JP6410316B2 - Polyester resin, composition using the same, and use thereof - Google Patents

Description

  In the present invention, a polyfunctional acid anhydride (A) obtained by introducing an acid anhydride group having a specific structure into a polyhydric alcohol compound is further reacted with a compound (B) having one or more hydroxyl groups in the molecule. It is related with the polyester resin (C) obtained by making it allow, its composition, and a use.

  The polyester resin is a resin derived from a polyfunctional carboxylic acid compound and a hydroxyl group-containing compound, and is a material used in a wide range of applications, also called an alkyd resin. Generally, it is widely used for applications such as paints, printing inks, and adhesives (Patent Document 1). However, these existing polyester compounds have a problem of relatively low heat resistance.

  On the other hand, there are some efforts regarding polyfunctional acid anhydrides as acid anhydride materials with high heat resistance (Patent Document 2 and Patent Document 3). However, there is no description about the point which makes the polyester resin by the condensation reaction with a hydroxyl-containing compound starting from the polyfunctional acid anhydride described here.

JP 2006-206860 A JP 2009-242793 A JP 2012-025670 A

  An object of the present invention is to obtain a polyester resin and an alkyd resin having high heat resistance.

  The polyester resin (C) obtained by reacting the compound (B) having one or more hydroxyl groups in the molecule with the polyfunctional acid anhydride (A) having a specific structure has excellent heat resistance. Found to have.

That is, the present invention relates to (1) a polyhydric alcohol (a) having three or more hydroxyl groups in one molecule and a nuclear hydrogenated trimellitic anhydride halide (b-1) or a nuclear hydrogenated trimellitic anhydride halide (b -1) and a polyfunctional acid anhydride (A) obtained by reacting a mixture of trimellitic anhydride (b-2) with a compound (B) having one or more hydroxyl groups in one molecule. The polyester resin (C) obtained in this way.
(2) The polyhydric alcohol (a) is represented by the following general formula (1)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ独立して、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は水素原子、水酸基、炭素数１〜１１の炭化水素基、もしくは炭素数１〜４のヒドロキシアルキル基を表し、Ｒ^２は水酸基、もしくは炭素数１〜４のヒドロキシアルキル基を表す。ｌは０〜１１、ｍとｎはそれぞれ１〜１１の整数を表す。）
で表される一分子中に３つ以上の水酸基を含有する多価アルコール（ａ−１）である前記ポリエステル樹脂（Ｃ）に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1; Represents an integer of ˜11.)
It is related with the said polyester resin (C) which is a polyhydric alcohol (a-1) which contains three or more hydroxyl groups in 1 molecule represented by these.

(3) The polyhydric alcohol (a-2) obtained by reacting the polyhydric alcohol (a) with one or more selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester to the polyhydric alcohol (a). It relates to a certain polyester resin (C).
(4) The polyester resin (C), wherein the polyhydric alcohol (a) is tris (2-hydroxyethyl) isocyanurate.
(5) Polyfunctional acid anhydride (A), compound (B) having one or more hydroxyl groups in one molecule, soybean oil, linseed oil, castor oil, coconut oil, coconut oil, etc. The present invention relates to a modified alkyd resin (C ′) obtained by reacting a resin, rosin resin, urethane resin or the like.
(6) The present invention relates to a resin composition containing the polyester resin (C) or the modified alkyd resin (C ′).
(7) It is related with the said resin composition which is a film forming material.

  The polyester resin (C) or modified alkyd resin (C ′) of the present invention can provide a resin composition that can be a tough and highly heat-resistant film. The resin composition of the present invention exhibits particularly excellent properties such as adhesion to an inorganic material such as a metal material and a glass material and corrosion resistance. The resin composition of the present invention is suitable for applications such as paints, printing inks and adhesives.

  The polyester resin (C) of the present invention is prepared by adding a nuclear hydrogenated trimellitic anhydride halide (b-1) or a nuclear hydrogenated trimellitic anhydride to a polyhydric alcohol (a) having three or more hydroxyl groups in one molecule. Polyfunctional acid anhydride (A) obtained by reacting a mixture of halide (b-1) and trimellitic anhydride halide (b-2), and compound (B) having one or more hydroxyl groups in one molecule It is obtained by reacting.

  The polyhydric alcohol (a) having three or more hydroxyl groups in one molecule used in the present invention is a portion forming the central skeleton of the polyfunctional acid anhydride (A). When the number of hydroxyl groups is 2 or less in one molecule, a strong resin layer cannot be finally formed.

  The polyhydric alcohol (a) has a structure represented by the following general formula (1), triols such as tris (2-hydroxyethyl) isocyanurate, cyclohexanetriol, cyclohexanetrimethanol, and sugars such as inositol. Derived polyols and the like are preferred.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ独立して、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は水素原子、水酸基、炭素数１〜１１の炭化水素基、もしくは炭素数１〜４のヒドロキシアルキル基を表し、Ｒ^２は水酸基、もしくは炭素数１〜４のヒドロキシアルキル基を表す。ｌは０〜１１、ｍとｎはそれぞれ１〜１１の整数を表す。） The following general formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1; Represents an integer of ˜11.)

In the above general formula (1), when l or m is 2 or more, a plurality of R ¹ , R ³ , R ⁴ , and R ⁶ are the same as R ¹ , R ³ , R ⁴ , and R ⁶ , respectively. Different substituents may be taken. For example, when 1 = 4, four R ^{1 s} may be the same or different from each other. R ³ , R ⁴ and R ⁶ are the same as R ¹ .

  Specific examples of the polyhydric alcohol (a) include triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxyalkylmethyl 1,4-butanediol, and tris (2-hydroxyethyl) isocyanurate. , Tetraols such as ditrimethylolpropane and pentaerythritol, and polyols such as dipentaerythritol and polyglycerin.

  Among these, when a polyhydric alcohol having 4 to 6 hydroxyl groups in the molecule represented by the general formula (1) is used, the obtained resin characteristics are excellent. In particular, pentaerythritol, ditrimethylolpropane, and dipentaerythritol are preferable from the viewpoint of good resin characteristics and easy availability of materials.

  In the present invention, the polyhydric alcohol (a-2) has a structure in which any one or more selected from the group consisting of alkylene oxides, cyclic ethers, and cyclic esters are added to the polyhydric alcohol (a). Refers to a compound. Moreover, polyhydric alcohol (a-2) can also optimize a resin characteristic according to a use.

In general formula (1), the hydrocarbon group represented by R ¹ refers to an atomic group composed of only carbon atoms and hydrogen atoms.

  As for carbon number of a hydrocarbon group, 1-11 are preferable. Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, linear or branched pentyl group, linear or branched Aliphatic hydrocarbon groups such as hexyl group, straight chain or branched heptyl group, straight chain or branched octyl group, alicyclic hydrocarbon groups such as cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, Examples thereof include aromatic groups such as phenyl group, tolyl group, naphthyl group, and methylnaphthyl group, and aromatic substituted alkyl groups such as benzyl group and naphthylmethyl group. Among these, in the present invention, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group is preferable in terms of good transparency of the resin of the present invention, and the present invention in which the methyl group and the ethyl group have good toughness and heat resistance. It is more preferable from the point of giving this resin.

The hydroxyalkyl group represented by R ¹ or R ² refers to an atomic group in which one or more hydrogen atoms of a linear or branched alkyl group are substituted with a hydroxyl group.

  As for carbon number of a hydroxyalkyl group, 1-4 are preferable. Specific examples include those in which one or more hydrogen atoms of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group are substituted with a hydroxyl group. Of these, in the present invention, one in which one hydroxyl group is substituted on the terminal carbon is preferable in terms of easy reaction. Hydroxymethyl group and hydroxyethyl group are more preferable from the viewpoint of good toughness and heat resistance of the resin of the present invention.

  The alkylene oxide used in the present invention refers to a compound having a three-membered cyclic ether.

  As for carbon number of alkylene oxide, 2-8 are preferable. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. These alkylene oxides may be one kind or a mixture of two or more kinds as required. Among these, at least one selected from ethylene oxide and propylene oxide is preferable in the present invention because it is easily available and inexpensive.

  The amount of alkylene oxide used is usually 0.1 to 6.0 equivalents of a 3-membered cyclic ether, preferably 0.2 to 2.0 equivalents, per equivalent of hydroxyl group of the polyhydric alcohol (a). . If it is this range, the heat resistance and toughness of the resin material obtained will be favorable.

  The cyclic ether used in the present invention is not particularly limited as long as it is a compound having a structure in which one or more carbons of a cyclic hydrocarbon having 4 or more members are substituted with oxygen.

  The cyclic ether is preferably a 4- to 6-membered ring, and specific examples include oxetane, tetrahydrofuran, and tetrahydropyran. These cyclic ethers may be one kind or a mixture of two or more kinds as necessary. Of these, tetrahydrofuran is preferred in the present invention because it is readily available and inexpensive.

  The usage-amount of cyclic ether is 0.1-6.0 equivalent of cyclic ether with respect to 1 equivalent of hydroxyl groups of a polyhydric alcohol (a), Preferably, it is 0.2-2.0 equivalent. Within this range, the resulting resin has good heat resistance and toughness.

  The cyclic ester used in the present invention is not particularly limited as long as it is a compound having a structure containing an ester bond in a cyclic hydrocarbon.

  It is preferable that carbon number of cyclic ester is 2-6. Specific examples of the cyclic ester include acetolactone, propiolactone, butyrolactone, valerolactone, caprolactone and the like. These cyclic esters may be one kind or a mixture of two or more kinds as required. Of these, caprolactone is preferred in the present invention because it is readily available and inexpensive.

  The usage-amount of cyclic ester is 0.1-6.0 equivalent of cyclic ester with respect to 1 equivalent of hydroxyl groups of a polyhydric alcohol (a), Preferably, it is 0.2-2.0 equivalent. If it is this range, the heat resistance and toughness of the resin material obtained will be favorable.

  Specific examples of the polyhydric alcohol (a-2) include trimethylolpropane ethylene oxide adduct, trimethylolpropane propylene oxide adduct, trimethylolpropane tetrahydrofuran adduct, trimethylolpropane caprolactone adduct, pentaerythritol ethylene. Oxide adduct, pentaerythritol propylene oxide adduct, pentaerythritol tetrahydrofuran adduct, pentaerythritol caprolactone adduct, dipentaerythritol ethylene oxide adduct, dipentaerythritol propylene oxide adduct, dipentaerythritol tetrahydrofuran adduct, dipentaerythritol caprolactone Adduct, tris (2-hydroxyethyl) isocyanurate ethylene oxide Id adduct, tris (2-hydroxyethyl) isocyanurate propylene oxide adduct, tris (2-hydroxyethyl) isocyanurate tetrahydrofuran oxide adduct, tris (2-hydroxyethyl) isocyanurate caprolactone oxide adduct, etc. .

  The anhydrous nuclear hydrogenated trimellitic acid halide (b-1) used in the present invention is used to introduce an acid anhydride group into a polyhydric alcohol to obtain a polyfunctional acid anhydride compound. Thereby, an acid anhydride group can be introduced without ring-opening esterification of the acid anhydride group. Since (b-1) is nuclear hydrogenated, there is little coloring even under heat and light resistance, and the resin is excellent in heat resistance and toughness while maintaining high optical properties. Therefore, (b-1) can be suitably used as a color resist material, an optical waveguide material, and the like that are required to have high transparency as a resin.

  The trimellitic anhydride halide (b-2) used in the present invention is also used for the same purpose as (b-1). By using this together, higher heat resistance can be exhibited.

  Examples of the halide (b-1) or (b-2) include a fluorinated product, a chlorinated product, a brominated product, and an iodinated product, and among them, a chlorinated product is preferable because of easy reaction.

  The synthesis of the polyfunctional acid anhydride (A) can be performed by a known method. There is no particular limitation on the method of adding the reagent in the reaction between the polyhydric alcohol (a) and the halide (b-1) or (b-2) (hereinafter “halides”), and any addition method can be adopted. For example, a method in which a polyhydric alcohol (a) and a basic substance are dissolved in a solvent, and the above-mentioned halides dissolved in the solvent are slowly added dropwise thereto, or conversely, the above-mentioned halide dissolved in a solvent if necessary A method of dropping a mixed solution of a polyhydric alcohol (a) and a basic substance into a mixture, a method of dropping a basic substance into a mixed solution of a halide and a polyhydric alcohol (a), and a polyhydric alcohol For example, a solution of the nuclear hydrogenated trimellitic anhydride halide and a solution of a basic substance may be simultaneously dropped into the solution of (a).

  In the reaction of the polyhydric alcohol (a) and halides in the presence of a basic substance, a hydrochloride formed by neutralization of the basic substance is generated as the reaction proceeds. By concentrating the back solution that has been removed by filtration, a crude product of the desired polyfunctional acid anhydride can be obtained in high yield. This is dissolved in a suitable solvent, washed with water, concentrated and dried under reduced pressure to obtain a polyfunctional acid anhydride having a high purity. Furthermore, a polyfunctional acid anhydride with higher purity can be obtained by performing recrystallization with an appropriate solvent as necessary.

  The use amount of the polyhydric alcohol (a) is usually a hydroxyl group equivalent, and is 0.6 to 1.0, preferably 0.8 to 1.0 with respect to the halides 1. If it is this range, all the hydroxyl groups of polyhydric alcohol (a) are esterified, and an unreacted halide does not remain in the system.

  The solvent that can be used in the reaction between the halide and the polyhydric alcohol (a) is not particularly limited as long as it is inert to the raw material, but tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane-bis (2- Ether solvents such as methoxyethyl) ether, aromatic amine solvents such as picoline and pyridine, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, dichloromethane and chloroform Halogen-containing solvents such as 1,2-dichloroethane, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, Phosphorus-containing solvents such as hexamethylphosphoramide, dimethylsulfur Sulfur-containing solvents such as oxide, ester solvents such as γ-butyrolactone, ethyl acetate, butyl acetate, nitrogen-containing solvents such as 1,3-dimethyl-2-imidazolidinone, phenol, o-cresol , M-cresol, p-cresol, o-chlorophenol, m-chlorophenol, aromatic solvents having a hydroxyl group such as p-chlorophenol, and the like. These solvents may be used alone or in combination of two or more.

  The solvents mentioned here include cyclic ethers and cyclic esters used in the production of polyhydric alcohol (a-2) from polyhydric alcohol (a). Halides are added to polyhydric alcohol (a). When making it react, reaction temperature is -10 degreeC-80 degreeC, Preferably it is 0 degreeC-70 degreeC, More preferably, it is 10 degreeC-60 degreeC. When the reaction temperature is higher than 80 ° C., the polyhydric alcohol (a) reacts with the cyclic ether or cyclic ester to obtain the polyhydric alcohol (a-2), and the reaction rate between the polyhydric alcohol (a) and halides. Decreases. The reaction time is not particularly limited, but is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction is usually carried out at normal pressure, but can be carried out under pressure or under reduced pressure as necessary.

  When the polyhydric alcohol (a) is reacted with a cyclic ether or cyclic ester to produce the polyhydric alcohol (a-2), the reaction temperature is 80 ° C to 250 ° C, preferably 90 ° C to 220 ° C, more preferably. 100 to 200 ° C. The reaction time is not particularly limited, but is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction is usually carried out at normal pressure, but can be carried out under pressure or under reduced pressure as necessary.

  The concentration of the solute in the reaction for obtaining the polyfunctional acid anhydride (A) is usually 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass in consideration of side reaction control and precipitation filtration step. . More preferably, it is carried out in the range of 10 mass% or more and 40 mass% or less.

  The reaction atmosphere is usually carried out under nitrogen. The reaction vessel may be a closed type reaction vessel or an open type reaction vessel, but in order to keep the reaction system in an inert atmosphere, an open type vessel that can be sealed with an inert gas is used.

  The basic substance is used to neutralize hydrogen chloride generated as the reaction proceeds. The type of basic substance used at this time is not particularly limited, but organic basic amines such as pyridine, triethylamine and N, N-dimethylaniline, and inorganic basic substances such as potassium carbonate and sodium hydroxide are used. be able to. Pyridine and triethylamine are preferable in that they can be obtained at low cost and are easy to operate because they are liquid and highly soluble. Moreover, an inorganic basic substance is preferable in that it can be obtained at low cost.

  The amount of the basic substance to be used is not particularly limited, but if it is used excessively, it will be mixed into the product and the purification load will increase, so it is usually 1.0% relative to the nuclear hydrogenated trimellitic anhydride halide. The mole times to 30 mole times, preferably 1.2 mole times to 20 mole times, more preferably 1.5 mole times to 10 mole times are employed.

  During the water washing operation, the polyfunctional acid anhydride (A) undergoes partial hydrolysis and changes to a polycarboxylic acid, which is produced by partial hydrolysis by heat treatment under reduced pressure. The polyvalent carboxylic acid thus obtained can be easily returned to the polyfunctional acid anhydride (A). The temperature employed in the heat treatment step under reduced pressure is 80 ° C. to 200 ° C., preferably 100 ° C. to 180 ° C., the degree of reduced pressure is 10 MPa or less, preferably 1 MPa or less, and is particularly limited to the upper limit of the heating time. However, it is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours.

  The polyfunctional acid anhydride (A) thus obtained can be further purified. As a purification method in that case, recrystallization, sublimation, washing, activated carbon treatment, column chromatography and the like can be arbitrarily performed. These purification methods can be repeated or combined. The purity of the polyfunctional acid anhydride (A) thus obtained is usually 90% or more, preferably 95% or more as an area ratio of peaks obtained by analysis such as gel permeation chromatography (hereinafter referred to as “GPC”). More preferably, it is 98% or more

  The compound (B) having one or more hydroxyl groups in one molecule used in the present invention is used for half-esterification of an acid anhydride group and a hydroxyl group by addition reaction, and further polyesterification by condensation reaction.

  Specifically, examples of the compound containing one hydroxyl group in one molecule include hydrocarbon monools such as methanol, ethanol, propanol, butanol, hexanol, octanol, decanol, stearyl alcohol, cyclohexanol and cyclohexanemethanol, and diethylene glycol. Mono, such as monoethyl ether and propylene glycol monomethyl ether, and polyalkylene glycol monoalkyl ethers.

  Examples of compounds containing two hydroxyl groups in one molecule include hydrocarbon diols such as ethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, octanediol, decanediol, cyclohexanediol, cyclohexanedimethanol, and diethylene glycol. , Polyalkylene glycols such as polyethylene glycol, tripropylene glycol, polypropylene glycol and polybutylene glycol.

  Examples of the compound containing three or more hydroxyl groups in one molecule include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxyalkylmethyl 1,4-butanediol, and tris (2-hydroxyethyl) isocyanate. Examples include triols such as nurate, tetraols such as ditrimethylolpropane and pentaerythritol, and polyols such as dipentaerythritol and polyglycerin.

  The number of hydroxyl groups possessed by the compound (B) is preferably 1 to 2 in one molecule. Thereby, an appropriate molecular weight can be imparted to the polyester resin. If only one molecule per molecule is used, the molecular weight does not increase, and if there are three or more molecules, gelation may occur. The molecular weight is controlled by, for example, mixing one molecule containing one hydroxyl group and one containing two hydroxyl groups.

  In addition, diol monovinyl ethers such as ethylene glycol monovinyl ether, propylene glycol monovinyl ether, and butylene glycol monovinyl ether can also be used.

  A known method can be applied to the reaction of the polyfunctional acid anhydride (A) and the compound (B) having one or more hydroxyl groups in one molecule.

  In this case, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is a reaction in which a reactant, that is, a polyfunctional acid anhydride (A), a compound (B), and a solvent or the like is added in some cases. It is 0.1-10 mass% with respect to the total amount of a thing. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of catalysts that can be used include inorganic acids such as sulfuric acid, organic acids such as toluenesulfonic acid and methanesulfonic acid, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. , Organic bases such as triphenylphosphine, triphenylstibine, and methyltriphenylstibine, and metal salts such as chromium octoate and zirconium octoate.

  This acid addition reaction can be carried out without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for this reaction.

  More preferably, in order to perform the condensation reaction when performing the esterification reaction, it is preferable to proceed the reaction while removing the generated moisture from the reaction system. For this purpose, it is also preferable to select a solvent suitable for removal from the reaction system using an azeotropic phenomenon.

  A preferable amount of the solvent to be used should be appropriately adjusted depending on the viscosity and use of the resin to be obtained, and is preferably 90 to 30% by mass, more preferably 80 to 50% by mass as a solid content.

Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white Examples include gasoline and solvent naphtha.
Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Glycol ethers, and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  The polyester resin (C) of the present invention is obtained by reacting with the other component (D) in addition to (A) and (B) for the purpose of optimizing the properties of the polyester resin during the reaction. Is also included.

  Examples of the other component (D) include monofunctional saturated fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid, monofunctional unsaturated fatty acids such as linolenic acid, linoleic acid and oleic acid, succinic acid, maleic acid and hexa And other carboxylic acid compounds such as bifunctional carboxylic acids such as hydrophthalic acid, adipic acid, and sebacic acid.

  Furthermore, the polyester resin (C) of the present invention includes a polyfunctional acid anhydride (A), a compound (B) having one or more hydroxyl groups in one molecule, and soybean oil, linseed oil, castor oil as other components (D), Also included are modified alkyd resins (C ′) obtained by appropriately combining and condensing animal oils and vegetable oils such as coconut oil, coconut oil, tung oil, phenol resins, rosin resins, urethane resins and the like.

  Polyfunctional acid anhydride (A), compound (B) having one or more hydroxyl groups in one molecule, soybean oil, linseed oil, castor oil, coconut oil, coconut oil, etc., Tung oil and vegetable oils, phenolic resin, rosin resin A known method can be applied to the reaction of urethane resin or the like.

  A color pigment (E), extender pigment (F), curing agent (G), and other components are added to the polyester resin (C) or modified alkyd resin (C ′) of the present invention to obtain the resin composition of the present invention. You can also.

  The color pigment (E) used in the present invention is used to make the resin composition of the present invention a coloring material. These are classified into organic pigments and inorganic pigments depending on the constitution, and these are appropriately selected according to the intended color and application.

  Organic pigments are classified according to their basic skeleton. For example, isoindolinone type, isoindoline type, azomethine type, plan tra planon type, anthrone type, xanthene type, diketopyrrolopyrrole type, perylene type, perinone type, quinacridone type, indigoid type, dioxazine type, phthalocyanine type, etc. And polyazo pigments, azo pigments such as monoazo, disazo, and condensed disazo, lake pigments, and fluorescent pigments.

  Examples of inorganic pigments include titanium dioxide, calcium carbonate, barium sulfate, zinc oxide, mica, carbon black, bengara, and aluminum flakes.

  The extender pigment (F) shown in the present invention is a pigment not intended for coloring, and is used for the purpose of adjusting the viscosity and flowability of the composition and the mechanical properties of the resin.

  For example, barium sulfate, calcium carbonate, talc, clay, glass flakes, glass beads, graphite, aluminum oxide, aluminum hydroxide, polystyrene beads, polyethylene beads, polypropylene beads, polytetrafluoroethane beads and the like can be mentioned.

  Moreover, the hardening | curing agent (G) shown by this invention is used in order to raise the crosslinking degree of resin further. For example, a compound having a functional group capable of reacting with the polyester resin (C) of the present invention can be used. For example, polyfunctional isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trinurate, and bisphenol type epoxy resins , Polyfunctional epoxy resins such as cresol novolac type epoxy resin and phenol novolak type epoxy resin, polyfunctional phenol resins such as diallyl phthalate resin, phenol novolak resin and cresol novolac resin, polyfunctionality such as melamine, methylolated melamine, benzoguanamine, etc. Amines and the like can also be used.

  Furthermore, as other materials, for the purpose of adapting the resin composition of the present invention to various uses, other components can be added up to 70 mass% of the resin composition of the present invention. Examples of other components include other resins, various additives, and volatile solvents added for viscosity adjustment for the purpose of imparting coating suitability. Examples of other components that can be used are shown below.

  Examples of other resins include other polyester resins, epoxy resins, phenol resins, urethane resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, Polyolefin resins and modified products thereof can also be used. These are preferably used in a range of up to 40% by mass.

  Examples of other additives include thermosetting materials such as melamine, metal dryers such as cobalt naphthenate, thixotropic agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, hydroquinone, hydroquinone monomethyl ether, and the like. Polymerization inhibitors, stabilizers, antioxidants, and the like can be used.

  Depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent may be added in the range of 50% by mass, more preferably up to 35% by mass of the resin composition of the present invention.

  In the present invention, the film forming material is used for the purpose of coating the surface of the substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, metal and other various adhesives. This applies to adhesive materials such as adhesives and adhesives, and resist materials. Furthermore, after the film-forming material is temporarily applied to a peelable substrate and formed into a film, it is pasted on the originally intended substrate to form a film. To do.

  There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

Synthesis Example 1: Synthesis 1 of polyfunctional acid anhydride (A)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, while the amount of anhydride chloride (b) listed in the table was listed (1.1 equivalents relative to the hydroxyl group in (a)). 45 g of tetrahydrofuran was added to make a homogeneous solution. The solution was cooled to 5 ° C. with stirring, and (a) described in the table was added in the amount shown in the table, and pyridine (1.2 equivalents relative to the hydroxyl group of (a)) and 54 g of tetrahydrofuran were added to make the solution uniform. Was gradually added dropwise while maintaining the liquid temperature at 10 ° C. or lower. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, then heated to 50 ° C., and the reaction was continued for 8 hours. Subsequently, the reaction solution was cooled to 20 ° C., and pyridine hydrochloride as an insoluble component was removed by filtration, and then the filtrate was concentrated. The concentrate was dissolved in 120 ml of ethyl acetate, washed 3 times with 30 ml of water, and then dried over anhydrous magnesium sulfate. After anhydrous magnesium sulfate was removed by filtration, the filtrate was concentrated, and the resulting concentrate was dissolved in 15 ml of ethyl acetate and recrystallized from toluene to obtain a product.

Comparative Synthesis Example 1: Synthesis of Bifunctional Acid Anhydride A polyfunctional acid anhydride was synthesized according to Synthesis Example 1. The results are shown in the following table together with Synthesis Example 1.

Abbreviations in Table TMP: Trimethylolpropane PE: Pentaerythritol PE4EO: Pentaerythritol 4 mol ethylene oxide adduct BPA2EO: Bisphenol A 2 mol ethylene oxide adduct BG: 1,3-butylene glycol THI: Tris (2-hydroxyethyl) isocyanurate HTAC: Nuclear hydrogenated trimellitic anhydride chloride TMAC: Trimellitic anhydride chloride

Example 1 Preparation of Polyester Resin (C) 20 mmol of polyfunctional acid anhydride (A) prepared in Synthesis Example 1 in a flask equipped with a stirrer, a Dean-Stark type reflux condenser and a stirrer (mass is described in the table) ) Toluene was added in an amount to give a solid content of 60% by mass relative to the total amount of (A) and (B), and toluenesulfonic acid was added as a catalyst in an amount of 0.3% by mass of the total amount including the solvent, and dissolved by stirring. .
Furthermore, the compound shown in the table as a compound (B) having one or more hydroxyl groups in one molecule was added, and the reaction was carried out for 5 hours under reflux using a Dean-Stark tube while removing condensed water.

Comparative Example 1 Preparation of Bifunctional Carboxy Group-Containing Reactive Compound In the same manner as in Example 1, the reaction was carried out using 20 mmol (mass described in the table) of the other bifunctional acid anhydrides described in the table.

Abbreviations in Table MW: Weight average molecular weight in terms of polystyrene by gel permeation chromatograph (GPC) PGM: Propylene glycol monomethyl ether HDO: Hexanediol 2EH: 2-Ethylhexyl alcohol (octanol)
EG: Ethylene glycol

Example 2: Preparation of castor oil-modified polyester resin (C) (modified alkyd resin (C ')) Polyfunctional acid prepared in Synthesis Example 1 in a flask equipped with a stirrer, Dean-Stark type reflux condenser, and stirrer 13.5 g (20 mmol) of anhydride (A), (B), and (D) are listed in the table, toluene is used as a solvent, based on the total amount of (A) and (B), and other components (D) An amount of solid content of 60% by mass was added, and toluenesulfonic acid as a catalyst was added by 0.3% by mass of the total amount including the solvent, and dissolved by stirring.
Furthermore, the compound shown in the table as a compound (B) having one or more hydroxyl groups in one molecule was added, and the reaction was carried out for 5 hours under reflux using a Dean-Stark tube while removing condensed water.

Abbreviations in Table CBO: Diethylene glycol monoethyl ether (also known as carbitol)

Example 3: Preparation of white coating composition 6 g of the polyester resin (C) solution synthesized in Examples 1 and 2 and Comparative Example 1 in terms of solid content (actual charge amount divided by 60 mass% solid content) Acrylic resin, 2 g of Dainar BR-80 (manufactured by Mitsubishi Rayon) as the other resin, and 5 g of titanium oxide pigment Typek CR-90 (Ishihara Sangyo Co., Ltd.) as the coloring pigment (E) are kneaded using a three-roll mill. A white paint composition was obtained.

  The obtained coating composition was applied onto a TFS substrate (tin-free steel plate) with a wire bar coater # 8, and the solvent was evaporated in an oven at 120 ° C. for 10 minutes to obtain a coating film.

Evaluation of metal coating materials <Evaluation of resin properties>
After drying, the hardness of the coating film was evaluated according to a pencil hardness test (JIS-K5600-5-4: 1999).
<Adhesion evaluation>
The adhesion to the metal substrate was evaluated according to a cross-cut peel test (JIS-K5600-5-6: 1999).
Evaluation criteria were also based on JIS-K5600 and evaluated according to the following classification.
Category 0: No peeling, good Classification 1: Slight peeling at the corners Category 2: Peeling at the corners Category 3: Peeling less than half of the squares Category 4: Peeling more than half of the squares Category 5: There is almost complete peeling, poor <impact resistance evaluation>
The impact resistance of the coating film was evaluated according to the DuPont impact test (JIS-K5600-5-6: 1999). The weight was 500 g, the impact type was 6.35 mm, and the drop height was 250 mm.
○: No cracking △: Cracking but no peeling ×: Peeling <Light resistance>
The obtained coating film was irradiated with ultraviolet light for 8 hours with a super UV tester (Iwasaki Electric), and the colorability of the white coating film after the irradiation was visually evaluated. The evaluation criteria are as follows.
◎: No discoloration ○: Slightly discolored to yellowish △: Yellow discoloration is observed ×: Discolored to brown

  From the above results, the polyester resin (C) and the modified alkyd resin (C ′) of the present invention obtained from the polyhydric alcohol (a) having three or more hydroxyl groups in one molecule are less than three in one molecule. It was shown that the coating composition can be excellent in adhesion, impact resistance and light resistance as compared with a polyester resin obtained from an alcohol having a hydroxyl group.

  The polyester resin (C) and modified alkyd resin (C ′) of the present invention are suitable for coating materials and printing inks that have little discoloration and excellent adhesion.

Claims (8)

Polyhydric alcohol (a) having three or more hydroxyl groups in one molecule and nuclear hydrogenated trimellitic anhydride halide (b-1) or nuclear hydrogenated trimellitic anhydride halide (b-1) and trimellitic anhydride Polyester resin (C) obtained by reacting compound (B) having one or more hydroxyl groups in one molecule with polyfunctional acid anhydride (A) obtained by reacting a mixture of halide (b-2) . The polyhydric alcohol (a) is represented by the following general formula (1)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1; The polyester resin (C) according to claim 1, which is a polyhydric alcohol (a-1) containing three or more hydroxyl groups in one molecule represented by ˜11. The polyhydric alcohol (a) is a polyhydric alcohol (a-2) obtained by reacting the polyhydric alcohol (a) with one or more selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester. 1. The polyester resin (C) according to 1. The polyester resin (C) according to claim 1, wherein the polyhydric alcohol (a) is tris (2-hydroxyethyl) isocyanurate. The polyfunctional acid anhydride (A) according to claim 1, the compound (B) having one or more hydroxyl groups in one molecule, and soybean oil, linseed oil, castor oil, coconut oil, coconut oil, etc. , Modified alkyd resin (C ′) obtained by reacting phenol resin, rosin resin, urethane resin and the like. The resin composition containing the polyester resin (C) as described in any one of Claims 1 thru | or 4. A resin composition comprising the modified alkyd resin (C ′) according to claim 5. The resin composition according to claim 7, which is a film forming material.