JP2005075973A - Method for producing oligo(meth)acrylate-including composition, oligo(meth)acrylate- including composition therefrom, method for hardening the same and hardened product by the hardening method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple method for producing an oligo(meth)acrylate-including composition that can replace the conventional method that includes complicated steps and provide the oligo(meth)acrylate-including composition. <P>SOLUTION: This simple method for producing the oligo(meth)acrylate-including composition comprises following two steps: the first step where a mixture including (A) one or more selected from a group consisting of polybasic acid anhydrides, polybasic acids and polybasic esters, (B) one or more selected from the compounds bearing one or more (meth)acryloyl groups in one molecule and (C) at least one selected from the group including esterification catalysts and/or transesterification catalysts is allowed to react whereby polyester (meth)acrylate-including composition and the second step where (D) one or more selected from the compound bearing one or more of isocyanate groups in one molecule are added to the reaction mixture obtained at the first step. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing an oligo (meth) acrylate-containing composition, an oligo (meth) acrylate-containing composition obtained by the production method, a method for curing the composition, and a cured product obtained by the curing method. In particular, the present invention provides a simple method for producing an oligo (meth) acrylate-containing composition typified by polyester (meth) acrylate useful for various uses, and an oligo (with improved cured material properties obtained by the production method. It relates to a (meth) acrylate-containing composition.

  From the standpoint of environmental improvement, the present inventors, for example, at the time of molding a reinforced plastic (hereinafter referred to as “FRP”), impregnating a glass resin with a polyester resin and curing the styrene contained in the resin. Research has been done to improve the situation exposed to However, in spite of efforts from various fields over 20 years, this problem has not been solved sufficiently.

  This includes a current polyester resin, that is, an α, β-unsaturated carboxylic acid (or an acid anhydride thereof) as a component, an optional polybasic acid (or an acid anhydride thereof), and a desired polyvalent acid. In a resin in which an unsaturated polyester obtained by esterification with an alcohol is dissolved in a styrene monomer, the molecular weight (Mn) of the unsaturated polyester as the main component is usually about 1,500 to 3,000, and it has a very high viscosity at room temperature. The main reason is that it is extremely difficult to reduce the content of styrene as a polyester resin to 30% by mass or less in view of workability during molding because it is a liquid or almost solid. Because of these difficulties, there is still no success in providing polyester resins that do not contain volatile styrene or have a reduced content to a level that does not cause operational problems.

  On the other hand, attempts have been made to add a styrene volatilization inhibitor such as wax to the polyester resin for the purpose of preventing volatilization of styrene. However, even when a styrene volatilization inhibitor is added in this way, when the styrene content is about 20% by mass in order to ensure workability, the volatilization amount should be negligible in practice. Is known to be virtually impossible.

  As described above, as long as the conventional unsaturated polyester is used as the main component of the polyester resin, the use of styrene is indispensable. Therefore, it can be said that it is difficult to improve the fundamental working environment.

  On the other hand, a so-called polyester having one or more acryloyl groups and / or methacryloyl groups (hereinafter, collectively referred to as “(meth) acryloyl groups”) in one molecule and having a polyester skeleton ( It is generally known that oligo (meth) acrylates such as (meth) acrylate have a lower viscosity than the molecular weight. If this oligo (meth) acrylate can be replaced with an unsaturated polyester of a polyester resin, or even a part thereof can be replaced with this, it can be expected that the amount of styrene used in the polyester resin can be reduced due to its low viscosity. In this case, it is considered possible to develop a polyester resin containing no styrene.

  Here, “(meth) acrylate” means “acrylate” and / or “methacrylate”. Similarly, “(meth) acrylic acid” represents “acrylic acid” and / or “methacrylic acid”.

  By the way, as a manufacturing method of the conventional general polyester (meth) acrylate and the resin composition containing this acrylate, the following methods are mentioned, for example. That is,

  1) First, an acid catalyst such as sulfuric acid or para-toluenesulfonic acid is added to a raw material composition comprising (meth) acrylic acid, a desired carboxylic acid (or acid anhydride thereof) and a polyhydric alcohol, and further benzene or toluene. An aromatic solvent such as the above is added and heated at a temperature of about 80 to 100 ° C. or under reflux of the solvent to carry out esterification and simultaneously remove water formed by azeotroping with the solvent;

  2) Next, after neutralizing the acid catalyst with alkali, washing with water is repeated as many times as necessary, and water and solvent are distilled off to obtain the desired polyester (meth) acrylate or the acrylate-containing resin composition. Is the method. Such a method is described in detail in “Functional Acrylic Resin”, Techno System Co., Ltd., May 25, 1985, first edition, first volume, page 439, “36.2.1 Polyester Acrylate”. There is.

  As a typical example of the prior art in which (meth) acrylic acid ester or (meth) acrylic acid, polyhydric alcohol, carboxylic acid or carboxylic anhydride is reacted, Japanese Patent No. 2615605 (Patent Document 1) can be mentioned. According to the patent specification, after reacting at 99 ° C. to 115 ° C. with toluene as a solvent in the presence of a sulfuric acid catalyst, washing with a 10% sodium hydroxide aqueous solution and further washing with 10% ammonium sulfate water, 80 ° C. And toluene was distilled off under reduced pressure.

  Japanese Patent No. 2975173 (Patent Document 2) can be given as a typical example of using an epoxy compound as a diol component instead of using the above polyhydric alcohol. According to the patent specification, a reaction product of an epoxy compound and (meth) acrylic acid, that is, (meth) acrylic acid ester and carboxylic acid or carboxylic acid anhydride is heated at 90 ° C. to 95 ° C. in the presence of a catalyst. A method for obtaining an unsaturated group-containing carboxylic acid compound having an acid value of 98 mg-KOH / g to 119 mg-KOH / g, that is, an oligo (meth) acrylate composition, by reacting at a reaction temperature for 20 to 30 hours is described. Yes. Thus, when not reacting for a long time at the temperature of 130 degrees C or less, the target resin is not obtained.

  One of the main reasons for such a complicated method and the necessity of a long-time reaction is that a polyester produced by polymerization of a highly polymerizable (meth) acryl group during the esterification reaction For example, a side reaction such as gelling of (meth) acrylate may be caused, and the practicality of polyester (meth) acrylate may be impaired.

  However, since such a method requires a remarkably large number of steps and time, the cost of the final resin is not as high as that of a general-purpose resin even if the cost of raw materials is not so high when industrially implemented. It has the disadvantage of being far beyond.

  For this reason, the resin containing polyester (meth) acrylate is limited in its use, and is used only for a part of photo-curing resin, and is only used for special adhesives. Only.

  As a method for suppressing gelation of (meth) acrylate or oligo (meth) acrylate (the above-mentioned side reaction), a method of adding a polymerization inhibitor and reacting while blowing oxygen (or air) is known. If a large amount of a polymerization inhibitor is used while blowing a high concentration of oxygen, synthesis may be possible at 140 ° C or higher, but the polymerization inhibitor added when the resulting resin is cured and molded significantly inhibits curability. There is a risk that. Therefore, when a polymerization inhibitor is added in a large amount and synthesized, it is necessary to remove the polymerization inhibitor by other separation methods such as distillation and extraction before molding. Therefore, it is considered that gelation of the (meth) acryloyl group cannot be avoided when a polymerization inhibitor that does not interfere with curing during curing molding is added and reacted at a temperature exceeding 140 ° C.

  Attempts have been made to solve these problems, and representative examples thereof include JP-A No. 2002-226564 (Patent Document 3) and International Publication No. 03/000768 (Patent Document 4). Patent Document 3 describes a production method in which an oligo (meth) acrylate is obtained in a short time at a reaction temperature of 140 ° C. or higher using a titanium compound as a catalyst. Furthermore, Patent Document 4 describes a production method that can easily obtain an oligo (meth) acrylate composition with little coloring at a reaction temperature of 140 ° C. or higher using an antimony compound as a catalyst in a short time. ing. These production methods enable the reaction time to be remarkably shortened, and the oligo (meth) acrylate-containing composition obtained by the production method has almost the same curing characteristics as known styrene-containing unsaturated polyesters. Although it has been confirmed that it has physical properties of a cured product, further improvement in performance has been demanded for oligo (meth) acrylate compositions from the viewpoint of demands for improving various properties of materials in recent years.

  In particular, regarding the improvement of water resistance in the cured product of the above-described composition, there is a great demand for such performance improvement. The oligo (meth) acrylate-containing composition obtained by the production method described in JP-A No. 2002-226564 and WO 03/000768 described above has a hydroxyl group or a reaction raw material or a reaction intermediate from its characteristics. Compounds such as 2-hydroxyethyl (meth) acrylate having a carboxylic acid group or 2- (meth) acryloyloxyalkylphthalic acid are included. Generally, in unsaturated polyester resin compositions, if a large amount of a compound having a hydroxyl group or a carboxyl group is contained, the water resistance of the cured product is lowered because these functional groups are hydrophilic. It has been known. Even in a general application of the oligo (meth) acrylate-containing composition, the esterification reaction can be carried out to reduce the concentration of the compound to a level at which the water resistance of the cured product does not decrease, but further reduction is required. In this case, it is assumed that it is difficult to consider the ease of gelation.

  Of course, it is possible to purify the oligo (meth) acrylate-containing composition by a conventionally known method and remove these compounds. However, if a complicated purification process is performed, the “simple manufacturing process” that is a feature of the manufacturing method may be lost, and this is not a preferable method.

  In addition, a method has been proposed in which the concentration of a compound having a hydroxyl group or a carboxyl group is relatively lowered by mixing other resins, but this is not an absolute reduction in content, and thus is fundamental. It is clear that this is not a proper solution.

  From the above viewpoint, there is a demand for a method for easily obtaining an oligo (meth) acrylate-containing composition with improved water resistance while maintaining the resin physical properties and cured physical properties specific to polyester (meth) acrylate.

Japanese Patent No. 2615605 (pages 3 to 5) Japanese Patent No. 2975173 (pages 2 to 5) JP 2002-226564 A (pages 4 to 5) International Publication No. 03/000768 pamphlet (pages 4-20)

  An object of the present invention is to provide a simple production method instead of a production method of an oligo (meth) acrylate represented by polyester (meth) acrylate and the like and a composition containing the (meth) acrylate by a conventional complicated process, and the production method. It is providing the obtained oligo (meth) acrylate containing composition.

  Another object of the present invention is to provide a method for producing an oligo (meth) acrylate-containing composition having improved cured product properties, particularly water resistance.

  As a result of intensive studies, the present inventors have adopted a method including two specific steps, so that purification steps such as washing and distillation, which are conventionally known methods, are unnecessary, and an oligo (meta) having excellent water resistance. ) It has been found that acrylate-containing compositions can be produced.

  This invention (I) is a manufacturing method of the oligo (meth) acrylate containing composition characterized by including the following 1st processes and 2nd processes.

(First step)
A step of reacting a mixture containing the following (A), (B) and (C) to obtain a polyester (meth) acrylate-containing composition (A) From a polybasic acid anhydride, a polybasic acid and a polybasic acid ester At least one or more (C) esterification catalyst and / or transesterification catalyst selected from compounds having at least one or more (B) one or more (meth) acryloyl groups in the molecule selected from the group consisting of

(Second step)
The reaction mixture obtained in the first step is added with the following (D) and reacted to obtain an oligo (meth) acrylate-containing composition (D) From a compound having one or more isocyanate groups in the molecule At least one or more selected

  The present invention (II) relates to an oligo (meth) acrylate-containing composition obtained by the production method of the present invention (I).

  The present invention (III) relates to a method for curing an oligo (meth) acrylate-containing composition, wherein a radical initiator is added to the oligo (meth) acrylate-containing composition of the present invention (II) and cured.

  The present invention (IV) relates to a cured product characterized by being cured by the curing method of the present invention (III).

  Furthermore, this invention contains the following aspects, for example.

[1] A method for producing an oligo (meth) acrylate-containing composition comprising the following first step and second step.
(First step)
A step of reacting a mixture containing the following (A), (B) and (C) to obtain a polyester (meth) acrylate-containing composition (A) From a polybasic acid anhydride, a polybasic acid and a polybasic acid ester (B) at least one selected from compounds having one or more (meth) acryloyl groups in the molecule (C) at least one selected from esterification catalysts and / or transesterification catalysts that's all

(Second step)
The step of adding the following (D) to the reaction mixture obtained in the first step and reacting it to obtain an oligo (meth) acrylate-containing composition (D) From a compound having one or more isocyanate groups in the molecule At least one or more selected

  [2] The method for producing an oligo (meth) acrylate-containing composition according to [1], wherein the first step is performed in a range of 140 ° C to 210 ° C.

  [3] The oligo (1) or [2] described above, wherein, in the first step, in addition to (A), (B) and (C), (E) a mixture containing an alkylene monoepoxide is reacted. A method for producing a (meth) acrylate-containing composition.

  [4] In any one of [1] to [3], the reaction is performed using a mixture containing (F) a polyhydric alcohol in addition to (A), (B) and (C) in the first step. A method for producing an oligo (meth) acrylate-containing composition according to claim 1.

  [5] The polybasic acid anhydride of (A) is malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride and 1,2-cyclohexanedicarboxylic acid The method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [4], which is at least one selected from the group consisting of acid anhydrides.

  [6] (A) is a reaction mixture containing a polybasic acid anhydride and / or a polybasic acid ester obtained by reacting a polybasic acid with an alkylene monoepoxide and / or a purified product of the polybasic acid ester. The manufacturing method of the oligo (meth) acrylate containing composition in any one of [1]-[4] characterized by the above-mentioned.

  [7] (A) is a reaction mixture containing a polybasic acid anhydride and / or a polybasic acid ester obtained by reacting a polybasic acid with a monoalcohol and / or a purified product of the polybasic acid ester. The manufacturing method of the oligo (meth) acrylate containing composition in any one of [1]-[4] characterized.

  [8] (A) is a reaction mixture containing a polybasic acid ester and / or a polybasic acid ester obtained by reacting a polybasic acid with a polyhydric alcohol and / or a purified product of the polybasic acid ester. The method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [4].

  [9] A reaction mixture containing (A) a polybasic acid ester obtained by reacting a polybasic acid anhydride and / or polybasic acid with a monoalcohol, and a polybasic acid ester obtained by reacting a polyhydric alcohol. And / or the method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [4], wherein the polybasic acid ester is a purified product.

  [10] The method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [9], wherein (B) is (meth) acrylic acid.

  [11] The (B) is a reaction mixture containing (meth) acrylic acid ester obtained by reacting (meth) acrylic acid and an alkylene monoepoxide and / or a purified product of the (meth) acrylic acid ester. The method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [9].

  [12] The (B) is a reaction mixture containing (meth) acrylic acid ester obtained by reacting (meth) acrylic acid and monoalcohol and / or a purified product of the (meth) acrylic acid ester, The manufacturing method of the oligo (meth) acrylate containing composition in any one of [1]-[9].

  [13] (B) includes (meth) acrylic acid and / or an ester compound obtained by reacting (meth) acrylic acid with a monoalcohol and a (meth) acrylic acid ester obtained by reacting a polyhydric alcohol. The method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [9], which is a reaction mixture and / or a purified product of the (meth) acrylic acid ester.

  [14] (C) The esterification catalyst and / or transesterification catalyst is titanium, antimony, cobalt, zinc, lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, strontium, barium, radium, zirconium, hafnium, The oligo according to any one of [1] to [13], characterized in that it is at least one organic and / or inorganic compound containing one or more elements selected from the group consisting of manganese, germanium and aluminum. A method for producing a (meth) acrylate-containing composition.

  [15] (C) The esterification catalyst and / or transesterification catalyst is titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, antimony trioxide, triphenylantimony, antimony potassium tartrate , Antimony acetate, cobalt acetate, cobalt acetate tetrahydrate, cobalt naphthenate, cobalt oxide, cobalt carbonate, acetylacetonatocobalt, cobalt stearate, zirconium acetate, zirconium acetate hydrate, acetylacetonatozirconium, zirconium tetra Propoxide, zirconium tetrabutoxide, zirconium oxide, zirconium hydroxide, zinc acetate, zinc acetate dihydrate, acetylacetonato zinc, lithium acetate, lithium acetate tetrahydrate, lithium hydroxide Lithium, acetylacetonatolithium, sodium acetate, sodium acetate trihydrate, sodium hydroxide, sodium acetylacetonate, potassium acetate, potassium hydroxide, potassium acetylacetonate, rubidium acetate, rubidium hydroxide, cesium acetate, water The method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [14], which is at least one selected from the group consisting of cesium oxide, francium acetate, and magnesium acetate.

  [16] (D) is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, difinylmethane-4,4′-diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, p -Phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, xylylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane Triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-he Containing at least one selected from the group consisting of samethylene triisocyanate, bicycloheptane triisocyanate and trimethylhexamethylene diisocyanate [1] to [15] A method for producing the composition.

  [17] At least one selected from the group consisting of (E) ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide, and glycidyl (meth) acrylate. It is a seed | species or more, The manufacturing method of the oligo (meth) acrylate containing composition in any one of [3 or [5]-[16] characterized by the above-mentioned.

  [18] (F) is ethylene glycol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-butanediol, 1,4 -Butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, o-xylene glycol M-xylene glycol, p-xylene glycol, 1,2-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, Bisphenol A, Hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F, hydrogenated bisphenol F, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, pentaerythritol, dipentaerythritol, trimethylol The method for producing an oligo (meth) acrylate-containing composition according to any one of [4] to [17], which is at least one selected from the group consisting of propane and ditrimethylolpropane.

  [19] The method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [18], wherein a reaction is carried out in the presence of a polymerization inhibitor.

  [20] The method for producing an oligo (meth) acrylate-containing composition according to any one of [1] to [19], wherein the reaction is performed in the presence of oxygen.

  [21] An oligo (meth) acrylate-containing composition obtained by the production method according to any one of [1] to [20].

  [22] A method for curing an oligo (meth) acrylate-containing composition, wherein a radical initiator is added to the oligo (meth) acrylate-containing composition according to [21] and cured.

  [23] A cured product, which is cured by the curing method according to [22].

  According to the present invention having the above-described configuration, an oligo (meth) acrylate-containing composition that has conventionally required a production method by a number of steps can be produced by a simple method. Moreover, according to this invention, an oligo (meth) acrylate containing composition can be manufactured in a short time under high temperature which was not thought by the common sense in a prior art. Moreover, according to the present invention, an oligo (meth) acrylate-containing composition that has been conventionally expensive and can only be used for special purposes can be provided at a low cost by a simple method, and used for a wide range of uses. be able to. In particular, according to the present invention, it is possible to produce a resin that does not contain a reactive diluent monomer typified by styrene, or has a reduced amount of use so as not to affect the working environment. Furthermore, according to the present invention, it is possible to provide oligo (meth) acrylate having high water resistance.

  Hereinafter, the present invention will be described more specifically with reference to the drawings as necessary. In the following description, “parts” and “%” representing the quantity ratio are based on mass unless otherwise specified.

(Invention (I))
First, the present invention (I) will be described. This invention (I) is a manufacturing method of the oligo (meth) acrylate containing composition characterized by including the following 1st processes and 2nd processes.

First step Step of reacting a mixture containing the following (A), (B) and (C) to obtain a polyester (meth) acrylate-containing composition (A) Polybasic acid anhydride, polybasic acid and polybasic (B) at least one or more selected from compounds having one or more (meth) acryloyl groups in the molecule (C) esterification catalyst and / or transesterification catalyst

2nd process The process of adding the following (D) to the reaction mixture obtained at the 1st process, making it react, and obtaining an oligo (meth) acrylate containing composition (D) One or more isocyanate groups in a molecule | numerator At least one selected from compounds having

  In the first step described above, it is considered that (A) and (B) react in the presence of the catalyst (C) to produce a polyester (meth) acrylate having (meth) acryloyl groups mainly at both ends. As other products, a compound having a (meth) acryloyl group and a hydroxyl group in one molecule as a reaction intermediate, or a compound having a (meth) acryloyl group and a carboxyl group in one molecule is generated.

  In the second step, the reaction intermediate obtained in the first step and (D) mainly react, and a compound having a urethane bond or an amide bond in one molecule and having a (meth) acryloyl group is mainly used. It is thought to generate.

  Therefore, the target oligo (meth) acrylate can be obtained by these first and second steps.

((A) component)
The (A) polybasic acid anhydride, polybasic acid, and polybasic acid ester will be described.

  Examples of the polybasic acid anhydride in (A) include malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, 2-methylsuccinic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 4- Acid anhydride of methylcyclohexane-1,2-dicarboxylic acid, acid anhydride of endomethylenetetrahydrophthalic acid, acid anhydride of methylendomethylenetetrahydrophthalic acid, methyltetrahydrophthalic anhydride, phthalic anhydride, biphenyl-2,2 -Acid anhydride of dicarboxylic acid, acid anhydride of biphenyl-4,4'-dicarboxylic acid, trimellitic anhydride, pyromellitic anhydride, maleic acid methylcyclohexene tetrabasic acid anhydride and tetrabromophthalic acid Although an anhydride etc. are mentioned, it is not necessarily limited to these.

  Examples of the polybasic acid in (A) include malonic acid, succinic acid, glutaric acid, adipic acid, 2-methylsuccinic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexane. Dicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, methyltetrahydrophthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, biphenyl-2,2'-dicarboxylic acid Acid, biphenyl-3,3-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, trimellitic acid, pyromellitic acid, maleated methylcyclohexene tetrabasic acid, het acid and tetrabromophthalic acid, etc. Especially because it is limited to these No.

Examples of the polybasic acid ester in (A) include the following (a), (b), (c) and (d). This polybasic acid ester may be a reaction mixture containing (a), (b), (c) and (d), or a purified product.
(A) Polybasic acid ester obtained by reacting polybasic acid anhydride and / or polybasic acid with alkylene monoepoxide (b) Obtained by reacting polybasic acid anhydride and / or polybasic acid with monoalcohol (C) Polybasic acid ester obtained by reacting polybasic acid anhydride and / or polybasic acid with polyhydric alcohol (d) Polybasic acid anhydride and / or polybasic acid and monoalcohol Polybasic acid ester obtained by reacting polybasic acid ester with polyhydric alcohol

(Raw material for obtaining polybasic acid ester)
The alkylene monoepoxide, polybasic acid, polybasic acid anhydride, polyhydric alcohol and monoalcohol as raw materials used to obtain the polybasic acid esters (a), (b), (c) and (d) will be described. .

  Examples of the alkylene monoepoxide in the polybasic acid ester (a) include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide and glycidyl (meth). Examples thereof include, but are not limited to, acrylates.

  The polybasic acid anhydride and polybasic acid in the polybasic acid esters (a), (b), (c) and (d) are the same as the above-mentioned polybasic acid anhydride and polybasic acid.

  Examples of monoalcohols in the polybasic acid esters (b) and (d) include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and 1-butanol. 2-butanol, 2-methyl-1-butanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 1,3-dimethylpropanol, 1,1-dimethyl-1-propanol, 2-methyl-1-butanol, 2,2-dimethylpropanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 1,1- Dimethylbutanol, cyclohexanol, phenol, benzyl alcohol and naphthol Including without particular limitation thereto.

  Examples of the polyhydric alcohol in the polybasic acid esters (c) and (d) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3. -Butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexane Dimethanol, o-xylene glycol, m-xylene glycol, p-xylene glycol, 1,2-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, bis Enol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F, hydrogenated bisphenol F, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, pentaerythritol, dipentaerythritol , Trimethylolpropane, ditrimethylolpropane and the like, but are not particularly limited thereto.

  These starting materials can be used without any purification as long as they are usually commercially available, whether for reagents or for industrial use. Of course, it is preferable to use a higher purity from the viewpoint of suppressing side reactions. They can also be used alone or as a mixture.

(Specific examples of polybasic acid esters)
The polybasic acid esters (a), (b), (c) and (d) will be described more specifically with examples.

  “(A) Polybasic acid ester obtained by reacting polybasic acid anhydride and / or polybasic acid with alkylene monoepoxide” is, for example, a polybasic acid ester obtained by reacting ethylene oxide and succinic acid. Examples thereof include di (2-hydroxyethyl) succinate and mono (2-hydroxyethyl) succinate.

  As "(b) polybasic acid ester obtained by reacting polybasic acid anhydride and / or polybasic acid with monoalcohol", for example, as polybasic acid ester obtained by reacting succinic acid and methanol, Examples include dimethyl succinate and monomethyl succinate.

  “(C) Polybasic acid ester obtained by reacting polybasic acid anhydride and / or polybasic acid with polyhydric alcohol” is obtained, for example, by reacting succinic anhydride with 1,3-propanediol. Examples of the polybasic acid ester include di (3-hydroxypropyl) succinate and mono (3-hydroxypropyl) succinate.

  Examples of “(d) polybasic acid ester obtained by reacting polybasic acid anhydride and / or polybasic acid with monoalcohol and polyhydric alcohol” include, for example, Examples of the polybasic acid ester obtained by reacting dimethyl acid with 1,3-propanediol include di (3-hydroxypropyl) succinate and methyl (3-hydroxypropyl) succinate.

  The compounds for obtaining the polybasic acid esters (a), (b), (c) and (d) are not limited to the above-mentioned compounds, and any equivalent compounds obtained by other production methods may be used. Further, it may be a reaction composition or a purified product. Of course, it is preferable to use a higher purity from the viewpoint of suppressing side reactions. They can also be used alone or as a mixture.

(Preferred type (A))
More preferable types of (A) are polybasic acid anhydrides, specifically, malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, trimellitic anhydride, tetrahydroanhydride Preference is given to acid anhydrides of phthalic acid and 1,2-cyclohexanedicarboxylic acid.

  The concentration of (A) is more preferably in the range of 10% by mass to 90% by mass with respect to the total mass of (A), (B) and (C). More preferably, it is 15 mass%-85 mass%. If it is less than 10% by mass or more than 90% by mass, the cured product properties of the resulting oligo (meth) acrylate-containing composition are expected to deteriorate, which is not preferable. However, the concentration is not limited to these.

((B) component)
Next, (B) a compound having one or more (meth) acryloyl groups in the molecule will be described.

Examples of the compound having one or more (meth) acryloyl groups in the molecule include the following (meth) acrylic acid esters (e), (f) and (g) in addition to (meth) acrylic acid.
(E) (meth) acrylic ester obtained by reacting (meth) acrylic acid and alkylene monoepoxide (f) (meth) acrylic ester obtained by reacting (meth) acrylic acid with monoalcohol (g) (Meth) acrylic acid and / or (meth) acrylic acid ester obtained by reacting (meth) acrylic acid with monoalcohol and (meth) acrylic acid ester obtained by reacting polyhydric alcohol

  The alkylene monoepoxide, monoalcohol and polyhydric alcohol used for obtaining the (meth) acrylic acid esters (e), (f) and (g) will be described.

  Examples of the alkylene monoepoxide in the (meth) acrylic acid ester (e) include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide, and glycidyl ( And (meth) acrylate.

  Examples of monoalcohols in (meth) acrylic acid esters (f) and (g) include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and 1 -Butanol, 2-butanol, 2-methyl-1-butanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 1,3-dimethyl Propanol, 1,1-dimethyl-1-propanol, 2-methyl-1-butanol, 2,2-dimethylpropanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 1, 1-dimethylbutanol, phenol, benzyl alcohol, naphthol, etc. That is, there is no particular limitation to these.

  Examples of the polyhydric alcohol in the (meth) acrylic acid ester (g) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, and 1,3-butane. Diol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol O-xylene glycol, m-xylene glycol, p-xylene glycol, 1,2-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2- Hydroxyethoxy) benzene, bisph Nord A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F, hydrogenated bisphenol F, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, pentaerythritol, dipentaerythritol , Trimethylolpropane, ditrimethylolpropane and the like, but are not particularly limited thereto.

  These starting materials can be used without any purification as long as they are usually commercially available, whether for reagents or for industrial use. Of course, it is preferable to use a higher purity from the viewpoint of suppressing side reactions. They can also be used alone or as a mixture.

(Specific examples of (meth) acrylic acid ester)
Hereinafter, (meth) acrylic acid esters (e), (f) and (g) will be described more specifically by way of examples.

  “(E) (Meth) acrylic acid ester obtained by reacting (meth) acrylic acid and alkylene monoepoxide” is, for example, 2 (meth) acrylic acid ester obtained by reacting acrylic acid with ethylene oxide. -Hydroxyethyl acrylate etc. are mentioned.

  “(F) (Meth) acrylic acid ester obtained by reacting (meth) acrylic acid and monoalcohol” is, for example, methyl acrylate as (meth) acrylic acid ester obtained by reacting acrylic acid with methanol. Etc.

  “(G) (Meth) acrylic acid and / or (meth) acrylic acid ester obtained by reacting (meth) acrylic acid and monoalcohol and (meth) acrylic acid ester obtained by reacting polyhydric alcohol” Examples of the (meth) acrylic acid ester obtained by reacting methyl acrylate with 1,3-propanediol include 3-hydroxypropyl acrylate and 1,3-propanediol diacrylate.

  The concentration of (B) is more preferably in the range of 10% by mass to 90% by mass with respect to the total mass of (A), (B) and (C). More preferably, it is 15 mass%-85 mass%. If it is less than 10% by mass or more than 90% by mass, the cured product properties of the resulting oligo (meth) acrylate-containing composition are expected to deteriorate, which is not preferable. However, the concentration is not limited to these.

((C) component)
(C) The esterification catalyst and / or the transesterification catalyst will be described.

  The esterification catalyst and / or transesterification catalyst may be a conventionally known catalyst, but preferably titanium, antimony, cobalt, zinc, lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, strontium, Organic and / or inorganic compounds containing one or more elements selected from the group consisting of barium, radium, zirconium, hafnium, manganese, germanium and aluminum are preferred. These catalysts are used as catalysts for esterification reactions and transesterification reactions. At the same time, it is considered that they play a role of preventing gelation due to polymerization of (meth) acryloyl groups. This is also clear from the fact that gelation is less likely to occur when these compounds are used as catalysts compared to conventional catalysts such as p-toluenesulfonic acid and sulfuric acid.

(Specific examples of compound (C))
Specific examples of the compound (C) include titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, antimony trioxide, triphenylantimony, antimony potassium tartrate, acetic acid. Antimony, cobalt acetate, cobalt acetate tetrahydrate, cobalt naphthenate, cobalt oxide, cobalt acetylacetonate, cobalt stearate, cobalt sulfate, cobalt nitrate, cobalt carbonate, lithium acetate, lithium acetate tetrahydrate, water Lithium oxide, acetylacetonatolithium, sodium acetate, sodium acetate trihydrate, sodium hydroxide, sodium acetylacetonate, potassium acetate, potassium hydroxide, potassium acetylacetonate, rubidium acetate, rubidium hydroxide, cesium acetate , Cesium hydroxide and francium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, lanthanum acetate, acetylacetone tributoxyzirconium, tetra-n-butoxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyhafnium, germanium tetra Examples include ethoxide, germanium oxide, aluminum triisopropylate, aluminum tri (secondary butyrate), aluminum diisopropylate monosecondary butyrate, aluminum ethylate, aluminum tris (acetylacetonate), zinc acetate and manganese acetate. However, the present invention is not limited to these.

  These compounds may be used alone and / or in combination of two or more. When selecting these compounds, the physical properties, safety, price, etc. of the obtained resin are taken into consideration in addition to the esterification catalyst effect and the gelation-suppressing effect at the time of reaction. To be elected.

(Suitable Compound (C))
More preferable compounds (C) include titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, antimony trioxide, triphenylantimony, antimony tartrate, antimony acetate, cobalt acetate , Cobalt acetate tetrahydrate, cobalt naphthenate, cobalt oxide, cobalt carbonate, acetylacetonatocobalt, cobalt stearate, zirconium acetate, zirconium acetate hydrate, acetylacetonatozirconium, zirconium tetrapropoxide, zirconium tet Rabtoxide, zirconium oxide, zirconium hydroxide, zinc acetate, zinc acetate dihydrate, acetylacetonato zinc, lithium acetate, lithium acetate tetrahydrate, lithium hydroxide, acetylacetona Lithium, sodium acetate, sodium acetate trihydrate, sodium hydroxide, sodium acetylacetonate, potassium acetate, potassium hydroxide, potassium acetylacetonate, rubidium acetate, rubidium hydroxide, cesium acetate, cesium hydroxide, francium acetate And magnesium acetate, and these compounds are highly effective in suppressing gelation during the reaction.

  A more preferable concentration of (C) is in the range of 10 ppm by mass to 1% by mass with respect to the total mass of the mixture containing (A) and (B). More preferably, it is the range of 100 mass ppm-5000 mass ppm. If it is less than 10 mass ppm, the reaction rate is extremely slow, and if it exceeds 1 mass%, the effect of suppressing gelation is not substantially changed. However, the concentration is not limited to these.

  The qualitative and quantitative determination of the component (C) can be performed by a conventionally known analysis method. For example, the qualitative and quantitative methods for cobalt compounds are described in detail in “New Experimental Chemistry Lecture 9 Analytical Chemistry I”, Maruzen Co., Ltd., published September 4, 1983, pp. 334, “14.2 Cobalt. Is described in the section. Compounds other than cobalt are also described in the same document.

  These starting materials can be used without any purification as long as they are usually commercially available, whether for reagents or for industrial use. Of course, it is preferable to use a higher purity from the viewpoint of suppressing side reactions. They can also be used alone or as a mixture.

((D) component)
(D) A compound having one or more isocyanate groups in the molecule will be described. In the first step, it is considered that a polyester (meth) acrylate having (meth) acryloyl groups at both ends is mainly produced. As other products, a compound having a (meth) acryloyl group and a hydroxyl group in one molecule as a reaction intermediate and a compound having a (meth) acryloyl group and a carboxyl group in one molecule are formed. (D) in the second step is considered to mainly react with the reaction intermediate obtained in the first step. In the reaction of (D) with a compound having a (meth) acryloyl group and a hydroxyl group in one molecule, a urethane bond is formed by the reaction between the hydroxyl group and the isocyanate group, and the (meth) acryloyl group and In the reaction of the compound having a carboxyl group and (D), it is considered that an amide bond is generated by the reaction of the carboxyl group and the isocyanate group.

  By these reactions, it is considered possible to reduce a compound having a hydroxyl group or a carboxyl group which is considered to be a cause of reducing water resistance. In addition, since the concentration of the reaction intermediate is considered to be lower than that of the main product in the first step, the concentration of the compound having a urethane bond and / or amide bond generated in the second step is considered to be lower than that of the main product. Therefore, it is considered that the resin properties and the cured product properties of the polyester (meth) acrylate-containing composition are hardly impaired.

(Specific examples of (D) compounds)
Specific examples of the compound (D) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, difinylmethane-4,4′-diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, hexa Methylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, xylylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octa 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene diisocyanate, and the like, but are not limited thereto.

  The molar equivalent of the isocyanate group (D) is preferably 0.1 molar equivalent to 1 molar equivalent, more preferably the total molar equivalent of hydroxyl group and carboxyl group in the reaction mixture obtained in the first step. 0.5 molar equivalent to 0.9 molar equivalent. If the molar equivalent of the isocyanate group in (D) exceeds 1 molar equivalent, the isocyanate group remains in the resulting oligo (meth) acrylate-containing composition, and the skin irritation derived from the isocyanate group may be increased. There is not preferable. On the other hand, when the molar equivalent of the isocyanate group (D) is less than 0.1 molar equivalent, it is considered that the effect of improving the properties of the cured product cannot be expected, which is not preferable. However, it is not limited to this range.

  In the first step of the present invention (I), in addition to (A), (B) and (C), (E) a mixture containing an alkylene monoepoxide is reacted, and then (D) is added to carry out the reaction. You can also When (E) is added and reacted, (B) preferably contains either methacrylic acid and / or acrylic acid.

(Mode in which (E) is added and reacted)
When the reaction is performed by adding (E), the reaction will be divided into the reaction early stage and the reaction late stage.

  It is considered that two reactions proceed at the initial stage of reaction. One is a reaction between a polybasic acid and / or polybasic acid anhydride in (A) and (D) an alkylene monoepoxide, which is a kind of (A). Reaction in which an acid ester is formed, and the other is a reaction in which (D) an alkylene monoepoxide and (meth) acrylic acid in (B) react to form (B) a (meth) acrylic acid ester It is. In the late stage of the reaction, it is considered that the esterification reaction or transesterification reaction with (A) and (B) produced in the early stage of the reaction proceeds.

  The reaction between (meth) acrylic acid and an alkylene monoepoxide at the initial stage of the reaction can provide a (meth) acrylic acid ester in a shorter time than the esterification reaction of (meth) acrylic acid and a polyhydric alcohol. Moreover, it is thought that the obtained (meth) acrylic acid ester has a boiling point higher than (meth) acrylic acid, and there is little possibility of distilling even at the reaction temperature of 140 degreeC or more. Therefore, an oligo (meth) acrylate-containing composition can be obtained more easily by adding (E).

  Examples of the (E) alkylene monoepoxide include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide, and glycidyl (meth) acrylate. .

  The amount of (E) is more preferably 1 to 20 mol with respect to 1 mol of (meth) acrylic acid in (B). More preferably, it is 1.1 mol-10 mol. When the amount of (E) exceeds 10 mol, the reaction in the late stage of the reaction in the first step is remarkably slow, which is not preferable. When the amount of (E) is less than 1 mol, (B) (meth) acrylic acid remains unreacted and is not preferable. However, the concentration is not limited to these.

(Aspect using (F))
In the first step of the present invention (I), a mixture containing (F) a polyhydric alcohol in addition to (A), (B) and (C) can be reacted. (F) A mixture containing a polyhydric alcohol is likely to have a longer reaction time than a reaction using a mixture containing an (E) alkylene monoepoxide, but various polyhydric alcohols may be used as raw materials. Since it is possible, it is thought that the obtained oligo (meth) acrylate containing composition and its hardened | cured material can be used for a wider use.

  Examples of (F) polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-butanediol, 1,4 -Butanediol, neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, o-xylene glycol M-xylene glycol, p-xylene glycol, 1,2-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, Bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F, hydrogenated bisphenol F, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, pentaerythritol, dipentaerythritol, trimethylolpropane and ditriol Examples include methylolpropane.

  A more preferable amount of (F) is 5 to 900 parts by mass when the total mass of (A), (B) and (C) is 100 parts by mass. More preferably, it is 10 mass parts-400 mass parts. If the amount of (F) is less than 5 parts by mass, the expected effect on the properties of the cured product cannot be obtained sufficiently. When the amount of (F) exceeds 900 parts by mass, (E) remains unreacted. The cured product properties of the resulting oligo (meth) acrylate-containing composition may be unfavorable. However, the concentration is not limited to these.

(Reaction temperature)
The reaction temperature of the present invention (I) will be described. The reaction temperature in the first step is preferably in the range of 140 ° C to 210 ° C, more preferably 160 ° C to 190 ° C. If it is lower than 140 ° C., the reaction rate may be remarkably lowered, which is not preferable. If the temperature exceeds 210 ° C., side reactions such as gelation may easily proceed, such being undesirable.

  The reaction temperature in the second step is preferably in the range of 0 ° C to 210 ° C, more preferably 0 ° C to 150 ° C. If it is less than 0 ° C, the reaction rate may be remarkably lowered, which is not preferable. If the temperature exceeds 210 ° C., side reactions such as gelation may easily proceed, such being undesirable.

(Aspect using a polymerization inhibitor, etc.)
In the present invention (I), an oligo (meth) acrylate-containing composition can be more stably produced by the presence of a polymerization inhibitor and oxygen. Although the kind of polymerization inhibitor is illustrated, it does not necessarily limit in particular. For example, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, tolquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p- Benzoquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t-butylparacresol hydroquinone monomethyl ether, Alpha naphthol, acetamidine acetate, acetamidine sulfate, phenylhydrazine hydrochloride, hydrazine hydrochloride, trimethylbenzylammonium chloride, laurylpyridinium chloride, cetyltrimethylammonium chloride, phenyl Limethylammonium chloride, trimethylbenzylammonium oxalate, di (trimethylbenzylammonium) oxalate, trimethylbenzylammonium malate, trimethylbenzylammonium tartrate, trimethylbenzylammonium glycolate, phenyl-β-naphthylamine, parabenzylaminophenol, di -Β-naphthylparaphenylenediamine, dinitrobenzene, trinitrotoluene, picric acid, cyclohexanone oxime, pyrogallol, tannic acid, resorcin, triethylamine hydrochloride, dimethylaniline hydrochloride, dibutylamine hydrochloride, etc. Not to do.

  A more preferable concentration of the polymerization inhibitor is 0.001 part by mass to 0.2 part by mass when the total mass of the mixture containing (A) and (B) is 100 parts by mass. More preferably, it is 0.005 mass part-0.15 mass part in a raw material. If the concentration of the polymerization inhibitor is less than 0.001 part by mass, not only may there be a risk of gelation during the reaction at high temperature, but the resulting oligo (meth) acrylate-containing composition will have a high molecular weight during storage. This is not preferable because components may be generated. If the concentration of the polymerization inhibitor exceeds 0.2 parts by mass, the polymerization property may be significantly deteriorated when the resulting resin composition is cured and molded, and the polymerization inhibitor is removed by distillation, extraction or other methods. Alternatively, it is not preferable because a large amount of an initiator, an accelerator, and an auxiliary accelerator must be used for curing. However, the concentration is not limited to these.

(Mode in which oxygen is present)
In order to suppress polymerization and gelation of the reaction solution at a high temperature, it is considered more effective that oxygen is present in the reaction solution in addition to the polymerization inhibitor. As a method for supplying oxygen into the reaction solution, any method may be used, such as a method of bubbling air with a blow-in tube, a method of supplying air to the reactor gas phase and supplying it to the reactor liquid phase by stirring. Even if air or oxygen diluted with an inert gas such as nitrogen is used to supply oxygen, any method may be used as long as the amount of oxygen necessary to suppress gelation is supplied.

(Invention (II))
Next, the present invention (II) will be described. The present invention (II) is an oligo (meth) acrylate-containing composition obtained in the present invention (I). For easier understanding, for example, an example of the composition of the present invention (II) will be shown with specific compounds.

(Example of composition of the present invention (II))
When the reaction is carried out using (A) phthalic anhydride, (B) 2-hydroxyethyl methacrylate (D) 2,4-tolylene diisocyanate, the compounds represented by the following formulas (1) to (4) are: Mainly obtained.

（式中ａは１〜５の整数を表す。） Formula (1)

(Wherein a represents an integer of 1 to 5)

（式中ｂおよびｃはそれぞれ独立した１〜５の整数を表す。） Formula (2)

(Wherein b and c each represent an independent integer of 1 to 5)

（式中ｄおよびｅはそれぞれ独立した１〜５の整数を表す。） Formula (3)

(In the formula, d and e each independently represent an integer of 1 to 5.)

（式中ｆおよびｇはそれぞれ独立した１〜５の整数を表す。） Formula (4)

(In the formula, f and g each independently represent an integer of 1 to 5.)

  In general, the reason is not clear, but if the concentration of hydroxyl group or carboxyl group is high, the curing characteristics may deteriorate. Perhaps the degree of influence varies depending on the type of curing agent. The resulting oligo (meth) acrylate-containing composition is thought to be less likely to deteriorate the curing characteristics because of its small number of hydroxyl groups and carboxyl groups.

  The resulting oligo (meth) acrylate-containing composition can be mixed with other radical curable resins and / or used alone. Moreover, a radical curable monomer can also be added and used.

  In order to suppress the polymerization reaction, a conventionally known polymerization inhibitor can be added to the resulting oligo (meth) acrylate-containing composition. In addition, conventionally known initiators, accelerators, co-promoters, and the like can be added in advance before curing and molding.

(Combination with various materials)
When using an oligo (meth) acrylate containing composition, it can be used together with conventionally well-known various materials. Examples of materials that can be used in combination include inorganic and / or organic reinforcing materials, fillers, mold release agents, antifoaming agents, and coloring agents.

  Specific examples of the inorganic and / or organic reinforcing agent include glass fiber, carbon fiber, aramid fiber, vinylon fiber, and metal fiber.

  Specific examples of the filler include calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, aluminum hydroxide, clay, talc, kaolin, diatomaceous earth, mica powder, glass fiber powder, powdered asbestos, silica gel, and rock wool. Is mentioned.

  Specific examples of the mold release agent include a metal salt of stearic acid represented by wax and zinc stearate.

  Specific examples of the antifoaming agent include silicone oil, polyvinyl ether, acrylate copolymer, and fluorine compounds.

(Invention (III))
The present invention (III) will be described. The present invention (III) is a curing method for curing the oligo (meth) acrylate-containing composition of the present invention (II). Examples of the method for curing the oligo (meth) acrylate-containing composition include room temperature curing, heat curing, photocuring, and electron beam curing. At room temperature curing, a radical initiator and an accelerator are added, and an auxiliary accelerator and the like are added and cured as necessary. Heat curing is performed after adding a radical initiator. In photocuring, light is irradiated after adding a radical initiator. In the electron beam curing, a radical initiator is added and then cured by irradiation with an electron beam.

  Specific examples of the radical initiator are described in “Polyester Resin Handbook”, Nikkan Kogyo Shimbun Co., Ltd., June 30, 1988, the first edition, 1st edition, pages 116-117, pages 214-216.

  Specific examples of the accelerator include cobalt naphthenate, copper naphthenate, manganese naphthenate, calcium naphthenate, cobalt stearate, copper stearate, cobalt octoate, N, N-dimethylaniline, N, N. -Diethylaniline, N, N-dimethylparatoluidine, pyridine, phenylmorpholine, diphenyl disulfide, paratoluenesulfonic acid, sodium dodecylsulfonic acid and the like. These accelerators include use alone or in combination.

  Specific examples of the co-promoter include acetylacetone, dimedone, dibenzoylmethane, acetylcyclopentane, acetoacetate, acetylbutyrolactone, dimethylacetoacetamide, and acetoacetylpyrrolidine.

  Although there is no restriction | limiting in particular about the usage-amount of the radical initiator in this invention (III), Preferably a hardening | curing agent is 0.1 mass part-5 mass parts or less with respect to 100 mass parts of resin compositions, More preferably, it is 0.8. 5 parts by mass or less and 2 parts by mass or less. If it is 0.1 parts by mass or less, the curing is extremely slow and the working efficiency is deteriorated. If the amount is more than 5 parts by mass, it is not preferable because the cost is not only such, but the physical properties of the cured product are known to deteriorate. However, the concentration is not limited to these.

(Invention (IV))
The present invention (IV) will be described. In the present invention (IV), an oligo (meth) acrylate-containing composition is cured by the curing method of the present invention (III). Generally, a cured product of a resin containing a large amount of hydroxyl groups and carboxyl groups is known to have low water resistance, and since the obtained cured product has few hydroxyl groups and carboxyl groups, it has better water resistance. It is thought that shows. In addition, the oligo (meth) acrylate-containing composition of the present invention (II) and the cured product of the present invention (IV) have no off-flavors such as styrene, are odorless or slightly odorous, and are considered to improve the working environment. It is done.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, these Examples show the outline | summary of this invention and this invention is not limited at all by these Examples.

Example 1
(1) Production of oligomethacrylate (OMA-1)
First step In a 1-liter separable flask equipped with a stirrer, a fractionation condenser, a thermometer, and a gas introduction tube, 625 g of 2-hydroxylethyl methacrylate (Mitsubishi Gas Chemical Co., Ltd .: containing 45 ppm of methoxyphenol), phthalic anhydride 296 g (manufactured by Wako Pure Chemical Industries, Ltd.), 0.74 g of hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.), 0.065 g of p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.), and triphenylantimony (Tokyo Chemical Industry) 0.92 g (manufactured by Co., Ltd.) was charged and the temperature was raised to 170 ° C. over about 1 hour while blowing air, and then the reaction solution was maintained at 170 ° C. to 175 ° C. for 1 hour. Thereafter, the inside of the reactor was gradually depressurized by drawing with a vacuum pump from the distillation condenser side while blowing air. Finally, the pressure in the system was reduced to 20 kPaA. The reaction temperature under reduced pressure was adjusted to 165 to 170 ° C. and reacted for 1 hour, and then cooling was started immediately. During the period from the start of temperature rise to the end of cooling, no solid matter or gel-like substance considered to be a high molecular weight component was produced. The final distillate amount after cooling to 25 ° C. was 23 g, and the reaction solution amount was 900 g.

Second step Tolylene diisocyanate (a mixture of about 80% by mass of 2,4-tolylene diisocyanate and 20% by mass of 2,6-tolylene diisocyanate, manufactured by Wako Pure Chemical Industries, Ltd.) was obtained in the reaction mixture obtained in the first step. 90 g was added dropwise over 5 minutes. The temperature of the reaction solution rose to 70 ° C. At the same time as the temperature of the reaction solution started to drop, the reaction solution was heated to 80 ° C., reacted at 80 ° C. for 1 hour, and then immediately cooled. 30 parts by mass of phenoxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester PO) was added to 70 parts by mass of the resulting oligomethacrylate-containing composition to obtain oligomethacrylate (OMA-1).

(2) Evaluation of oligo (meth) acrylate The acid value, hydroxyl value, and room temperature curability were measured based on JIS K 6901 (1999).
The above-mentioned “acid value” indicates “total acid value”, and its measuring method is Method B (total acid value), which is an indicator method.
The viscosity was measured by a method according to JIS-6901. Specifically, the following method was used.
(Viscosity measurement of Example 1)
Viscosity is a TV-20 type viscometer cone plate type (manufactured by Toki Sangyo Co., Ltd., model name TVE-20H), measuring temperature 25 ° C., rotor name “1 ° 34 ′ × R 24”, measuring range “U”, The rotation was performed at 50 rpm (measured value upper limit 1024 mPa · s).
(Measurement of viscosity in Comparative Example 2)
Viscosity is a TV-20 type viscometer cone plate type (manufactured by Toki Sangyo Co., Ltd., model name TVE-20H), measuring temperature 25 ° C., rotor name “1 ° 34 ′ × R 24”, measuring range “R”, The rotation was performed at 50 rpm (measured value upper limit 256 mPa · s).
(Measurement of viscosity in Comparative Example 3)
The viscosity is a TV-20 viscometer cone plate type (manufactured by Toki Sangyo Co., Ltd., model name TVE-20H), measuring temperature 25 ° C., rotor name “1 ° 34 ′ × R 24”, measuring range “H”, The rotation was performed at 50 rpm (measured value upper limit 128 mPa · s).
The gelation time was determined by a method based on JIS K-6901 “5.9 Room Temperature Curing Properties”.
The water resistance was evaluated by the following method.
Add 100 parts by mass of the oligo (meth) acrylate-containing composition with 0.5 parts by mass of dimethylacetoacetamide, 0.05 parts by mass of pt-butylcatechol (manufactured by Kishida Chemical Co., Ltd.), and 0.5 parts by mass of cobalt naphthenate. And adjusted to 25 ° C. with sufficient stirring. Furthermore, after adding 1.0 part by mass of methyl ethyl ketone peroxide and stirring sufficiently, when poured into a 3 mm × 200 mm × 200 mm mold, heat generation started after about 20 minutes and hardening occurred after 60 minutes. After 12 hours, it was heated in an oven at 120 ° C. for 2 hours. The plate cooled to near room temperature and removed from the mold was cut into 30 mm × 30 mm × 3 mm to obtain 12 test pieces.
Subsequently, 100 ml of pure water and three test pieces were put in a 200 ml autoclave and sealed, and left in an oven controlled at 90 ° C. for 8 hours. The autoclave was removed from the oven and immediately cooled with water. When it was cooled to 30 ° C. or lower, the test piece was taken out and examined for appearance.
Similarly to the case of 90 ° C., three test pieces were used, and the test was performed while controlling the oven temperature to 100 ° C., 110 ° C., and 120 ° C., respectively.
Appearance inspection is ○ when no change is observed in any of the test pieces, △ when there are one or more test pieces with bubbles or cloudiness, and when there are one or more test pieces with cracks Was marked with x.

  The room temperature curability was determined by adding 100 parts by mass of the resulting oligo (meth) acrylate-containing composition to 0.5 parts by mass of cobalt naphthenate (manufactured by Wako Pure Chemical Industries, Ltd., cobalt content of about 6% by mass), dimethylacetoacetamide ( 0.5 parts by mass of Wako Pure Chemical Industries, Ltd.) and 1 part by mass of methyl ethyl ketone peroxide (Nippon Yushi Co., Ltd., trade name “Permec N”) were added, and the room temperature curing characteristics were examined.

  The isocyanate group content was measured based on JIS K 7301 (1995). The isocyanate group content was 1% by mass or less.

(3) A simple method for quantifying high molecular weight components by gel permeation chromatography (GPC).
A solution obtained by diluting the reaction solution 500 times by mass with chloroform was used as a measurement sample, and the high molecular weight component was measured by GPC. The high molecular weight component in this specification refers to a peak of 3000 or more in terms of polystyrene, and the quantification thereof was performed by a simple area percentage method (the ratio of the target peak to the area of all detected peaks).

Column KG, K-801, K-802 (Showa Denko KK)
Thermostatic chamber Shodex OVEN AO-50 (Constant oven temperature: 40 ° C)
Liquid feed pump Shodex DS-4 (flow rate: 1 ml / min)
UV detector Shodex UV-41 (measurement wavelength: 254 nm)
Eluent Chloroform (Kanto Chemical Co., Ltd., special grade)
The high molecular weight component of 3000 or more in GPC analysis was 1% or less.

Comparative Example 1
(1) Production of oligo (meth) acrylate (OMA-2)
Reaction was performed in the same manner as in the first step of Example 1 to obtain 900 g of OMA-2.
(2) Evaluation of oligo (meth) acrylate The acid value, hydroxyl value, and room temperature curability were measured in the same manner as in Example 1.
(3) A simple method for quantitative determination of high molecular weight components by gel permeation chromatography (GPC).

  When the high molecular weight component was quantified in the same manner as in Example 1, the high molecular weight component of 3000 or more by GPC analysis was 1% or less.

Comparative Example 2 Production of oligo (meth) acrylate (OMA-3)
Oligomethacrylate (OMA-3) was obtained in the same manner as Comparative Example 1 except that 30 parts by mass of phenoxyethyl methacrylate was added to 70 parts by mass of OMA-2 of Comparative Example 1.

(2) Evaluation of oligo (meth) acrylate The acid value, hydroxyl value, and room temperature curability were measured in the same manner as in Example 1.
(3) A simple method for quantitative determination of high molecular weight components by gel permeation chromatography (GPC).

  When the high molecular weight component was quantified in the same manner as in Example 1, the high molecular weight component of 3000 or more by GPC analysis was 1% or less.

  The results obtained from the above examples and comparative examples are summarized in Table 1.

Claims (23)

The manufacturing method of the oligo (meth) acrylate containing composition characterized by including the following 1st processes and 2nd processes.
(First step)
A step of reacting a mixture containing the following (A), (B) and (C) to obtain a polyester (meth) acrylate-containing composition (A) From a polybasic acid anhydride, a polybasic acid and a polybasic acid ester (B) at least one selected from compounds having one or more (meth) acryloyl groups in the molecule (C) at least one selected from esterification catalysts and / or transesterification catalysts Above (second process)
The step of adding the following (D) to the reaction mixture obtained in the first step and reacting it to obtain an oligo (meth) acrylate-containing composition (D) From a compound having one or more isocyanate groups in the molecule At least one or more selected   The method for producing an oligo (meth) acrylate-containing composition according to claim 1, wherein the first step is carried out in the range of 140 ° C to 210 ° C.   The oligo (meth) according to claim 1 or 2, wherein, in the first step, a mixture containing (E) an alkylene monoepoxide is reacted in addition to (A), (B) and (C). A method for producing an acrylate-containing composition.   The reaction is carried out using a mixture containing (F) a polyhydric alcohol in addition to (A), (B) and (C) in the first step. Of producing an oligo (meth) acrylate-containing composition.   The polybasic acid anhydride of (A) is malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride and 1,2-cyclohexanedicarboxylic acid anhydride The method for producing an oligo (meth) acrylate-containing composition according to any one of claims 1 to 4, wherein the composition is at least one selected from the group consisting of products.   (A) is a reaction mixture containing a polybasic acid ester and / or a polybasic acid ester obtained by reacting a polybasic acid with an alkylene monoepoxide and / or a purified product of the polybasic acid ester. The manufacturing method of the oligo (meth) acrylate containing composition in any one of Claims 1-4.   (A) is a reaction mixture containing a polybasic acid anhydride and / or a polybasic acid ester obtained by reacting a polybasic acid with a monoalcohol and / or a purified product of the polybasic acid ester. The manufacturing method of the oligo (meth) acrylate containing composition in any one of Claims 1-4.   (A) is a reaction mixture containing a polybasic acid anhydride and / or a polybasic acid ester obtained by reacting a polybasic acid with a polyhydric alcohol and / or a purified product of the polybasic acid ester, The manufacturing method of the oligo (meth) acrylate containing composition in any one of Claims 1-4 which do.   (A) a reaction mixture comprising a polybasic acid anhydride and / or a polybasic acid ester obtained by reacting a polybasic acid with a monoalcohol, and a polybasic acid ester obtained by reacting a polyhydric alcohol and / or The method for producing an oligo (meth) acrylate-containing composition according to any one of claims 1 to 4, which is a purified product of the polybasic acid ester.   (B) is (meth) acrylic acid, The manufacturing method of the oligo (meth) acrylate containing composition in any one of Claims 1-9 characterized by the above-mentioned.   (B) is a reaction mixture containing (meth) acrylic acid ester obtained by reacting (meth) acrylic acid and alkylene monoepoxide and / or a purified product of the (meth) acrylic acid ester. The manufacturing method of the oligo (meth) acrylate containing composition in any one of Claims 1-9.   The (B) is a reaction mixture containing (meth) acrylic acid ester obtained by reacting (meth) acrylic acid and monoalcohol and / or a purified product of the (meth) acrylic acid ester. The manufacturing method of the oligo (meth) acrylate containing composition in any one of Claims 1-9.   (B) a reaction mixture containing (meth) acrylic acid and / or an ester compound obtained by reacting (meth) acrylic acid and a monoalcohol, and a (meth) acrylic acid ester obtained by reacting a polyhydric alcohol; The method for producing an oligo (meth) acrylate-containing composition according to any one of claims 1 to 9, wherein the method is a purified product of the (meth) acrylic acid ester.   (C) The esterification catalyst and / or transesterification catalyst is titanium, antimony, cobalt, zinc, lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, strontium, barium, radium, zirconium, hafnium, manganese, germanium The oligo (meth) acrylate according to any one of claims 1 to 13, which is at least one organic and / or inorganic compound containing one or more elements selected from the group consisting of aluminum and aluminum. The manufacturing method of a containing composition.   (C) The esterification catalyst and / or transesterification catalyst is titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, antimony trioxide, triphenylantimony, antimony tartrate, antimony acetate , Cobalt acetate, cobalt acetate tetrahydrate, cobalt naphthenate, cobalt oxide, cobalt carbonate, acetylacetonatocobalt, cobalt stearate, zirconium acetate, zirconium acetate hydrate, acetylacetonatozirconium, zirconium tetrapropoxide , Zirconium tetrabutoxide, zirconium oxide, zirconium hydroxide, zinc acetate, zinc acetate dihydrate, acetylacetonato zinc, lithium acetate, lithium acetate tetrahydrate, lithium hydroxide, Lithium acetylacetonate, sodium acetate, sodium acetate trihydrate, sodium hydroxide, sodium acetylacetonate, potassium acetate, potassium hydroxide, potassium acetylacetonate, rubidium acetate, rubidium hydroxide, cesium acetate, cesium hydroxide The method for producing an oligo (meth) acrylate-containing composition according to claim 1, wherein the composition is at least one selected from the group consisting of francium acetate and magnesium acetate.   (D) is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, difinylmethane-4,4′-diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate , Transcyclohexane 1,4-diisocyanate, xylylene diisocyanate, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethyle The oligo (meth) acrylate-containing composition according to any one of claims 1 to 15, wherein the composition is at least one selected from the group consisting of triisocyanate, bicycloheptane triisocyanate and trimethylhexamethylene diisocyanate. Manufacturing method.   (E) is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, styrene oxide and glycidyl (meth) acrylate. It exists, The manufacturing method of the oligo (meth) acrylate containing composition in any one of Claim 3 or Claims 5-16.   (F) is ethylene glycol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol. Neopentyl glycol, 1,6-hexanediol, 1,9-nonanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, o-xylene glycol, m- Xylene glycol, p-xylene glycol, 1,2-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, bisphenol A, Hydrogenated bis Enol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F, hydrogenated bisphenol F, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, pentaerythritol, dipentaerythritol, trimethylolpropane and The method for producing an oligo (meth) acrylate-containing composition according to any one of claims 4 to 17, wherein the composition is at least one selected from the group consisting of ditrimethylolpropane.   The method for producing an oligo (meth) acrylate-containing composition according to any one of claims 1 to 18, wherein a reaction is carried out in the presence of a polymerization inhibitor.   The method for producing an oligo (meth) acrylate-containing composition according to any one of claims 1 to 19, wherein the reaction is carried out in the presence of oxygen.   21. An oligo (meth) acrylate-containing composition obtained by the production method according to claim 1.   A method for curing an oligo (meth) acrylate-containing composition, comprising adding a radical initiator to the oligo (meth) acrylate-containing composition according to claim 21 and curing the composition.   A cured product, which is cured by the curing method according to claim 22.