if it is not branched, it will have low curability.

The total carbon number of component (a) is not particularly limited as long as it is 9 or more, but it should be 20 or less in order to obtain a polyester poly(meth)acrylate that has a relatively low viscosity and is easy to handle. Preferred examples of aliphatic saturated dibasic acids or dibasic acid anhydrides include methylhexahydrophthalic acid, YH-306 (manufactured by Yuka Shell Epoxy ■; dibasic acid having 10 side chain carbon atoms), Examples include dodecylsuccinic acid and its anhydride.

○Polyhydric alcohol The polyhydric alcohol used in the present invention [hereinafter referred to as component (b)] is a polyhydric alcohol having three or more hydroxyl groups bonded to a primary carbon, that is, three or more primary hydroxyl groups in one molecule, and is preferable. Specific examples include trimethylolpropane,
Examples include pentanylthritol and dipentaerthritol.

If you use a polyhydric alcohol that has a hydroxyl group bonded to a secondary carbon, that is, a secondary hydroxyl group in its molecule, the esterification reaction between the secondary hydroxyl group and the carboxyl group will not proceed, so the product will contain free hydroxyl groups. As a result of remaining, there is a problem that the product emulsifies when mixed with lipophilic liquids.

O fatty acids The fatty acids used in the present invention (hereinafter referred to as component (c)) are saturated and unsaturated fatty acids having 10 to 20 carbon atoms, and preferred specific examples include capric acid, lauric acid, myristic acid, and valmitic acid. , stearic acid, oleic acid, coconut oil fatty acid, bran oil fatty acid, linseed oil fatty acid, tung oil fatty acid, and castor oil fatty acid.

○ (meth)acrylic acid (meth)acrylic acid used in the present invention [hereinafter (d
) component] may be one that is widely and generally used industrially.

(Reaction ratio of each component) In order to obtain a polyester poly(meth)acrylate having both lipophilicity and curability in the present invention, each component must be reacted within the following range.

That is, when reacting A mole of component (a), B mole of component (b), C mole of component (c), and D mole of component (d), the above A, B, C, and D are each The value must satisfy the following conditions at the same time.

(1) 3 ≦ N 2 If it is smaller than 0.9 or larger than 1.1, unreacted hydroxyl groups or carboxyl groups remain in the product, which impairs the emulsification resistance of the polyester poly(meth)acrylate, that is, the miscibility with lipophilic liquids. There is a problem with the decline. When the value of the molar ratio D/C of fatty acid and (meth)acrylic acid is larger than 5, the number of added moles of fatty acid becomes too small, the lipophilicity of the polyester poly(meth)acrylate decreases, and D/C becomes 2. If it is smaller, the content of (meth)acryloyl groups in the polyester poly(meth)acrylate becomes too small, resulting in a problem that the curability of the polyester poly(meth)acrylate decreases.

(Manufacturing method) The manufacturing method of the present invention can be carried out as follows. That is, component (a), component (b), component (c) and component (d) are placed in a reactor preferably equipped with a stirrer, a thermometer and a water separator.
Predetermined amounts of ingredients are added in random order and heated. At this time,
It is preferable that a reaction solvent that also serves as a dehydration entrainer, an esterification catalyst, and a polymerization inhibitor are added at the same time.

Water produced during the reaction is removed from the system as an azeotrope with the reaction solvent, and the end point of the reaction may be determined by the amount of water produced as a by-product.

After the reaction is completed, the reaction solution is washed with water, the aqueous layer is separated and removed, and the solvent in the organic layer is distilled off under reduced pressure to obtain the target compound, polyester poly(meth)acrylate.

In order to cure the polyester poly(meth)acrylate obtained as described above, it may be irradiated with active energy rays such as ultraviolet rays or electron beams, left at room temperature in the presence of a radical polymerization catalyst, or heated. It is preferable to contain a photosensitizer when curing by irradiation with ultraviolet rays, and a thermal decomposition type initiator such as peroxide when curing at room temperature or by heating.

The polyester poly(meth)acrylate obtained by the present invention has both fast curing properties and lipophilic properties, and also has a low viscosity, so it can be used in various applications that require these properties, especially in coatings and lithographic printing. It is useful as a vehicle for ink, etc.

In order to utilize the polyester poly(meth)acrylate obtained by the present invention as a vehicle for paints or lithographic printing inks, it is necessary to contain commonly used additives such as pigments, sensitizers, stabilizers, and waxes. good.

[Examples and comparative examples]

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 299 g (1°15 mol) of dodecylsuccinic anhydride (branched aliphatic saturated dibasic acid anhydride having a total carbon number of 12) was placed in a reactor equipped with a stirrer, a thermometer, and a water separator. ), pentaerythritol 312.8g (2.3 mol), oleic acid 323.7g (1.15 mol), acrylic acid 414
．． 0 g (5,75 mol), 26 g p-toluenesulfonic acid, l phenothiazine.

1,350 g of toluene were charged and heated while stirring. When the internal temperature reached 105°C, water produced by the reaction began to flow out as an azeotrope with toluene. Water was removed from the system using a water separator.

The reaction was completed 6 hours after the start of the reaction, and the amount of water was 140°2ml.
He was a distiller. After the reaction was completed, the reaction solution was washed with water, the aqueous layer was separated, and the solvent was distilled off under reduced pressure to obtain 1125 g of the desired polyester poly(meth)acrylate. This product is designated as compound 1.

Example 2 269.5 g (1,15
The reaction was carried out in exactly the same manner as in Example 1 except that mol) was used,
1070 g of polyester poly(meth)acrylate was obtained. This product is designated as compound 2.

Example 3 647.4 g (2.3 moles) of oleic acid, 3 acrylic acid
The reaction was carried out in exactly the same manner as in Example 1 except that 31.2 g (4.6 mol) was used, and 1230 g of polyester poly(meth)acrylate was obtained. This product is designated as compound 3.

Comparative Example 1 Phthalic acid, which is a non-branched aromatic dibasic acid, was
The reaction was carried out in exactly the same manner as in Example 1, except that 70.2 g (1.15 mol) was used, and 1070 g of polyester poly(meth)acrylate was obtained. This product is designated as compound 4.

Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that 971.1 g (3.45 mol) of oleic acid and 248.4 g (3.45 mol) of acrylic acid were used (mol of acrylic acid relative to oleic acid). The ratio was 1), and 1,380 g of polyester (poly(meth)acrylate) was obtained. This product is designated as compound 5.

Viscosity, kerosene solubility, and curability were evaluated using Compounds 1 to 5 obtained in Examples 1 to 3 and Comparative Examples 1 to 2, and the results shown in Table 1 below were obtained.

Table 1 In addition, evaluation of various characteristics was performed by the following method.

<Viscosity> The viscosity (25° C.) of Compounds 1 to 5 was measured using an E-type viscometer (VISCO NICEMD type manufactured by Tokyo Rika Kogyo Co., Ltd.) (unit: CρS).

<Kerosine Solubility> Kerosene was added to 10.0 g of Compounds 1 to 5 until the solution became cloudy, and the amount of kerosene added up to the cloudy point was measured. Note that the greater the amount of kerosene added, the more 1. This shows that the desired lipophilicity is large.

<Curability> A sample prepared by adding 5@tX photoinitiator [trade name Irgacure 651 manufactured by Nippon Ciba Geigy] to compounds 1 to 5 and coating it on a substrate with a thickness of 5μ was placed on a conveyor and heated at 80kW. /cm condensing high pressure mercury lamp (focal length 1
The coating film on the sample was cured by passing it under 0cs+), and the maximum conveyor speed (unit: m/min) that could eliminate the tank on the surface of the coating film was defined as curability.

(C) [Effects of the Invention] The polyester poly(meth)acrylate obtained by the present invention is a compound that has high lipophilicity, fast curing property, and low viscosity, and is particularly useful as, for example, a paint or a lithographic printing ink. be.

By producing a lithographic printing ink using the polyester poly(meth)acrylate provided by the present invention, it satisfies various properties, and in particular, productivity can be significantly improved due to the fast curing speed. Its industrial value is extremely large.

Claims (1)

[Claims] 1. (a) A mole of a branched aliphatic saturated dibasic acid and/or anhydride of the branched aliphatic acid having a total number of carbon atoms of 9 or more, (b) N in the molecule. B mol of polyhydric alcohol having a primary hydroxyl group, (c) C mol of fatty acid having 10 to 20 carbon atoms, and (d) D mol of acrylic acid and/or methacrylic acid of polyester polyacrylate and/or polyester polymethacrylate for esterifying. Production method. However, the above A, B, C, and D are numerical values that simultaneously satisfy the following conditions. (1) 3≦N (2) 0.9≦(N×B)/(2×A+C+D)≦1.
1 (3) 2≦D/C≦5