KR102127775B1 - Multifunctional acid anhydride, thermosetting resin composition, prepreg and cured article - Google Patents

Abstract

(Task) It is to obtain a resin composition that provides a cured product excellent in transparency, heat resistance, toughness, and color resistance, and particularly those having properties suitable for optical parts.
(Solution) Obtained by reacting a mixture of polyhydric alcohol (A) containing at least three hydroxyl groups in one molecule with trimellitic anhydride and anhydrous trimellitic anhydride or nuclear hydrogenated trimellitic anhydride Polyfunctional acid anhydride, polyhydric alcohol (A), polyhydric alcohol (B) obtained by reacting at least one selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester, trimellitic anhydride, and nuclear hydrogenation anhydride It is a thermosetting resin composition containing a polyfunctional acid anhydride obtained by reacting a trimellitic acid halide with a compound having at least one epoxy group in one molecule with the polyfunctional acid anhydride.

Description

Multifunctional acid anhydride, thermosetting resin composition, prepreg and cured product {MULTIFUNCTIONAL ACID ANHYDRIDE, THERMOSETTING RESIN COMPOSITION, PREPREG AND CURED ARTICLE}

The present invention relates to a polyfunctional acid anhydride, a thermosetting resin composition containing the polyfunctional acid anhydride, and a cured product thereof. The cured product of the present invention has properties excellent in transparency, heat resistance, toughness, and color resistance.

The acid anhydride has excellent performance as a crosslinking agent, a condensing agent, etc., such as high thermal stability, transparency, good electrical properties, chemical resistance, etc., and has good condensation formation and reactivity, and is widely used as a raw material for polymer production. It is also known that acid anhydrides can also be used as curing agents for epoxy resins.

The curable resin composition containing an epoxy resin is a resin excellent in heat resistance, and is used in a wide range of fields. Recently, the use of the composition in the field related to optoelectronics has attracted attention. In particular, with the recent advance in information technology, in order to smoothly transmit and process vast amounts of information, it has been converted to signal transmission by conventional electrical wiring, and optical technologies, optical waveguides, blue LEDs, and optical light are being developed while technologies utilizing optical signals are being developed. In the field of optical components such as semiconductors, it is desired to develop a resin composition that provides a cured product excellent in transparency, toughness, and heat resistance.

As the acid anhydride in the curable resin composition containing an epoxy resin, aromatic acid anhydrides and alicyclic acid anhydrides are well known. Examples of the use of the aromatic acid anhydride include, for example, acid 3 anhydride in Patent Document 1. However, this compound is not easily sufficient in transparency and color resistance because it is easy to absorb aromatic-derived coloring and short-wavelength light. In addition, examples of the use of the alicyclic acid anhydride include, for example, methylcyclohexene dicarboxylic acid anhydride in Patent Document 2, tetracarboxylic acid anhydride having a tricyclo ring in Patent Document 3, and tetracarboxylic acid having an ester group in Patent Document 4 2 Anhydride is mentioned. Although these hardened|cured materials provide high transparency, the heat resistance is not enough similarly because a skeleton is flexible and bifunctional compared with an aromatic acid anhydride. Moreover, although the isocyanurate compound of patent document 5 is trifunctional, transparency of the hardened|cured material is not sufficient by coloring derived from isocyanurate.

Japanese Patent Publication No. Hei 3-059031 Japanese Patent Publication No. 55-36406 Japanese Patent Publication No. 2005-320383 Japanese Patent Publication No. 2007-284414 Japanese Patent Publication No. 2012-025670

An object of the present invention is to obtain a polyfunctional acid anhydride that provides a cured product excellent in toughness, heat resistance, transparency, and color resistance, and a thermosetting resin composition containing the polyfunctional acid anhydride.

The present inventors are a compound obtained by reacting a mixture of a polyhydric alcohol having three hydroxyl groups in at least one molecule with a nuclear hydrogenated trimellitic anhydride and a trimellitic anhydride halide, or a nuclear hydrogenated trimellitic anhydride halide. It has been found that a cured product having toughness, heat resistance, and color resistance is provided while maintaining high optical properties, leading to the present invention.

That is, the present invention, the following general formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, and R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are hydrogen atoms, hydroxyl groups, and 1 to 11 carbon atoms. Represents a hydrocarbon group 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 integers of 1 to 11, respectively. Obtained by reacting a mixture of a polyhydric alcohol (A) containing at least three hydroxyl groups with one nucleus anhydrous trimellitic anhydride and trimellitic anhydride, or a nuclear hydrogenated trimellitic anhydride It relates to polyfunctional acid anhydrides.

Further, the polyhydric alcohol (B) obtained by reacting the polyhydric alcohol (A) with at least one selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester, and trimellitic anhydride with nuclear hydrogenation and trimellitic anhydride The present invention relates to a polyfunctional acid anhydride obtained by reacting a mixture of halides or trimellitic anhydride added with nuclear hydrogen.

Further, 10% or more and 75% or less of the total number of hydroxyl groups of the polyhydric alcohol (A) or (B) is reacted with trimellitic anhydride, and the remaining hydroxyl group and trimellitic anhydride with nuclear hydrogen reaction are obtained. It relates to polyfunctional acid anhydrides.

In addition, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ of the general formula (1) are alkyl groups of the polyhydric alcohol (A) or the polyhydric alcohol (A) having 1 to 4 carbon atoms. A mixture of polyhydric alcohol (B) obtained by reacting at least one selected from the group consisting of renoxide, cyclic ether, and cyclic ester with trimellitic anhydride and nuclear trimellitic anhydride, or trimellitic anhydride with nuclear hydrogen It relates to a polyfunctional acid anhydride obtained by reacting with a triacid halide.

Moreover, it is related with the polyfunctional acid anhydride whose said polyhydric alcohol (A) or (B) is a 3-6 hexavalent alcohol.

Moreover, the said polyhydric alcohol (A) is related to the polyfunctional acid anhydride which is trimethylol or dipentaerythritol.

In addition, the polyhydric alcohol (B) is a dipentaerythritol ethylene oxide adduct, dipentaerythritol propylene oxide adduct, dipentaerythritol tetrahydrofuran adduct, dipentaerythritol caprolactone adduct, polyfunctional acid anhydride It is about.

In addition, the polyhydric alcohol (B) relates to a polyfunctional acid anhydride which is a pentaerythritol 4 mol ethylene oxide adduct, a dipentaerythritol 6 mol ethylene oxide adduct, and a dipentaerythritol 4 mol caprolactone adduct.

Moreover, it is related with the thermosetting resin composition containing the compound which has at least 1 epoxy group in 1 molecule, and the said polyfunctional acid anhydride.

Moreover, it is related with the thermosetting resin composition containing the said polyfunctional acid anhydride in which the compound which has at least 1 epoxy group in 1 molecule is 1 or more types chosen from aliphatic type epoxy resin, aromatic type epoxy resin, and copolymer type epoxy resin.

Further, the present invention relates to a thermosetting resin composition comprising the polyfunctional acid anhydride, wherein at least one compound having at least one epoxy group in the molecule is selected from aliphatic epoxy resins and aromatic epoxy resins.

Further, the present invention relates to a thermosetting resin composition containing the polyfunctional acid anhydride, wherein the aliphatic epoxy resin is an epoxy resin having an aliphatic cyclic structure.

Also, the aromatic epoxy resin is selected from (4-(4-(1,1-bis(p-hydroxyphenyl)-ethyl)-α,α-dimethylbenzyl)phenol) type epoxy resin and bisphenol A epoxy resin. It relates to the thermosetting resin composition containing the said polyfunctional acid anhydride which is 1 or more types.

Moreover, it is related with the thermosetting resin composition containing the said polyfunctional acid anhydride in which the compound which has at least 1 epoxy group in the said 1 molecule is a copolymerized epoxy resin.

In addition, a thermosetting resin composition comprising particles (C-1) or fibers (C-2) that are not compatible with the polyhydric alcohol (A), trimellitic anhydride, and trimellitic anhydride with nuclear hydrogenation It is about.

Moreover, it is related with the said thermosetting resin composition in which the said particle (C-1) is an inorganic particle.

Moreover, it is related with the said thermosetting resin composition in which the said fiber (C-2) is glass fiber.

Further, the fiber (C-2) relates to the thermosetting resin composition, which is a glass cross formed by spinning glass fibers and further woven.

Further, it relates to a prepreg in which the thermosetting resin composition is given a shape in a semi-cured state.

Moreover, it is related with the varnish which added a solvent to the said thermosetting resin composition.

Moreover, it is related with the hardened|cured material which hardened the said thermosetting resin composition.

Moreover, it is related with the said thermosetting resin hardened|cured material whose difference of the optical refractive index of a thermosetting resin after hardening and a particle (C-1) or a fiber (C-2) is 0.005 or less.

The polyfunctional acid anhydride of the present invention can be used as a curing agent for epoxy resins. The thermosetting resin composition of the present invention has good stability, and the cured product of the present invention is excellent in transparency, toughness, heat resistance, and color resistance, and paints and FRPs for civil engineering construction, paints and resists in the field of printed wiring boards and semiconductors, etc. It is suitable for electrical and electronic materials such as ink, adhesives, sealants, and encapsulants, and furthermore, LED encapsulants or optical waveguides requiring high transparency, liquid crystal displays, plasma displays, EL displays, display devices such as portable devices, and solar cells.

1 is a ¹ H-NMR spectrum chart of the polyfunctional acid anhydride obtained in Example 1-1.
2 is a ¹ H-NMR spectrum chart of the polyfunctional acid anhydride obtained in Example 1-6.

(Form for carrying out the invention)

The polyhydric alcohol (A) used in the present invention is a compound having the following structure and having three hydroxyl groups in at least one molecule.

The following general formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, and R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are hydrogen atoms, hydroxyl groups, and 1 to 11 carbon atoms. Represents a hydrocarbon group 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 represents 0 to 11, m and n represent integers of 1 to 11 ).

In the general formula (1), one, or, R ^1, R ^3, that is the plurality, if m is 2 or more R ^4, R ⁶ are, each R ^1, R ^3, R ^4, R ⁶ are different substituents You may take For example, in the case of 1=2, four R ^{1 s} may be four identical substituents, some of them may be the same, others may be different, or all different substituents. R ³ , R ⁴ and R ⁶ are the same as R ¹ .

Specific examples of the polyhydric alcohol (A) include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,4-butanetriol, 2-hydroxy-2-methyl-1,4-butanediol, 1, 2,5-pentanetriol, 1,3,5-pentanetriol, 3-methylpentane-1,3,5-triol, 1,2,6-hexanetriol, 1,2,8-octanetriol Triols such as all, 1,2,9-nonanetriol, 1,2,10-decanetriol, 1,1,2,2-ethane tetraol, ditrimethylolpropane, erythritol, pentaerythritol, 1,2,3,5-pentanetetraol, 1,2,4,5-pentanetetraol, 1,1,5,5-pentanetetraol, 1,2,5,6-hexanetetraol, 1, And tetraols such as 2,7,8-octanetetraol and 1,2,9,10-decanetetraol, and polyols such as dipentaerythritol and polyglycerin.

Among them, a polyhydric alcohol having 3 to 6 hydroxyl groups in one molecule is excellent as a curing agent. In particular, pentaerythritol, ditrimethylolpropane, and dipentaerythritol are preferable in view of good properties of the cured product cured using the above curing agent and ease of material availability.

In the present invention, polyhydric alcohol (B) refers to a compound obtained by addition polymerization of polyhydric alcohol (A) to any one or more selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester. In addition, the polyhydric alcohol (B) may be optimized for reactivity or properties of the cured product depending on the application.

Specific examples of the polyhydric alcohol (B) include trimethylolpropane ethylene oxide adduct, trimethylolpropane propylene oxide adduct, trimethylolpropane tetrahydrofuran adduct, trimethylolpropanecaprolactone 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 And adducts and dipentaerythritol caprolactone adducts.

The hydrocarbon group in R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ refers to an atomic group composed of only carbon atoms and hydrogen atoms.

The hydrocarbon group preferably has 1 to 11 carbon atoms. As a specific example, a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, linear or branched pentyl group, straight chain or branched hexyl group, straight chain or branched Aliphatic hydrocarbon groups such as heptyl group, straight chain or branched octyl group, alicyclic hydrocarbon groups such as cyclohexyl group, methylcyclohexyl group, and ethylcyclohexyl group; and aromatic groups such as phenyl group, tolyl group, naphthyl group and methylnaphthyl group. , Aromatic substituted alkyl groups such as a benzyl group and a naphthylmethyl group. Among them, in the present invention, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group is preferable from the viewpoint of good transparency of the cured product of the present invention, and a methyl group and an ethyl group are more preferable from the viewpoint of providing the cured product of the present invention having good toughness and heat resistance.

The hydroxyalkyl group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ refers to an atomic group in which one or more hydrogen atoms of a straight-chain or branched alkyl group are substituted with hydroxyl groups.

The hydroxyalkyl group preferably has 1 to 4 carbon atoms. As a specific example, what substituted one or two or more hydrogen atoms of a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group with a hydroxyl group is mentioned. Among them, in the present invention, it is preferable that one hydroxyl group is substituted on the terminal carbon from the viewpoint of easy reaction. The hydroxymethyl group and the hydroxyethyl group are more preferable from the viewpoint of good toughness and heat resistance of the cured product of the present invention.

The alkylene oxide used in the present invention refers to a compound having a 3-membered ring cyclic ether.

The alkylene oxide preferably has 2 to 8 carbon atoms. Examples include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. These alkylene oxides may be used alone or in combination of two or more. Especially, if it is at least 1 sort(s) selected from ethylene oxide and propylene oxide, it is easy to obtain and is cheap, and it is preferable in this invention.

The amount of the alkylene oxide used is usually 0.1 to 6.0 equivalents, preferably 0.2 to 2.0 equivalents, of a 3-membered cyclic ether relative to 1 equivalent of the hydroxyl group of the polyhydric alcohol (A). If it is this range, heat resistance and toughness of the hardened|cured material obtained are 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 at least one carbon is substituted with oxygen in a cyclic hydrocarbon having 4 or more rings.

The cyclic ether is preferably a 4 to 6-membered ring, and specific examples thereof include oxetane, tetrahydrofuran, tetrahydropyran, and the like. These cyclic ethers may be used alone or in combination of two or more. Especially, since tetrahydrofuran is easy to obtain and cheap, it is preferable in this invention.

The amount of cyclic ether used is 0.1 to 6.0 equivalents, preferably 0.2 to 2.0 equivalents, per 1 equivalent of the hydroxyl group of the polyhydric alcohol (A). If it is this range, heat resistance and toughness of the hardened|cured material obtained are favorable.

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 a cyclic ester is 2-6. Acetactone, propiolactone, butyrolactone, valerolactone, caprolactone, etc. are mentioned as a specific example of a cyclic ester. These cyclic esters may be used alone or in combination of two or more. Among them, caprolactone is preferred in the present invention because it is easy to obtain and inexpensive.

The use amount of the cyclic ester is 0.1 to 6.0 equivalents, preferably 0.2 to 2.0 equivalents, of the cyclic ester with respect to 1 equivalent of the hydroxyl group of the polyhydric alcohol (A). If it is this range, heat resistance and toughness of the hardened|cured material obtained are favorable.

The trimellitic anhydride (1,2,4-benzenetricarboxylic acid-1,2-anhydride halide) used in the present invention is used to introduce an acid anhydride group into a polyhydric alcohol and to form a polyfunctional acid anhydride compound. do. Thereby, an acid anhydride group can be introduce|transduced without involving ring-opening esterification of an acid anhydride group. In addition, it is excellent in heat resistance from an aromatic derived rigid skeleton.

The nuclear hydrogenated trimellitic anhydride (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride halide) used in the present invention is used for the same purpose as the trimellitic anhydride. In addition, since nuclear hydrogen is added, coloring is low even under heat and light resistance, and the cured product is excellent in toughness while maintaining high optical properties.

Examples of the trimellitic anhydride and the trimellitic anhydride added with nuclear hydrogen include fluoride, chloride, bromide and iodide, and among them, chloride is preferred for ease of reaction.

In the present invention, the used molar ratio of the mixture of trimellitic anhydride and trimellitic anhydride added with nuclear hydrogen is 1:99 to 99:1, preferably 30:70 to 70:30 when the total number of moles is 100. to be. The reaction ratio of the hydroxyl group of the polyhydric alcohol (A) or (B) with a mixture of trimellitic anhydride and trimellitic anhydride with nuclear hydrogen is approximately, of trimellitic anhydride and trimellitic anhydride with nuclear hydrogen. Matches the molar ratio. As the polyfunctional acid anhydride of the present invention, 5% or more and 95% or less of the total number of hydroxyl groups of the polyhydric alcohol (A) or (B) react with trimellitic anhydride anhydride, and the remaining hydroxyl groups and anhydrous tris with nuclear hydrogenation Melitic acid halide is reacted, preferably 10% or more and 75% or less of the total number of hydroxyl groups of the polyhydric alcohol (A) or (B) react with anhydrous trimellitic acid halide, and the remaining hydroxyl groups and nuclear hydrogen are added This is a reaction of trimellitic anhydride halide.

The polyfunctional acid anhydride of the present invention can be synthesized by a known method. Each of the reaction of polyhydric alcohol (A) or (B) with a mixture of trimellitic anhydride and trimellitic anhydride with nuclear hydrogen or trimellitic anhydride with nuclear hydrogen (hereinafter referred to as "halides") There is no restriction|limiting in particular in the addition method of a compound, and arbitrary addition method can be employ|adopted. For example, the above-mentioned halide dissolved in a solvent if the polyhydric alcohol (A) or (B) and a basic substance are dissolved in a solvent, and the above halides dissolved in the solvent are slowly added dropwise thereto, or vice versa. A method of dropping a mixed solution of a polyhydric alcohol (A) or (B) with a basic substance in a stream, a method of dropping a basic substance into a mixed solution of a halide and a polyhydric alcohol (A) or (B), furthermore, a polyhydric alcohol A method of dropping a halide solution and a basic substance solution simultaneously in the solution of (A) or (B) may be employed.

In the reaction of the polyhydric alcohol (A) or (B) in the presence of a basic substance with halides, the basic substance is neutralized and hydrochloride produced by the reaction proceeds. After removing this hydrochloride by filtration, the filtrate is concentrated to obtain a crude product of the polyfunctional acid anhydride of the present invention in high yield. This was dissolved in a suitable solvent, concentrated after washing with water, and then dried under reduced pressure to obtain a polyfunctional acid anhydride having high purity. Moreover, polyfunctional acid anhydride with higher purity is obtained by recrystallization with a suitable solvent as needed.

The amount of the polyhydric alcohol (A) or (B) is usually used as the hydroxyl group equivalent, when the sum of the hydroxyl group equivalents of the mixture of trimellitic anhydride and trimellitic anhydride anhydride is set to 1.0, or anhydrous trihydric anhydride When the hydroxyl group equivalent of melitic acid halide is set to 1.0, it is 0.6 to 1.0, preferably 0.8 to 1.0. In this range, the hydroxyl groups of the polyhydric alcohol (A) or (B) are all esterified, so that no trimellitic anhydride and anhydrous trimellitic anhydride hydride remain in the system.

The solvent usable in the reaction of the halide with the polyhydric alcohol (A) or (B) is not particularly limited as long as it is inert with respect to the raw material, but tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane-bis Ether solvents such as (2-methoxyethyl) ether, aromatic amine solvents such as picoline and pyridine, ketone-based solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene, dichloro Halogen-containing solvents such as methane, chloroform, 1,2-dichloroethane, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, and N,N-dimethylformamide Amide-based solvents such as, phosphorus-containing solvents such as hexamethylphosphoramide, sulfur-containing solvents such as dimethyl sulfoxide, etc., ester-based solvents such as γ-butyrolactone, ethyl acetate, and butyl acetate, 1,3-dimethyl-2 And nitrogen-containing solvents such as imidazolidinone, aromatic solvents having hydroxyl groups such as phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, and p-chlorophenol. Can. These solvents may be used alone or in combination of two or more.

When the halide is reacted with the polyhydric alcohol (A), the reaction temperature is -10°C to 80°C, preferably 0°C to 70°C, more preferably 10°C to 60°C. The solvents contained herein include cyclic ethers or cyclic esters used when preparing polyhydric alcohols (B) from polyhydric alcohols (A). When the reaction temperature is higher than 80°C, cyclic ethers or cyclic esters are used for polyhydric alcohols (A). By reacting, polyhydric alcohol (B) is obtained, and the reaction rate between polyhydric alcohol (A) and halide 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 also be carried out under pressure or under reduced pressure if necessary.

When polyhydric alcohol (A) is reacted with cyclic ether or cyclic ester to produce polyhydric alcohol (B), the reaction temperature is 80°C to 250°C, preferably 90°C to 220°C, more preferably 100°C to 200 ℃. 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 also be carried out under pressure or under reduced pressure if necessary.

The concentration of the solute in the solvent in the reaction for obtaining a polyfunctional acid anhydride is usually 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass in consideration of the side reaction control and filtration steps of precipitation. In this reaction, the solute is more preferably 10% by mass or more and 40% by mass or less in a solvent.

Usually, the reaction atmosphere is performed under nitrogen. The reaction vessel may be either a closed-type reaction vessel or an open-type reaction vessel, but in order to keep the reaction system in an inert atmosphere, in the case of an open-type, one that can be sealed with an inert gas is used.

The basic substance is used to neutralize the hydrogen chloride that occurs as the reaction proceeds. The type of the basic substance used at this time is not particularly limited, and organic tertiary amines such as pyridine, triethylamine, N,N-dimethylaniline, and inorganic basic substances such as potassium carbonate and sodium hydroxide can be used. Pyridine and triethylamine are preferable in that they are available at low cost or because the solubility in liquid is abundant, so that the reaction operation becomes easy. Moreover, an inorganic basic substance is preferable at the point which can be obtained at low cost.

The amount of the basic substance to be used is not particularly limited, but if it is excessively used, it may be incorporated into the product or the purification load may be increased. Therefore, the total mole number of halides is 1.0 to 30 mole times, preferably 1.2 to 20 mole times, more preferably 1.5 to 10 mole times are used.

During the water washing operation, the polyfunctional acid anhydride undergoes some hydrolysis and changes to a polyvalent carbon acid, but by heating under reduced pressure, the resulting polyvalent carbon acid can be easily returned to the polyfunctional acid anhydride. The temperature of the heat treatment under reduced pressure is 80°C to 200°C, preferably 100°C to 180°C, and the degree of reduced pressure is 50 KPa or less, preferably 10 KPa or less, and the upper limit of the heating time is not particularly limited. Usually, it is 10 minutes-48 hours, Preferably it is 30 minutes-24 hours.

It is also possible to further purify the polyfunctional acid anhydride of the present invention thus obtained. As a purification method in that case, recrystallization, sublimation, washing, activated carbon treatment, column chromatography, and the like can be optionally performed. Further, these purification methods may be repeated, or may be performed in combination. The purity of the polyfunctional acid anhydride of the present invention thus obtained is, for example, an area ratio of a peak obtained by an analysis such as gel permeation chromatography (hereinafter referred to as "GPC"), usually 90% or more, preferably 95% or more, and more preferably 98% or more.

It is preferable to preserve|save the polyfunctional acid anhydride at the low temperature which avoided high humidity in order to prevent the ring opening of an acid anhydride ring by hydrolysis. Specifically, when stored in a refrigerator in a container with good sealability, it withstands long-term storage. In addition, regarding the polyfunctional acid anhydride, it may be used in the next polymerization reaction immediately after purification to prevent moisture absorption. The storage period at that time is usually within 100 hours, preferably within 50 hours, and more preferably within 24 hours.

The thermosetting resin composition can also be constituted by combining the polyfunctional acid anhydride of the present invention with a compound that undergoes curing reaction. At this time, the compound having an acid anhydride group and a functional group capable of reacting by heat is not particularly limited, but a compound having an epoxy group is particularly preferably used.

At this time, in order to obtain a suitable thermosetting composition, it is preferable to use a compound containing at least two of the functional groups capable of reacting with an acid anhydride group.

Any compound having at least one epoxy group in one molecule may be used as the compound having an epoxy group represented in the present invention. Hereinafter, an aromatic epoxy resin, an aliphatic epoxy resin, and a copolymer epoxy resin as a compound having at least one epoxy group in one molecule suitably used in the present invention will be described.

Examples of the aromatic epoxy resin include cresol novolac type epoxy resins, phenol novolac type epoxy resins, biphenyl-phenol type epoxy resins, and novolac type epoxy resins such as naphthol type epoxy resins, bisphenol A type epoxy resins, and bisphenol F type epoxy Bisphenol type epoxy resin, such as resin, bisphenol S type epoxy resin, trisphenolmethane type epoxy resin, glyoxal type epoxy resin, (4-(4-(1,1-bis(p-hydroxyphenyl)-ethyl)- and α,α-dimethylbenzyl)phenol)-type epoxy resins. Among these, in the present invention, considering heat resistance and color resistance, bisphenol A type epoxy resin, (4-(4-(1,1-bis(p-hydroxyphenyl)-ethyl)-α,α-dimethylbenzyl )Phenol) type epoxy resin is preferred.

Examples of the aliphatic epoxy resin include an epoxy resin having an aliphatic cyclic structure and an epoxy resin not having an aliphatic cyclic structure. The epoxy resin having an aliphatic cyclic structure is characterized by having at least one cyclic aliphatic structure in one molecule. For example, terpendiphenol, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and aliphatic cyclic dienes (dicyclopentadiene, norbornadiene, hexa) Cyclohexyl structures in the molecule, such as polycondensates with hydroxyindenes) and glycidyl ethers derived from modified products thereof, hydrogenated bisphenol (bisphenol A, bisphenol F) type epoxy resins, alicyclic epoxy resins, etc. The epoxy resin which has, the epoxy resin which has a dicyclopentadiene structure, the epoxy resin which has a triglycidyl isocyanurate structure, etc. are mentioned. Specifically, for example, cyclohexanediol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate, 2,2-bis(hydroxyalkyl)-1 And 1,2-epoxy-4-(2-oxyranyl)cyclohexane adducts of -butanol.

As a compound etc. which have at least 1 epoxy group in 1 molecule which does not have an aliphatic cyclic structure, glycidyl ethers derived from linear or branched alcohols, such as hexane diglycidyl ether, are mentioned.

As the copolymerized epoxy resin, a monomer having an unsaturated double bond and an epoxy group, for example, glycidyl (meth)acrylate, hydroxyethyl (meth)acrylate glycidyl ether, hydroxybutyl (meth)acrylate glycol It is a copolymer of a monomer, such as a cidyl ether, and other monomers having a polymerizable unsaturated group. The other monomers are not particularly limited, and any monomers having both the above-mentioned unsaturated double bonds and epoxy groups can be used as long as they can be copolymerized. For example, vinyl compounds such as ethylene, propylene, styrene, vinyl acetate, and vinyl chloride, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl ( Glycols such as alkyl (meth)acrylates such as meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxybutyl (meth)acrylate Ether mono(meth)acrylates, ethylene glycol methyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monoethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth) And glycol ether monoalkyl ether (meth)acrylates such as acrylates.

The particles (C-1) used in the resin composition of the present invention include, for example, polymethyl methacrylate, polystyrene, and nylon as organic particles, and talc, fired clay, and unfired clay as inorganic particles. , Silicates such as mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, barium sulfate, and sulfuric acid Sulfates or sulfites such as calcium and calcium sulfite, borates such as zinc borate, barium metaborate, aluminum borate, calcium borate and sodium borate, nitrides such as aluminum nitride, boron nitride and silicon nitride, fluorides such as magnesium fluoride and calcium fluoride And colloidal solutions dispersed in a fine powder or a solvent containing no dispersing solvent, which can be obtained from the market and used. In addition, these may be used alone or in combination of two or more. Dispersing solvents include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ketones such as dimethyl dimethylacetamide, esters such as ethyl acetate and butyl acetate, and non-polar solvents such as toluene and xylene, and the thermosetting resin composition of the present invention It is good to select and use what is dissolved in each component of. In addition, inorganic particles are preferred from the viewpoint of dimensional stability. In particular, alumina and silica are preferred from the viewpoint of versatility and low cost.

The fiber (C-2) used in the resin composition of the present invention is carbon fiber, glass fiber, casein fiber, peanut protein fiber, corn protein fiber, soybean protein fiber, algin fiber, chitin fiber, met fiber, rubber fiber, cellulose fiber , Nylon fiber, polyvinylidene chloride fiber, polyvinyl chloride fiber, polyester fiber, polyacrylonitrile fiber, modacrylic fiber, polyethylene fiber, polypropylene fiber, polystyrene fiber, polyetherester fiber, polyurethane fiber, etc. Can. These may be used alone or in combination of two or more. Among them, glass fibers are preferred from the viewpoint of versatility. In addition, there are various types of glass fibers, such as woven fabrics, nonwoven fabrics, and knitted fabrics, and there are no particular limitations on the type in the present invention, but a cured product having excellent dimensional stability when cured by impregnating the thermosetting resin composition of the present invention is obtained. In order, a glass cross is suitable. In consideration of adhesion to the thermosetting resin composition of the present invention, it is preferable that the glass fibers are treated with a silane coupling agent.

Particles (C-1) and fibers (C-2) may be used either alone or in combination depending on the obtained performance.

Other components may be included in the resin composition of the present invention. Examples of these other components include inorganic fillers, antioxidants, light stabilizers, and ultraviolet absorbers.

The antioxidant that can be used in the resin composition of the present invention is not limited as long as it is a known general substance such as a phenol-based, sulfur-based, or phosphorus-based antioxidant. However, considering the features of the present invention, it is preferable to select one that is colorless and hard to be colored even when used for a long time as a heat during curing or as a circuit board after sealing.

Examples of phenolic antioxidants include monophenols, bisphenols, and high molecular weight phenols.

As specific examples of the sulfur-based antioxidant, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate Nate etc. are mentioned.

Examples of phosphorus-based antioxidants include phosphites and oxaphosphaphenanthrene oxides.

These antioxidants may be used alone, but two or more of them may be used in combination. The amount of the antioxidant used is usually 0.008 to 1 part by mass, preferably 0.01 to 0.5 part by mass, relative to 100 parts by mass of the resin composition of the present invention. Further, in the present invention, phosphorus-based antioxidants are preferred.

As the light stabilizer which can be used for the resin composition of the present invention, a known general one can be used, and there is no particular limitation. However, in view of the features of the present invention, it is preferable to select a material that is colorless and hard to be colored even when used for a long time or heat during curing. Hindered amines etc. are mentioned as a typical example of these.

As the ultraviolet absorber that can be used in the resin composition of the present invention, a known general one can be used, and there is no particular limitation. As an ultraviolet absorber, a benzotriazole type, a hydroxyphenyl triazine type, etc. are mentioned, It is also possible to use together with the said light stabilizer.

In the present invention, it is preferable to use an ultraviolet absorber with low colorability over time. For example, propanoic acid-2-[4-[4,6-bis([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl]-3- Hydroxyphenyl]-isooctyl ester (for example, TINUVIN 479, manufactured by Chiba Japan Co., Ltd.) and the like.

When improving the color resistance of the present invention, a hydroxyphenyltriazine-based ultraviolet absorber and a hindered amine-based light stabilizer are used together.

In the resin composition of the present invention, butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide Resin components, such as a system resin, a polyimide resin, and a silicone resin, can also be added as needed.

Silane coupling agents, release agents, leveling agents, surfactants, dyes, pigments, organic light-diffusing fillers and the like can also be added to the resin composition of the present invention.

A well-known general metal salt can also be added to the resin composition of the present invention for the purpose of improving heat resistance and light resistance. For example, metal salts of carbonic acid (zinc salts such as 2-ethylhexanoic acid, stearic acid, behenic acid, myristic acid, tin salts, zirconium salts) or phosphoric acid ester metals (zinc salts such as octyl phosphoric acid and stearyl phosphoric acid), And metal compounds such as alkoxy metal salts (tributylaluminum, tetrapropylzirconium, etc.) and acetylacetone salts (acetylacetone zirconium chelate, acetylacetone titanium chelate, etc.). These may be used alone or in combination of two or more. By adding a metal salt, the heat resistance and color resistance of the present invention can be improved.

In the resin composition of the present invention, it is also generally performed to add a curing catalyst to accelerate the reaction by heat, to accelerate the reaction in response to heat, or to adjust the curing temperature. As long as they have the effect of accelerating the curing reaction, well-known general ones can be used.

As the curing catalyst, for example, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyano Ethyl-2-undecylimidazole, 2,4-diamino-6-(2'-methylimidazole(1'))ethyl-s-triazine, 2,4-diamino-6-(2 '-Undecylimidazole(1'))ethyl-s-triazine, 2,4-diamino-6-(2'-ethyl-4-methylimidazole(1'))ethyl-s-tri Azine, 2,4-diamino-6-(2'-methylimidazole(1'))ethyl-s-triazine-isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2 :3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxyalkylimidazole, 2-phenyl-4-hydroxyalkyl-5-methylimidazole , Various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and these imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid , Salts with polyvalent carbon acids such as naphthalenedicarboxylic acid, maleic acid and oxalic acid, amides such as dicyandiamide, and diaza compounds such as 1,8-diaza-bicyclo(5,4,0)undecene-7 And salts such as tetraphenyl borate and phenol novolac, salts with the above polyvalent carbon acids, or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, acetyltrimethylammonium bromide, trioctylmethylammonium bromide, and triphenylphosphine Phosphine or phosphonium compounds, such as tri(toluyl)phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenyl borate, hexafluorostibin phosphonium salt, 2,4,6-trisaminomethyl And organic metal compounds such as phenols such as phenol, tin octylate, cobalt octylate, zinc octylate, zirconium octylate, nickel octylate, and cobalt naphthenate. Moreover, the microcapsule type curing catalyst which used a hardening accelerator as a microcapsule is mentioned.

Which of these curing catalysts to use should be appropriately selected according to the required properties. The curing catalyst is usually used in the range of 0.001 to 15 parts by mass based on 100 parts by mass of the total resin in the resin composition of the present invention.

The thermosetting resin composition of this invention can mix each component uniformly by the method similar to a conventionally well-known method, and can be set as the hardened|cured material. For example, an epoxy resin, an acid anhydride curing agent, and a curing accelerator, and other components, if necessary, are thoroughly mixed until necessary to obtain uniformity using an extruder, kneader, roll, or the like to obtain a thermosetting resin composition of the present invention. . Since the thermosetting resin composition of the present invention is a solid at room temperature, after melting, it is molded using a mold or transfer molding machine, and further, a method such as curing by heating is exemplified.

In addition, the thermosetting resin composition of the present invention, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetic acid It can be used as a varnish by diluting with solvents such as ethyl, butyl acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. Since the thermosetting resin composition of the present invention is usually solid at room temperature, it is easier to handle by diluting with a solvent and more preferable. In particular, when using by impregnating a glass cloth, dilution with a solvent is performed.

The solvent can be used as one kind or a mixture of two or more kinds of solvents in consideration of viscosity and drying speed when using the thermosetting resin composition of the present invention. The use ratio of the solvent depends on the workability and drying speed at the time of use, but is usually 10 to 200 parts by mass, preferably 15 to 100 parts by mass, relative to 100 parts by mass of the thermosetting resin composition of the present invention.

In the case of obtaining the thermosetting resin composition of the present invention diluted with a solvent, it can also be prepared by mixing and dissolving each component according to the conventional method. For example, the varnish of the thermosetting resin composition can be obtained by adding each component to a round bottom flask with a stirring device and a thermometer and stirring at 40 to 80°C for 0.5 to 6 hours. At this time, the varnish of the epoxy resin, and the varnish of the acid anhydride curing agent + curing catalyst or additive are adjusted separately, and the method of mixing in use is particularly preferable. As described above, when the fine particles are added, treatment may be performed by a generally known dispersing method, such as a high-speed stirrer such as a homo mixer or a sand mill, a microfluidizer, or a triaxial roll.

The varnish of the thermosetting resin composition of the present invention thus obtained is molded by a known method, dried, and then cured by further heating. For example, it can be poured into a mold, heated and dried, and then cured, or a bar coater, air knife coater, die coater, gravure coater, offset printing, flexo printing, screen printing, etc. It is applied to an alternative metal plate or release film, and after heating and drying, the method of curing is impregnated with a glass cloth, followed by heating and drying, and then applied to a glass or transparent plastic substrate. And a method of use as a coating agent used together. In the thermosetting resin composition of the present invention, since the curing agent volatilizes during curing, the composition ratio of the film does not change and the refractive index does not change, so that a stable transparent film can be obtained. For this reason, it is suitable also for manufacture of an optical sheet. Moreover, the surface of the cured film does not become rough or the physical properties of the cured film change due to the volatilization of the curing agent, so that a smooth and excellent hardness film can be obtained.

The drying temperature of the varnish of the thermosetting resin composition of the present invention depends on the solvent and the air volume used, but is usually preferably 60 to 200°C. It is also possible to obtain a prepreg by impregnating the varnish with a glass fiber sheet-like substrate such as a glass cloth and drying the solvent to make the thermosetting resin composition of the present invention semi-cured. The drying conditions at this time are not particularly limited, but the temperature is preferably 100 to 180°C, and the time is preferably 1 to 30 minutes.

The prepreg provided with the thermosetting resin composition of the present invention in a semi-cured state is also included in the present invention.

The cured product obtained by curing the thermosetting resin composition of the present invention is also included in the present invention. A cured product obtained by drying and curing the prepreg in which the thermosetting resin composition of the present invention is impregnated into fibers is also included in the present invention. As described above, the thermosetting resin composition of the present invention is suitable for the production of an optical sheet because there is no change in refractive index due to volatilization of the curing agent during curing. Moreover, as a curing temperature and time of the thermosetting resin composition of this invention, it is 2 to 200 hours at 80-200 degreeC. As a curing method, although it can be hardened at once at high temperature, you may harden for a long time at low temperature of 150 degreeC or less. The curing reaction may be performed by raising the temperature in stepwise, such as initial curing between 80°C and 150°C and post-curing between 100°C and 200°C.

As the glass cross for producing the prepreg, a known commercially available one can be used. Among them, E glass, which is generally used for resin strengthening, has few alkali metal oxides and is suitable for use in the present invention as an alkali free glass. There are various commercially available glass cloths, such as woven fabrics, nonwoven fabrics, and knitted fabrics using glass fibers, and the type of the present invention is not particularly limited, but the cured product is smooth when impregnated and cured by impregnating the thermosetting resin composition of the present invention. In order to obtain, it is suitable that the irregularities of the surface of the glass cross are small. When considering the conditions of drying and semi-hardening when producing the prepreg, the thickness of the glass cross is usually 100 µm or less, preferably 50 µm or less. A prepreg may be produced using a thickness of about 25 µm or less, and two to several sheets may be overlapped and integrated with each other during curing to form an optical sheet of the present invention. The diameter of the glass fiber used for the glass cloth is preferably small, considering transparency and the like, and preferably 10 µm or less. Further, in consideration of adhesion to the thermosetting resin composition of the present invention, it is preferable that the glass fibers are treated with a silane coupling agent. The refractive index is 1.51 to 1.57, and is generally available, and 1.55 to 1.57 are more preferable.

In this invention, it is preferable that the refractive index of the hardened|cured material of this invention is small from the refractive index of the glass fiber used. Specifically, the difference from the refractive index of the glass fiber is preferably ±0.01, more preferably the difference is ±0.005. When the refractive index of the cured product of the present invention is within this range, an optical sheet excellent in transparency, smoothness and hardness is obtained. By further applying, drying, and curing the thermosetting resin composition of the present invention on these optical sheets, it is also possible to obtain an optical sheet having better transparency and smoothness.

The thermosetting resin cured product of the present invention can be used as a substitute for glass used in display devices such as liquid crystal displays, plasma displays, EL displays, portable devices, and solar cells. In addition, liquid crystal display device peripheral materials such as light guide plates, prism sheets, polarizing plates, retardation plates, viewing angle correction films, adhesives, polarizer protective films, and the like, antireflection films, front panels for touch panels, optical correction films, etc. You can also use

(Example)

Next, the present invention will be described in more detail by examples. In addition, this invention is not limited at all by the following Example. In the synthesis of the compound, the reaction was terminated when the disappearance of the raw alcohols was confirmed by gel permeation chromatography (hereinafter referred to as "GPC"). In addition, in the examples, TMAC is trimellitic anhydride, HTAC is trimellitic anhydride with nuclear hydrogenation, THF is tetrahydrofuran, TMP is trimethylolpropane, DPE is dipentaerythritol, PE4EO Denotes a pentaerythritol 4 mol ethylene oxide adduct, DE6EO a dipentaerythritol 6 mol ethylene oxide adduct, DPE4C a dipentaerythritol 4 mol caprolactone adduct, MEK represents methyl ethyl ketone, respectively.

Synthesis Example 1: Synthesis of dipentaerythritol 4-mol caprolactone adduct (DPE4C)

To a flask equipped with a stirrer, a reflux cooling tube, and a stirrer, while purging nitrogen, 45.66 g (400 mmol) of caprolactone was added to 25.43 g (100 mmol) of dipentaerythritol and stirred at 180° C. for 12 hours, 71.09 g of dipentaerythritol 4-mol caprolactone adduct was obtained.

Synthesis Example 2: Preparation of copolymerized epoxy resin

30 g of glycidyl methacrylate, 30 g of methyl methacrylate, 40 g of butyl methacrylate, 200 g of methyl ethyl ketone as a solvent, as a reaction initiator, while nitrogen purging is carried out in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device 1 g of azobisisobutyronitrile was added, and polymerization was performed at 80°C for 5 hours.

After completion of the reaction, the solvent was distilled off under heating and reduced pressure to 90°C to obtain a copolymer-type epoxy resin. The molecular weight of the obtained copolymer-type epoxy resin was a polystyrene equivalent number average molecular weight of 15,000 by GPC, the same weight average molecular weight of 30,000, and an epoxy equivalent of 470 g/eq.

Example 1-1: Synthesis of polyfunctional acid anhydride

36 g of THF was added to 23.34 g (108 mmol) of HTAC while purging nitrogen in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device to obtain a uniform solution. After stirring this solution to 5°C while stirring, 10.08 g (127.5 mmol) of pyridine and 54 g of THF were added to 4.44 g (33 mmol) of TMP to maintain a uniform solution, and the liquid temperature was maintained at 10°C or lower. While dropping slowly. 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 the insoluble portion of pyridine hydrochloride was filtered off, and then the filtrate was concentrated. The concentrate was dissolved in 120 ml of ethyl acetate, washed three times with 30 ml of water, and dried over anhydrous magnesium sulfate. After removing the anhydrous magnesium sulfate by filtration, the filtrate was concentrated, the resulting concentrate was dissolved in 15 ml of ethyl acetate, and recrystallized from toluene to obtain 16.7 g (yield 75.2%) of the product.

It was confirmed that this product was the desired compound from ¹ H-NMR.

¹ H-NMR (chloroform-d1, δppm): 0.90-0.92 (m, 3H), 1.48-2.49 (m, 23H), 3.11-3.41 (m, 6H), 4.04 (s, 6H)

Example 1-2: Synthesis of polyfunctional acid anhydride

12 g of THF was added to 7.78 g (36 mmol) of HTAC while nitrogen purging was carried out in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device to obtain a uniform solution. After the solution was cooled to 5° C. while stirring, the solution uniformly added by adding 3.36 g (47.5 mmol) of pyridine and 18 g of acetone to 1.40 g (5.5 mmol) of DPE was slowly added dropwise while maintaining the liquid temperature at 10° C. or lower. did. 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 the insoluble portion of pyridine hydrochloride was filtered off, and then the filtrate was concentrated. The concentrate was dissolved in 40 ml of ethyl acetate, washed three times with 10 ml of water, and dried over anhydrous magnesium sulfate. After removing the anhydrous magnesium sulfate by filtration, the filtrate was concentrated, the resulting concentrate was dissolved in 5 ml of ethyl acetate, and recrystallized with toluene to obtain 5.24 g (yield 71.3%) of the product.

Examples 1-3 to 1-4

In Example 1-2, a polyfunctional acid anhydride was synthesized in the same manner except that the polyhydric alcohol was used in Table 1.

Example 1-5: Synthesis of polyfunctional acid anhydride

120 g of THF was added to 78.6 g (363 mmol) of HTAC while purging nitrogen to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device to obtain a uniform solution. After the solution was cooled to 5°C while stirring, 33.6g (475mmol) of pyridine and 180g of THF were added to 28.5g (55mmol) of PE4EO, and a uniform solution was slowly 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 the insoluble portion of pyridine hydrochloride was filtered off, and then the filtrate was concentrated. The obtained concentrate was dissolved in 400 ml of ethyl acetate, washed three times with 100 ml of water, and dried over anhydrous magnesium sulfate. After the anhydrous magnesium sulfate was filtered off, the filtrate was concentrated, the resulting concentrate was dissolved in 40 ml of ethyl acetate, and recrystallized from toluene to obtain 74.7 g (yield 77.1%) of the product.

Examples 1-6 to 1-14, Comparative Examples 1-1

In Example 1-5, polyfunctional acid anhydride was synthesized in the same manner except that HTAC was used as a mixture of TMAC and HTAC, and polyhydric alcohol was described in Table 2.

It was confirmed from ¹ H-NMR that the polyfunctional acid anhydride of Example 1-6 was the desired compound. 2 shows a chart of ¹ H-NMR.

¹ H-NMR (dimethylsulfoxide-d6, δppm): 0.79-1.00 (m, 3H), 1.20-2.73 (m, 15.5H), 3.05-3.57 (m, 3H), 3.93-4.58 (m, 6H) , 8.13-8.53 (m, 4.5H)

Example 2-1: Preparation of resin composition

35 g of the alicyclic polyfunctional acid anhydride obtained in Example 1-1, 10 g of an aliphatic epoxy resin EHPE-3150 (manufactured by Daicel, Epoxy equivalent 181), aromatic epoxy resin NC-6300 (Nippon Kayaku ( Note) Preparation: 27 g of (4-(4-(1,1-bis(p-hydroxyphenyl)-ethyl)-α,α-dimethylbenzyl)phenol) type epoxy resin, epoxy equivalent 206, total chlorine 550 ppm) Similarly, 23 g of RE-310S (manufactured by Nippon Kayaku Co., Ltd.: liquid bisphenol A epoxy resin, epoxy equivalent 185, total chlorine content 500 ppm), 0.3 g of zinc octylate as other components, and 41 g of methyl ethyl ketone as a dilution solvent The combined ones were heated to 70°C and mixed to obtain a resin composition having a solid content of 70% by mass.

Note) EHPE-3150: 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol

Examples 2-2 to 2-14, Comparative Examples 2-1 to 2-2

A resin composition having a solid content of 70% by mass was prepared in the same manner as in Example 2-1 except that the polyfunctional acid anhydride and MEK were listed in Table 3.

Example 2-15: Preparation of resin composition

10 g of the polyfunctional acid anhydride obtained in Example 1-3, 50 g of the glycidyl methacrylate copolymer of Synthesis Example 2, 1 g of triphenylphosphine as a curing catalyst, and 40 g of methyl ethyl ketone as a solvent were heated to 50° C., By mixing, a resin composition having a solid content of 60% by mass was obtained.

Example 2-16: Preparation of resin composition

The same procedure as in Example 2-1 was carried out except that 35 g of the polyfunctional acid anhydride obtained in Example 1-1 and MEK as a diluting solvent was 41 g, and further a methyl ethyl ketone dispersion of colloidal silica (30% by mass solid content, Nissan) 137 g of organosilica sol (ORGANOSILICASOL) MEK-ST; hereinafter MEK-ST) manufactured by Kagaku Kogyo Co., Ltd. was added to obtain a dilute composition of the resin composition of the present invention having a solid content of 59% by mass.

Comparative Example 2-3: Preparation of resin composition

17g for 1,2,4,5-cyclohexanetetracarboxylic acid anhydride, 23g for RE-310S (manufactured by Nippon Kayaku Co., Ltd.: liquid bisphenol A epoxy resin, epoxy equivalent 185, total chlorine amount 500ppm), and other components As a result, a resin composition dilution composition having a solid content of 70% by mass was obtained in the same manner as in Example 2-1, except that 0.3 g of zinc octylate and 33 g of acetone as a dilution solvent were used.

Comparative Example 2-4: Preparation of resin composition

10 g of hydrogenated trimellitic anhydride, 50 g of glycidyl methacrylate copolymer of Synthesis Example 2, 1 g of triphenylphosphine as a curing catalyst, and 40 g of MEK as a solvent were heated to 50°C and mixed to obtain a solid content of 60. A resin composition having a mass% was obtained.

Examples 3-1 to 3-5, Comparative Examples 3-1 to 3-2

A 40 mm×25 mm×1 mm shape was produced with a heat-resistant release tape on a glass substrate, and the thermosetting resin compositions of Example 2 and Comparative Example 2 were molded to a thickness of about 800 μm, respectively, and dried at 80° C. for 50 minutes. . Vacuum defoaming was performed once during drying to remove bubbles. Thereafter, the mixture was cooled to room temperature and the state was confirmed. As a result, the thermosetting resin composition of the present invention was solid at room temperature.

Subsequently, it cured in a 140 degreeC dryer for 3 hours, and obtained the hardened|cured material of this invention. The glass transition points, toughness, and color resistance were measured for the obtained cured products, respectively, and are listed in Table 4.

Evaluation method and evaluation standard

(1) Glass transition temperature (Tg): The Tg point of the cured resin composition was measured in a viscoelasticity measurement system (DMS-6000: manufactured by Seiko Denshi Kogyo Co., Ltd.) at a tensile mode and a frequency of 1 Hz.

(2) Toughness: Both ends of the cured film of the cured resin composition were fixed by hand, and the state of the cured film when the central portion was pressed was observed. The judgment criteria are as follows.

◎: Even if it is pressed strongly, it does not crack and does not crack.

○: The gold does not crack and does not crack even when lightly pressed, but cracks when pressed strongly.

(Triangle|delta): When it presses weakly, it cracks, and when it presses hard, it cracks.

×: It is cracked when pressed lightly.

(3) Transparency: The appearance of the cured film of the resin composition was visually observed.

As apparent from the above results, the cured product of the present invention is excellent in heat resistance, toughness, and transparency. The polyfunctional acid anhydride of the present invention used in the cured products of Examples 3-1 to 3-5 has an acid anhydride of trifunctional or higher, and the alcohol having a parental structure is aliphatic and has a large molecular weight, thereby providing heat resistance and It can be considered that the toughness is excellent. On the other hand, it can be considered that the polyfunctional acid anhydride used in the cured product of Comparative Example 3-1 is bifunctional and has low molecular weight, which is inferior in heat resistance and toughness. The cured product of Comparative Example 3-2 is considered to be inferior in heat resistance and toughness in that the acid anhydride is monofunctional and low molecular weight.

Examples 3-6 to 3-14, Comparative Examples 3-3

The cured product of this invention was obtained like Example 3-1. The glass transition points, toughness, and color resistance were measured for the obtained cured products, respectively, and are listed in Table 5. Evaluation of toughness is the same as in Example 3-1.

Evaluation method and evaluation standard

(1) Glass transition temperature (Tg): The Tg point of the cured resin composition was measured in a viscoelasticity measurement system (DMS-6000: manufactured by Seiko Denshi Kogyo Co., Ltd.) at a tensile mode and a frequency of 1 Hz. The judgment criteria are as follows.

◎: Tg is 200°C or higher

○: Tg is 190°C or more and 199°C or less

△: Tg is 185°C or higher and 189°C or lower

×: Tg is 184° C. or less

(2) Yellowness: The initial yellowness (YI) of the cured film of the cured resin composition and the yellowness (YI) after standing at 230° C. for 20 minutes are measured by a spectrophotometer (U-3900H: Hitachi High Technologies Co., Ltd. ( The yellowness was measured by JIS K7105/JIS K7373, and the difference (yellowness: ΔYI) was determined.

◎: ΔYI is 0.4 or less

○: ΔYI is 0.5 or more and 0.7 or less

Δ: ΔYI is 0.8 or more and 1.0 or less

×: ΔYI is 1.1 or more

As apparent from the above results, the cured product of the present invention is excellent in heat resistance, toughness, and yellowness (color resistance). The polyfunctional acid anhydride of the present invention used in the cured products of Examples 3-6 to 3-14 has an acid anhydride of trifunctional or higher, and is excellent in heat resistance and toughness in that the alcohol to be the parent is aliphatic and has a large molecular weight. . Further, despite having an aromatic ring on the skeleton, it also has excellent coloring resistance in that it also has an aliphatic ring. On the other hand, since the polyfunctional acid anhydride used in the cured product of Comparative Example 3-3 has only an aromatic ring, yellowing degree is high and coloring resistance is insufficient.

Examples 3-15 to 3-20, Comparative Examples 3-4 to 3-5

MEK was added to the resin compositions of Examples 2-1, 2-3 to 2-5, 2-16 and Comparative Examples 2-1 to 2-2 to adjust the solid content to 50% by mass, and commercially available glass cross (E glass Cross: IPC106, manufactured by Unichika Co., Ltd. Type: about 30 μm thick, plain weave, optical refractive index 1.561) or glass fiber nonwoven fabric (E glass: about 750 μm thick, optical refractive index 1.560) was added and impregnated. After pulling up the glass cross, it was dried at 120°C for 7 minutes. The sheet after drying was a solid film. It was further sandwiched between mold release PET films and pressed at 150°C for 10 minutes, semi-cured to obtain a prepreg. Thereafter, the mixture was cured in a 150°C dryer for 3 hours to obtain a cured product of the present invention. Moreover, the resin composition of Example 2-16 was made like Example 3-1, and the hardened|cured material of this invention was obtained. Heat resistance, toughness, yellowness, and dimensional stability of each of these cured products were measured, and the results are shown in Table 6. Evaluation of heat resistance and yellowness was the same as in Example 3-6. Evaluation of toughness is the same as in Example 3-1.

Evaluation method and evaluation standard

(1) Dimensional stability: The coefficient of linear expansion (CTE) of the cured resin composition was measured at 200°C/10 minutes in a viscoelasticity measurement system (DMA/SS-6000: manufactured by Seiko Denshi Kogyo Co., Ltd.). The judgment criteria are as follows.

◎: CTE is less than 25ppm/K

○: CTE is 26ppm/K or more and 35ppm/K or less

△: CTE is 36ppm/K or more and 45ppm/K or less

×: CTE is 46 ppm/K or more

As apparent from the above results, the cured product of the present invention is excellent in heat resistance, toughness, color resistance, and dimensional stability. The polyfunctional acid anhydride of the present invention used in the cured product of Examples 3-15 to 3-20 has an acid anhydride of trifunctional or higher, and is also excellent in heat resistance and toughness in that the alcohol to be modeled is aliphatic and has a large molecular weight. You can think of. In addition, since it has a large number of saturated alicyclics, the color resistance is also excellent in the dimensional stability in the cured product of the present invention including a glass cloth and the like. On the other hand, in Comparative Example 3-4, since it does not have a saturated alicyclic, the yellowing degree is high, and the coloring resistance is insufficient. In addition, in Comparative Example 3-5, since it is an acid anhydride of a low molecular weight used, it can be considered that heat resistance and toughness are inferior.

Example 4

The transparency of the cured products of Examples 3-15 and 3-17 was evaluated. Evaluation of transparency confirmed the coloring visually, and the results are listed in Table 7.

week)

Glass cloth a (IPC106 type manufactured by Unichika Co., Ltd.: about 30㎛ thick, plain weave, optical refractive index 1.561)

Glass cross b (IPC3313 type manufactured by Nitto Boseki Co., Ltd.; approximately 75 µm thick, plain weave, optical refractive index of 1.554)

As apparent from the above results, by adjusting the refractive index of the thermosetting resin composition of the present invention based on the refractive index of the glass cloth, a cured product having no transparency and excellent transparency was provided.

The polyfunctional acid anhydride of the present invention and its thermosetting resin composition include electrical and electronic materials such as paints for civil construction and FRP, and paints in the field of printed wiring boards and semiconductors, resist ink, adhesives, sealants, and encapsulants, Mainly, it is suitable for a display device such as a liquid crystal display, a plasma display, an EL display, a portable device, or a cured product used in a solar cell.

Claims (19)

Formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, and R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are hydrogen atoms, hydroxyl groups, and 1 to 11 carbon atoms. Represents a hydrocarbon group 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 represents 0 to 11, m and n represent integers of 1 to 11 Polyhydric alcohol (A) containing at least three hydroxyl groups in one molecule represented by)
A polyfunctional acid anhydride obtained by reacting a mixture of trimellitic anhydride and trimellitic anhydride added with nuclear hydrogen or trimellitic anhydride added with nuclear hydrogen. The polyhydric alcohol (B) obtained by reacting the polyhydric alcohol (A) according to claim 1 with at least one selected from the group consisting of alkylene oxides, cyclic ethers, and cyclic esters.
A polyfunctional acid anhydride obtained by reacting a mixture of trimellitic anhydride and trimellitic anhydride added with nuclear hydrogen or trimellitic anhydride added with nuclear hydrogen. In the general formula (1) according to claim ¹ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are polyhydric alcohols (A) having 1 to 4 carbon atoms and a trimellitic anhydride anhydride. And a polyfunctional acid anhydride obtained by reacting a mixture of nuclear hydrogenated trimellitic anhydride or a nuclear hydrogenated trimellitic anhydride halide. The polyhydric alcohol (B) obtained by reacting the polyhydric alcohol (A) according to claim 3 with at least one selected from the group consisting of alkylene oxides, cyclic ethers, and cyclic esters, trimellitic anhydride, and trihydric anhydride A polyfunctional acid anhydride obtained by reacting a mixture of melitic acid halides or trimellitic anhydride with nuclear hydrogenation. According to claim 1,
Polyfunctional acid anhydride wherein the polyhydric alcohol (A) is trimethylol or dipentaerythritol. According to claim 2,
Polyfunctional acid anhydride wherein the polyhydric alcohol (B) is a dipentaerythritol ethylene oxide adduct, dipentaerythritol propylene oxide adduct, dipentaerythritol tetrahydrofuran adduct, or dipentaerythritolcaprolactone adduct. According to claim 2,
A polyfunctional acid anhydride wherein the polyhydric alcohol (B) is a pentaerythritol 4 mole ethylene oxide adduct, dipentaerythritol 6 mole ethylene oxide adduct, or dipentaerythritol 4 mole caprolactone adduct. A thermosetting resin composition comprising a compound having at least one epoxy group in one molecule and the polyfunctional acid anhydride according to claim 1 or 2. The method of claim 8,
A compound having at least one epoxy group in one molecule is at least one thermosetting resin composition selected from aliphatic epoxy resins, aromatic epoxy resins, and copolymerized epoxy resins. The method of claim 9,
A compound having at least one epoxy group in one molecule, at least one thermosetting resin composition selected from aliphatic epoxy resins and aromatic epoxy resins. The method of claim 9,
A thermosetting resin composition in which the aliphatic epoxy resin is an epoxy resin having an aliphatic cyclic structure. The method of claim 9,
Aromatic epoxy resin is selected from (4-(4-(1,1-bis(p-hydroxyphenyl)-ethyl)-α,α-dimethylbenzyl)phenol) type epoxy resin and bisphenol A epoxy resin Ideal thermosetting resin composition. The method of claim 8,
A thermosetting resin composition in which a compound having at least one epoxy group in one molecule is a copolymerized epoxy resin. The method of claim 8,
A thermosetting resin composition further comprising particles (C-1) or fibers (C-2) which are not compatible with polyhydric alcohol (A), trimellitic anhydride and trimellitic anhydride with nuclear hydrogenation. The method of claim 14,
A thermosetting resin composition wherein the particles (C-1) are inorganic particles. The method of claim 14,
A thermosetting resin composition in which the fibers (C-2) are glass fibers. The method of claim 16,
A thermosetting resin composition in which fibers (C-2) are glass crosses formed by spinning glass fibers and further woven. A prepreg in which the thermosetting resin composition according to claim 8 is given a shape in a semi-cured state. A cured product obtained by curing the thermosetting resin composition according to claim 8.

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