KR20150044007A - Multifunctional acid anhydride, thermosetting resin composition, prepreg and cured article - Google Patents

Abstract

A resin composition that offers a cured article with high transparency, heat resistance, hardiness, and epiphytical resistance, especially one that is appropriate for optical component, needs to be obtained. A thermosetting resin composition comprising: a mixture of polyhydric alcohol (A) containing at least three hydroxyl group from one molecule, trimellitic acid halide anhydride and trimellitic acid halide anhydride with hydrogen nucleus, or a multifunctional acid anhydride obtained by reacting trimellitic acid halide anhydride with hydrogen nucleus; a polyhydric alcohol (B) obtained by reacting alkylene oxide, cyclic ether, or at least one selected from the cyclic ether group, and a multifunctional acid anhydride obtained by reacting trimellitic acid halide anhydride with trimellitic acid halide anhydride with hydrogen nucleus; a compound comprising at least one epoxy group from multifunctional acid anhydride and one molecule.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyfunctional acid anhydride, a thermosetting resin composition, a prepreg, and a cured product. [0002] MULTIFUNCTIONAL ACID ANHYDRIDE, THERMOSETTING RESIN COMPOSITION, PREPREG AND CURED ARTICLE,

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

The acid anhydride has excellent performance as a crosslinking agent, a condensation agent and the like, such as high-temperature stability and transparency, good electrical properties or chemical resistance, and good formation of a condensate and reactivity, and is widely used as a raw material for producing a polymer. It is also known that the acid anhydride can also be used as a curing agent for an epoxy resin.

A curable resin composition containing an epoxy resin is excellent in heat resistance and has been used in a wide range of fields. In recent years, the composition has been attracting attention for use in the field of optoelectronics. Particularly, along with recent high-level informationization, in order to smoothly transmit and process vast amount of information, signal transmission by a conventional electric wiring has been changed and technologies utilizing optical signals have been developed, and optical waveguides, blue LEDs, In the field of optical components such as semiconductors, development of a resin composition which gives a cured product excellent in transparency, toughness and heat resistance has been desired.

As the acid anhydrides in the curable resin composition containing an epoxy resin, aromatic acid anhydrides and alicyclic acid anhydrides are well known. An example of the use of an aromatic acid anhydride is an acid anhydride of Patent Document 1, for example. However, this compound is not sufficient in transparency and color resistance because it is easy to absorb coloration of aromatic origin and light of short wavelength. Examples of the use of the alicyclic acid anhydride include methylcyclohexene dicarboxylic anhydride of Patent Document 2, tetracarboxylic acid dianhydride having a tricyclo ring of Patent Document 3, tetracarboxylic acid having an ester group of Patent Document 4 2 anhydride. Although these cured products give high transparency, the heat resistance is not sufficient in view of flexibility of the skeleton and bifunctionality as compared with the aromatic acid anhydrides. Further, the isocyanurate compound of Patent Document 5 is trifunctional, but the transparency of the cured product is not sufficient due to the coloration derived from isocyanurate.

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

The object of the present invention is to obtain a thermosetting resin composition comprising a multifunctional acid anhydride and a multifunctional acid anhydride which give a cured product excellent in toughness, heat resistance, transparency and color resistance.

The present inventors have found that a compound obtained by reacting a mixture of a polyhydric alcohol having at least three hydroxyl groups in at least one molecule with a mixture of nuclear hydrogenated anhydrous trimellitic acid halide and anhydrous trimellitic acid halide or a nuclear hydrogenated anhydrous trimellitic acid halide The present inventors have found that a cured product having toughness, heat resistance, and color resistance is imparted while maintaining high optical characteristics, and thus the present invention has been accomplished.

That is, the present invention provides a compound represented by the following general formula (1):

^{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6 are ^{independent, R 1, R 3, R} 4, R 5, R 6 is a hydrogen atom, a hydroxyl group, having a carbon number of 1 to 11, respectively 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 each represent an integer of 1 to 11; (A) containing at least three hydroxyl groups in a molecule, a mixture of a nuclear hydrogenated anhydrous trimellitic acid halide and anhydrous trimellitic acid halide, or a mixture of a hydrogenated anhydrous trimellitic acid halide and a polyhydric alcohol Polyfunctional acid anhydride.

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, a nuclease hydrogenated trimellitic acid halide and anhydrous trimellitic acid A halide-containing mixture or a nuclear hydrogenated anhydrous trimellitic acid halide.

Further, it is preferable that 10% to 75% of the total number of hydroxyl groups of the polyhydric alcohol (A) or (B) reacts with trimellitic anhydride halide and the remaining hydroxyl groups are reacted with the hydrogen peroxide-added trimellitic acid halide Polyfunctional acid anhydride.

(A) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 in the} general formula (1) are a hydroxyalkyl group having 1 to 4 carbon atoms or the alkyl group A mixture of a polyhydric alcohol (B) obtained by reacting at least one member selected from the group consisting of ethylene oxide, propylene oxide, isobutylene, ethylene oxide, propylene oxide, And a carboxylic acid anhydride.

Further, the polyhydric alcohol (A) or (B) is a polyfunctional acid anhydride having 3 to 6 alcohols.

Further, the present invention relates to a polyfunctional acid anhydride wherein the polyhydric alcohol (A) is trimethylol or dipentaerythritol.

The polyhydric alcohol (B) may be added to the polyfunctional acid anhydride, which is a dipentaerythritol ethylene oxide adduct, dipentaerythritol propylene oxide adduct, dipentaerythritol tetrahydrofuran adduct, dipentaerythritol caprolactone adduct, .

Further, the present invention relates to a polyfunctional acid anhydride wherein the polyhydric alcohol (B) is a pentaerythritol 4 mole ethylene oxide adduct, a dipentaerythritol 6 mole ethylene oxide adduct, or a dipentaerythritol 4 moles caprolactone adduct.

Further, the present invention relates to a thermosetting resin composition comprising a compound having at least one epoxy group in a molecule and the polyfunctional acid anhydride.

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

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

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

Further, when the aromatic epoxy resin is selected from (4- (1,1-bis (p-hydroxyphenyl) -ethyl) -?,? - dimethylbenzyl) phenol type epoxy resin and bisphenol A epoxy resin Wherein the polyfunctional acid anhydride is at least one selected from the group consisting of polyfunctional acid anhydrides.

The present invention also relates to a thermosetting resin composition comprising the polyfunctional acid anhydride, wherein the compound having at least one epoxy group in one molecule is a copolymerizable epoxy resin.

The thermosetting resin composition comprising the polyvalent alcohol (A), the trimellitic anhydride halide, and the particles (C-1) or the fibers (C-2) not compatible with the nucleus hydrogenated trimellitic acid halide .

Further, the present invention relates to the thermosetting resin composition wherein the particles (C-1) are inorganic particles.

Further, the present invention relates to the thermosetting resin composition wherein the fiber (C-2) is glass fiber.

Further, the present invention relates to the above-mentioned thermosetting resin composition, wherein the fiber (C-2) is a glass cloth made by spinning a glass fiber and further forming a woven fabric.

The present invention also relates to a prepreg in which the shape of the thermosetting resin composition is given in a semi-cured state.

Further, the present invention relates to a varnish obtained by adding a solvent to the thermosetting resin composition.

The present invention also relates to a cured product obtained by curing the thermosetting resin composition.

The present invention also relates to a thermosetting resin cured product in which the difference in optical refractive index between the thermosetting resin after curing and the particle (C-1) or the fiber (C-2) is 0.005 or less.

The polyfunctional acid anhydride of the present invention can be used as a curing agent for an epoxy resin. The thermosetting resin composition of the present invention is excellent in stability and the cured product of the present invention is excellent in transparency, toughness, heat resistance, and coloring resistance, and can be applied to coatings for civil engineering construction, FRP, printed wiring boards, It is suitable for an electric and electronic material such as an ink, an adhesive, a sealant, a sealing agent and the like, and also for a display device such as an LED encapsulant, an optical waveguide, a liquid crystal display, a plasma display, an EL display,

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.

(Mode 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.

(1): < EMI ID =

^{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6 are ^{independent, R 1, R 3, R} 4, R 5, R 6 is a hydrogen atom, a hydroxyl group, having a carbon number of 1 to 11, respectively 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 each represent an integer of 1 to 11; ).

R ¹ , R ³ , R ⁴ and R ^{6 which} are plural exist in the general formula (1), when R ¹ , R ³ , R ⁴ and R ⁶ are different from each other, . For example, when 1 = 2, four R ¹ groups may be the same substituent, some of them may be the same or different, or all substituents may be different. R ³ , R ⁴ and R ⁶ are also the same as R ¹ .

Specific examples of the polyhydric alcohol (A) include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,4-butanetriol, 2-hydroxy- 2,5-pentanetriol, 1,3,5-pentanetriol, 3-methylpentane-1,3,5-triol, 1,2,6-hexanetriol, 1,2,8- Triethanol, 1,1,2,2-ethanetetraol, ditrimethylol propane, erythritol, pentaerythritol, pentaerythritol, 1,2,3,5-pentanetetraol, 1,2,4,5-pentanetetraol, 1,1,5,5-pentanetetraol, 1,2,5,6-hexanetetraol, Tetraols such as 2,7,8-octanetetraol and 1,2,9,10-decanetetraol, polyols such as dipentaerythritol and polyglycerin, and the like.

Of these, use of a polyhydric alcohol having 3 to 6 hydroxyl groups in one molecule is excellent as a curing agent. Particularly preferred are pentaerythritol, ditrimethylol propane and dipentaerythritol because of good properties of the cured product cured using the above-mentioned curing agent and ease of obtaining the material.

In the present invention, the polyhydric alcohol (B) refers to a compound obtained by addition polymerization of at least one member selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester to the polyhydric alcohol (A). In addition, the polyhydric alcohol (B) may be optimized for reactivity or the 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, trimethylolpropane caprolactone adduct, pentaerythritol ethylene oxide adduct, Pentaerythritol tetrafluoroethylene, pentaerythritol propylene oxide adduct, pentaerythritol tetrahydrofuran adduct, pentaerythritol caprolactone adduct, dipentaerythritol ethylene oxide adduct, dipentaerythritol propylene oxide adduct, dipentaerythritol tetrahydrofuran Adducts, dipentaerythritol caprolactone adducts, and the like.

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

The number of carbon atoms of the hydrocarbon group is preferably 1 to 11. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a linear or branched pentyl group, A cyclohexyl group, an ethyl cyclohexyl group, or an alicyclic hydrocarbon group such as a phenyl group, a tolyl group, a naphthyl group or a methyl naphthyl group, or an aliphatic hydrocarbon group such as a methyl group, , Benzyl group, naphthylmethyl group, and other aromatic substituted alkyl groups. Among them, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group is preferable in view of good transparency of the cured product of the present invention, and the methyl group and the ethyl group are more preferable in terms of giving 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 means an atomic group in which at least one hydrogen atom of a linear or branched alkyl group is substituted with a hydroxyl group.

The number of carbon atoms of the hydroxyalkyl group is preferably 1 to 4. Specific examples thereof include those in which one or two 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. Among them, in the present invention, it is preferable that one hydroxyl group is substituted for the terminal carbon in view of easy reaction. A hydroxymethyl group and a hydroxyethyl group are more preferred because the hardenability and the heat resistance of the cured product of the present invention are good.

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

The alkylene oxide preferably has 2 to 8 carbon atoms. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like. These alkylene oxides may be one kind or a mixture of two or more kinds as required. Of these, at least one kind selected from ethylene oxide and propylene oxide is preferable in the present invention since it is easily available and inexpensive.

The amount of the alkylene oxide to be used is generally 0.1 to 6.0 equivalents, preferably 0.2 to 2.0 equivalents of a cyclic ether of a 3-membered ring, per 1 equivalent of the hydroxyl group of the polyhydric alcohol (A). Within this range, the resulting cured product has good heat resistance and toughness.

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 among cyclic hydrocarbons having 4 or more rings is substituted with oxygen.

The cyclic ether is preferably a 4- to 6-membered ring, and specific examples thereof include oxetane, tetrahydrofuran and tetrahydropyran. These cyclic ethers may be one kind or a mixture of two or more kinds as required. Among them, tetrahydrofuran is preferable in the present invention because it is easily available and inexpensive.

The amount of the cyclic ether to be used is 0.1 to 6.0 equivalents, preferably 0.2 to 2.0 equivalents, of a cyclic ether to 1 equivalent of the hydroxyl group of the polyhydric alcohol (A). Within this range, the resulting cured product 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 cyclic hydrocarbons.

The cyclic ester preferably has 2 to 6 carbon atoms. Specific examples of cyclic esters include acetolactone, propiolactone, butyrolactone, valerolactone and caprolactone. These cyclic esters may be one kind or a mixture of two or more kinds as required. Among them, caprolactone is preferable in the present invention because it is easily available and inexpensive.

The cyclic ester is used in an amount of 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). Within this range, the resulting cured product has good heat resistance and toughness.

The anhydrous trimellitic acid halide (1,2,4-benzenetricarboxylic acid-1,2-anhydride halide) used in the present invention is used for introducing an acid anhydride group into a polyhydric alcohol and converting it into a polyfunctional acid anhydride compound do. Accordingly, the acid anhydride group can be introduced without carrying out the ring-opening esterification of the acid anhydride group. It is also excellent in heat resistance from a rigid skeleton derived from an aromatic.

Nucleus hydrogenated anhydrous trimellitic acid halide (cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride halide) used in the present invention is used for the same purpose as the anhydrous trimellitic acid halide. In addition, since it is added with nuclear hydrogen, it is less discolored even in heat resistance and light resistance, and the cured product is excellent in toughness while maintaining high optical characteristics.

Examples of the trimellitic anhydride halide and the hydrogenated trimellitic anhydride halide include fluorides, chlorides, bromides and iodides. Of these, chlorides are preferred for ease of reaction.

In the present invention, the molar ratio of the used trimellitic anhydride halide and the hydrogenated trimellitic anhydride halide is 1: 99 to 99: 1, preferably 30: 70 to 70: 30, to be. The reaction ratio of the hydroxyl group of the polyhydric alcohol (A) or (B) with the mixture of the trimellitic acid anhydride halide and the nucleus hydrogenated trimellitic acid halide is approximately the ratio of the trimellitic anhydride halide to the nuclease hydrogenated trimellitic acid halide Molar ratio. As the polyfunctional acid anhydride of the present invention, at least 5 to 95% of the total number of hydroxyl groups of the polyhydric alcohol (A) or (B) reacts with anhydrous trimellitic acid halide, and the remaining hydroxyl groups and N- Preferably at least 10% but not more than 75% of the total number of hydroxyl groups of the polyhydric alcohol (A) or (B) is reacted with anhydrous trimellitic acid halide, and the remaining hydroxyl groups and nuclear hydrogen addition And anhydrous trimellitic acid halide.

The synthesis of the polyfunctional acid anhydride of the present invention can be carried out by a known method. In the reaction of the polyhydric alcohol (A) or (B) with a mixture of anhydrous trimellitic acid halide and nuclear hydrogenated anhydrous trimellitic acid halide or with a hydrogenated anhydrous trimellitic acid halide (hereinafter referred to as "halide") The method of adding the compound is not particularly limited, and any addition method may be employed. For example, a method of dissolving a polyhydric alcohol (A) or (B) and a basic substance in a solvent and then slowly adding the halide in the solvent, or conversely, the above-mentioned halide A method in which a mixed solution of a polyhydric alcohol (A) or a basic substance (B) and a basic substance is dropped in a stream, a method in which a basic substance is dropped into a mixed solution of a halide and a polyhydric alcohol (A) or (B) A method in which a solution of a halide and a solution of a basic substance are simultaneously dripped into the solution of (A) or (B).

In the reaction of a polyhydric alcohol (A) or (B) in the presence of a basic substance with a halide, a basic substance is neutralized at the same time as the reaction progresses, thereby generating a hydrochloride. The hydrochloride is removed by filtration, and the filtrate is concentrated to obtain a crude product of the polyfunctional acid anhydride of the present invention at a high yield. This is dissolved in an appropriate solvent, washed with water, concentrated, and then dried under reduced pressure to obtain a polyfunctional acid anhydride having a high purity. If necessary, recrystallization is carried out with a suitable solvent to obtain a polyfunctional acid anhydride having a higher purity.

The amount of the polyhydric alcohol (A) or (B) to be used is usually the hydroxyl group equivalent, and when the sum of the hydroxyl equivalent of the mixture of the trimellitic anhydride halide and the hydrogenated anhydrous trimellitic acid halide is 1.0, When the hydroxyl group equivalent of the melitic acid halide is 1.0, it is 0.6 to 1.0, preferably 0.8 to 1.0. Within this range, the hydroxyl groups of the polyhydric alcohol (A) or (B) are all esterified, and the anhydrous trimellitic acid halide and the hydrogenated anhydrous trimellitic acid halide are not left in the system.

The solvent that can be used in the reaction of the halide and 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- (2-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, Halogen-containing solvents such as methane, chloroform, 1,2-dichloroethane and the like, organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, And the like; ester-based solvents such as γ-butyrolactone, ethyl acetate, butyl acetate and the like; esters such as 1,3-dimethyl- An aromatic solvent having a hydroxyl group such as phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p- . These solvents may be used alone or in combination of two or more.

When the polyhydric alcohol (A) is reacted with the halide, the reaction temperature is -10 ° C to 80 ° C, preferably 0 ° C to 70 ° C, and more preferably 10 ° C to 60 ° C. Examples of the solvent include cyclic ethers and cyclic esters used in producing the polyhydric alcohol (B) from the polyhydric alcohol (A). When the reaction temperature is higher than 80 ° C, the polyhydric alcohol (A) The polyhydric alcohol (B) is obtained, and the reaction rate of the polyhydric alcohol (A) and the halide is lowered. The reaction time is not particularly limited, but is generally from 10 minutes to 48 hours, preferably from 30 minutes to 24 hours. The reaction is usually carried out at normal pressure, but may be carried out under pressure or under reduced pressure, if necessary.

When the polyhydric alcohol (A) is reacted with the cyclic ether or the cyclic ester to produce the polyhydric alcohol (B), the reaction temperature is 80 to 250 캜, preferably 90 to 220 캜, more preferably 100 to 200 캜 / RTI > The reaction time is not particularly limited, but is generally from 10 minutes to 48 hours, preferably from 30 minutes to 24 hours. The reaction is usually carried out at normal pressure, but may be carried out under pressure or under reduced pressure, if necessary.

The concentration of the solute in the solvent in the reaction for obtaining the polyfunctional acid anhydride is usually from 5% by mass to 50% by mass, preferably from 10% by mass to 40% by mass, from the viewpoint of controlling the side reaction and filtering the precipitate. In the present reaction, the solute is more preferably in a range of 10 mass% or more and 40 mass% or less in the solvent.

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

The basic substance is used to neutralize the hydrogen chloride generated with the progress of the reaction. The kind of the basic substance to be used is not particularly limited, but organic tertiary amines such as pyridine, triethylamine and N, N-dimethylaniline, and inorganic basic substances such as potassium carbonate and sodium hydroxide can be used. Pyridine and triethylamine are preferable because they are available at low cost and because they are rich in solubility in a liquid, thereby facilitating the reaction operation. Inorganic basic materials are also preferable because they can be obtained at low cost.

Although the amount of the basic substance to be used is not particularly limited, it is usually 1.0 to 30 moles per mole of the total molar amount of the halides, when the total number of moles of the halides is 1.0, 1.2 molar equivalents to 20 molar equivalents, and more preferably 1.5 molar equivalents to 10 molar equivalents.

In the water washing operation, the polyfunctional acid anhydride undergoes partial hydrolysis to change into polyvalent carboxylic acid, but the polyvalent carboxylic acid thus produced can be easily returned to the polyfunctional acid anhydride by heat treatment under reduced pressure. The temperature of the heat treatment under this reduced pressure is 80 to 200 占 폚, preferably 100 to 180 占 폚, the degree of vacuum is 50 KPa or less, preferably 10 Kpa or less, and the upper limit of the heating time is not particularly limited, But is usually from 10 minutes to 48 hours, preferably from 30 minutes to 24 hours.

The polyfunctional acid anhydride of the present invention thus obtained can be further purified. As the purification method in this case, it can be arbitrarily carried out by recrystallization, sublimation, washing, activated carbon treatment, column chromatography or the like. These purification methods may be repeated or combined. The purity of the polyfunctional acid anhydride of the present invention thus obtained is, for example, an area ratio (ratio) of a peak obtained by an analysis of gel permeation chromatography (hereinafter referred to as "GPC") or the like, 95% or more, and more preferably 98% or more.

Preservation of the polyfunctional acid anhydride is preferably carried out at a low temperature avoiding high humidity in order to prevent the opening of the acid anhydride ring by hydrolysis. Specifically, when the container is stored in a refrigerator in a container having good sealability, it is resistant to long-term storage. The polyfunctional acid anhydride may be used in the subsequent polymerization reaction immediately after the purification to prevent moisture absorption. The storage period at that time is usually within 100 hours, preferably within 50 hours, more preferably within 24 hours.

The multifunctional acid anhydride of the present invention and a compound capable of undergoing curing reaction may be combined to form a thermosetting resin composition. In this case, the compound having an acid anhydride group and a functional group capable of reacting with heat is not particularly limited, but a compound having an epoxy group is preferably used.

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

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

Examples of the aromatic epoxy resin include novolak type epoxy resins such as cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl-phenol type epoxy resin and naphthol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy Bisphenol S type epoxy resin, bisphenol type epoxy resin such as bisphenol type epoxy resin, trisphenol methane type epoxy resin, glyoxyl type epoxy resin, (4- (4- (1,1-bis (p- ?,? - dimethylbenzyl) phenol) type epoxy resins. Among them, in the present invention, in consideration of heat resistance and coloring resistance, a bisphenol A type epoxy resin, (4- (4- (1,1-bis (p- hydroxyphenyl) -ethyl) -α, ) Phenol) type epoxy resin is preferable.

Examples of the aliphatic epoxy resin include an epoxy resin having an alicyclic structure and an epoxy resin having no aliphatic cyclic structure. The epoxy resin having an aliphatic cyclic structure is characterized by having at least one cyclic aliphatic structure in one molecule. (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and an aliphatic cyclic diene (dicyclopentadiene, norbornadiene, (Bisphenol A, bisphenol F) -type epoxy resin, alicyclic epoxy resin, etc., which are derived from a polycondensation product of a polycondensation product of a polycondensate and a modified product thereof, , An epoxy resin having a dicyclopentadiene structure, and an epoxy resin having a triglycidyl isocyanurate structure. Specific examples thereof include cyclohexanediol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, 2,2-bis (hydroxyalkyl) -1 -Butane-1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts of butanol.

Examples of the compound having at least one epoxy group in a molecule not having an aliphatic cyclic structure include glycidyl ethers derived from a straight-chain or branched alcohol such as hexane diglycidyl ether.

Examples of the copolymerizable epoxy resin include monomers having an unsaturated double bond and an epoxy group such as glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate glycidyl ether, hydroxybutyl (meth) And a monomer having another polymerizable unsaturated group are copolymerized with each other. The other monomer is not particularly limited, and any monomer can be used as far as it can copolymerize with a monomer having both unsaturated double bonds and an epoxy group. (Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate and the like. Examples of the vinyl monomer include vinyl compounds such as ethylene, propylene, styrene, vinyl acetate and vinyl chloride; (Meth) acrylates such as hydroxyethyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate, (Meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, And glycol ether monoalkyl ether (meth) acrylates such as acrylate.

Examples of the particles (C-1) used in the resin composition of the present invention include polymethyl methacrylate, polystyrene and nylon as the organic particles, and talc, calcined clay, , 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, sulfuric acid Calcium sulfate 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 As a colloidal solution in which fine powder containing no dispersing solvent or a solvent is dispersed into the market Emitter can be used to get. These may be used alone or in combination of two or more. Examples of the dispersion solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and dimethyl dimethylacetamide, esters such as ethyl acetate and butyl acetate, and nonpolar solvents such as toluene and xylene. The thermosetting resin composition May be selected and used. Further, inorganic particles are preferable from the viewpoint of dimensional stability. Particularly, alumina and silica are preferable in view of versatility and low cost.

The fiber (C-2) used in the resin composition of the present invention may be any of carbon fiber, glass fiber, casein fiber, peanut protein fiber, corn protein fiber, soybean protein fiber, algin fiber, chitin fiber, mannan fiber, , Nylon fibers, polyvinylidene chloride fibers, polyvinyl chloride fibers, polyester fibers, polyacrylonitrile fibers, modacrylic fibers, polyethylene fibers, polypropylene fibers, polystyrene fibers, polyetherester fibers and polyurethane fibers. . These may be used alone or in combination of two or more. Of these, glass fibers are preferable from the viewpoint of versatility. There are no particular limitations on the kind of the glass fibers used in the present invention. Examples of the glass fibers include, but are not limited to, those obtained by impregnating the thermosetting resin composition of the present invention and obtaining a cured product excellent in dimensional stability In order to achieve this, a glass cloth is suitable. In consideration of adhesion with the thermosetting resin composition of the present invention, the glass fiber is preferably treated with a silane coupling agent.

The particles (C-1) and the fibers (C-2) may be either one or both of them depending on the performance to be obtained.

The resin composition of the present invention may contain other components. Examples of the other components include an inorganic filler, an antioxidant, a light stabilizer, and an ultraviolet absorber.

The antioxidant that can be used in the resin composition of the present invention is not particularly limited as long as it is a known antioxidant such as phenol-based, sulfur-based, phosphorus-based antioxidant. However, in view of the characteristics of the present invention, it is preferable to select colorless, heat at the time of curing, and those which are difficult to be colored even when they are used for a long time as a circuit board after sealing.

Examples of the phenol-based antioxidant include monophenols, bisphenols, and polymeric phenols.

Specific examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate Nate and so on.

Examples of the phosphorus antioxidant include phosphites, oxaphosphphenanthrene oxides and the like.

These antioxidants may be used alone or in combination of two or more. The amount of the antioxidant to be used is usually 0.008 to 1 part by mass, preferably 0.01 to 0.5 part by mass based on 100 parts by mass of the resin composition of the present invention. In the present invention, a phosphorus-based antioxidant is preferable.

As the photostabilizer that can be used in the resin composition of the present invention, a known photostabilizer 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, heat at the time of curing, or a material that is hardly colored even when used for a long period of time. Representative examples thereof include hindered amines and the like.

As the ultraviolet absorber that can be used in the resin composition of the present invention, a known ultraviolet absorber can be used, and there is no particular limitation. Examples of the ultraviolet absorber include benzotriazole-based, hydroxyphenyltriazine-based, and the like, and they can be used in combination with the light stabilizer.

In the present invention, it is preferable to use an ultraviolet absorber having a low coloring ability over time. For example, there may be mentioned propanoic acid-2- [4- [4,6-bis ([1,1'-biphenyl] -4- Hydroxyphenyl] -isooctyl ester (for example, TINUVIN 479, manufactured by Chiba Japan K.K.).

In order to improve the intrinsic coloring property of the present invention, a hydroxyphenyltriazine-based ultraviolet absorber and a hindered amine light stabilizer are used together.

The resin composition of the present invention may contain various additives such as a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, Based resin, a silicon-based resin, and the like may be added as needed.

A silane coupling agent, a releasing agent, a leveling agent, a surfactant, a dye, a pigment, and an organic light diffusion filler may be added to the resin composition of the present invention.

For the purpose of improving the heat resistance and the light resistance property, a known general metal salt may be added to the resin composition of the present invention. (Zinc salts such as stearic acid, behenic acid and myristic acid, tin salts and zirconium salts), phosphoric acid ester metal (zinc salts such as octylphosphoric acid and stearylphosphoric acid) Metal compounds such as alkoxy metal salts (tributyl aluminum, tetrapropyl zirconium and the like), acetylacetone salts (acetylacetone zirconium chelate, acetylacetone titanium chelate and the like) and the like. These may be used alone or in combination of two or more. By adding the metal salt, the heat resistance and coloring resistance of the present invention can be improved.

In the resin composition of the present invention, in order to accelerate the reaction by heat, a curing catalyst is generally added in order to accelerate the reaction in response to heat or adjust the curing temperature. Any of those known in the art may be used as far as they have the effect of accelerating the curing reaction.

Examples of the curing catalyst include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2- Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl- Ethyl-2-undecylimidazole, 2,4-diamino-6- (2'-methylimidazole (1 ')) ethyl- (1 ')) ethyl-s-triazine, 2,4-diamino-6- (2'-ethyl-4-methylimidazole 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, Imidazoles and salts with polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid, amides such as dicyandiamide, Diacid compounds such as bicyclo (5,4,0) undecene-7, salts thereof such as tetraphenylborate and phenol novolac, salts with polyvalent carboxylic acids or phosphines, tetrabutylammonium bromide, acetyl Ammonium salts such as trimethylammonium bromide and trioctylmethylammonium bromide; organic bases such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, hexafluorostinophosphonium salt and the like Phosphines, phosphonium compounds, 2,4,6-trisaminomethylphenol and other phenols, tin octylate, cobalt octylate, zinc octylate, zirconium octylate, There may be mentioned organometallic compounds such as cobalt naphthenate. Further, a microcapsule-type curing catalyst in which a curing accelerator is microcapsules can be given.

Which of these curing catalysts to be used should be appropriately selected depending on the required characteristics. The curing catalyst is used in an amount of usually 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 the present invention can be uniformly mixed with each component in the same manner as the conventionally known method to obtain the cured product. For example, the thermosetting resin composition of the present invention is obtained by thoroughly mixing the epoxy resin and the acid anhydride curing agent and, if necessary, the curing accelerator and other components, as necessary, using an extruder, a kneader, a roll or the like until they become uniform . Since the thermosetting resin composition of the present invention is a solid at room temperature, it is possible to use a method such as molding after melting, molding using a casting mold or a transfer molding machine, and further curing by heating.

In addition, the thermosetting resin composition of the present invention is preferably a thermosetting resin composition containing at least one selected from the group consisting of toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, dimethylformamide, dimethylacetamide, It may be diluted with a solvent such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like and used as a varnish. Since the thermosetting resin composition of the present invention is usually solid at room temperature, it is more preferable that the thermosetting resin composition is diluted with a solvent and used. Particularly, when the glass cloth is impregnated with the glass cloth, dilution with a solvent is performed.

The solvent can be used as one or more mixed solvents in consideration of the viscosity and the drying speed when the thermosetting resin composition of the present invention is used. The solvent is used in an amount of usually 10 to 200 parts by mass, preferably 15 to 100 parts by mass, per 100 parts by mass of the thermosetting resin composition of the present invention, depending on workability at the time of use and drying speed.

In the case of obtaining the thermosetting resin composition of the present invention which is diluted with a solvent, the components can be prepared by mixing and dissolving them in accordance with a conventional method. For example, each component is put into a round bottom flask equipped with a stirrer and a thermometer, and stirred at 40 to 80 DEG C for 0.5 to 6 hours to obtain a varnish of a thermosetting resin composition. At this time, a method of adjusting the varnish of the epoxy resin, the acid anhydride curing agent + the curing catalyst and the varnish of the additive separately and mixing them at the time of use is particularly preferable. As described above, in the case of adding fine particles, the treatment may be carried out by a generally known dispersing method such as a homomixer, a sand mill, a high-speed stirrer, a microfluidizer, or a three-axis roll.

The varnish of the thermosetting resin composition of the present invention thus obtained is molded by a known method, dried and further cured by heating. For example, a method of pouring the resin into a mold, followed by heating and drying, followed by curing, or by a known method such as a bar coater, an air knife coater, a die coater, a gravure coater, offset printing, flexo printing, A method in which the composition is coated on a metal plate or a release film or the like and heated and dried, followed by curing, a method in which the composition is impregnated with a glass cloth, followed by heating and drying and then curing; A method for use as a coating agent used together, and the like. In the thermosetting resin composition of the present invention, since the curing agent volatilizes at the time of curing, the composition ratio of the film is changed and the refractive index is not changed, so that a stable transparent film can be obtained. Therefore, it is suitable for the production of an optical sheet. In addition, since the surface of the cured film is not roughened due to the volatilization of the curing agent, or the physical properties of the cured film are not changed, a smooth and excellent hardness film can be obtained.

The drying temperature of the varnish of the thermosetting resin composition of the present invention is usually from 60 to 200 캜 although it depends on the solvent and air volume to be used. It is also possible to obtain a prepreg by impregnating the glassy sheet-like base material such as a glass cloth with the varnish and drying the solvent so that the thermosetting resin composition of the present invention is semi-cured. The drying conditions at this time are not particularly limited, but the temperature is preferably 100 to 180 DEG C and the time is preferably 1 to 30 minutes.

The present invention also includes a prepreg in which the thermosetting resin composition of the present invention is shaped in a semi-cured state.

The cured product obtained by curing the thermosetting resin composition of the present invention is also included in the present invention. The present invention also includes a cured product obtained by preparing a prepreg impregnated with a thermosetting resin composition of the present invention in a fiber, followed by drying and curing. 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 the refractive index caused by volatilization of the curing agent during curing. The curing temperature and time of the thermosetting resin composition of the present invention are from 80 to 200 占 폚 for 2 to 200 hours. As the curing method, it is possible to cure at one time at a high temperature, but it may be cured at a low temperature of 150 DEG C or less for a long time. The initial curing may be performed at 80 to 150 占 폚, and post-curing may be performed at 100 占 폚 to 200 占 폚.

As the glass cloth for preparing the prepreg, a known commercially available glass cloth can be used. Among them, E glass which is generally used for resin reinforcement is less alkali metal oxide and is suitable as an alkali-free glass for the use of the present invention. There are no particular restrictions on the type of glass cloth used in the present invention. Examples of the commercially available glass cloth include a woven fabric using glass fiber, a nonwoven fabric, a knitted fabric, etc. In the present invention, In order to obtain this, it is preferable that the surface roughness of the glass cloth is small. Considering the conditions of drying and semi-curing at the time of preparing the prepreg, the thickness of the glass cloth is usually 100 占 퐉 or less, preferably 50 占 퐉 or less. A prepreg may be prepared using a material having a thickness of about 25 mu m or less and two or more sheets may be superimposed upon each other at the time of curing to form an optical sheet of the present invention. The diameter of the glass fiber used for the glass cloth is preferably as small as possible in consideration of transparency and the like and is preferably 10 占 퐉 or less. In consideration of adhesion with the thermosetting resin composition of the present invention, the glass fiber is preferably treated with a silane coupling agent. The refractive index is 1.51 to 1.57, which is generally available, more preferably 1.55 to 1.57.

In the present invention, it is preferable that the refractive index of the cured product of the present invention is smaller than the refractive index of the glass fiber used. Specifically, it is preferable that the difference from the refractive index of the glass fiber is ± 0.01, and it is more preferable that 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 can be obtained. It is also possible to obtain an optical sheet having superior transparency and smoothness by applying, drying and curing the thermosetting resin composition of the present invention on these optical sheets.

The thermosetting resin cured product of the present invention can be used as a substitute for glass used for a display device such as a liquid crystal display, a plasma display, an EL display, a portable device, or a solar cell. In addition, materials surrounding the liquid crystal display such as a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correcting film, an adhesive, and a polarizer protective film, Can also be used.

(Example)

Next, the present invention will be described in more detail with reference to Examples. The present invention is not limited at all by the following examples. In the synthesis of the compound, the reaction was terminated at the time when disappearance of the starting alcohol was confirmed by gel permeation chromatography (hereinafter referred to as "GPC"). In the examples, TMAC is anhydrous trimellitic chloride, HTAC is nuclear hydrogenated anhydrous trimellitic chloride, THF is tetrahydrofuran, TMP is trimethylolpropane, DPE is dipentaerythritol, PE4EO , DE6EO represents a dipentaerythritol 6 mole ethylene oxide adduct, DPE4C represents a dipentaerythritol 4 mole caprolactone adduct, and MEK represents methyl ethyl ketone.

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

45.66 g (400 mmol) of caprolactone was added to 25.43 g (100 mmol) of dipentaerythritol while nitrogen purge was carried out, and the mixture was stirred at 180 ° C for 12 hours, To obtain 71.09 g of dipentaerythritol 4-mol caprolactone adduct.

Synthesis Example 2: Preparation of copolymerizable 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, and 200 g of methyl ethyl ketone as a reaction initiator were added to a flask equipped with a stirrer, a reflux condenser, 1 g of azobisisobutyronitrile was added, and polymerization reaction was carried out at 80 DEG C for 5 hours.

After completion of the reaction, the reaction mixture was heated to 90 占 폚 and the solvent was distilled off under reduced pressure to obtain a copolymer type epoxy resin. The resulting copolymer-type epoxy resin had a number average molecular weight of 15,000 in terms of polystyrene by GPC, a weight average molecular weight of 30,000, and an epoxy equivalent of 470 g / eq.

Example 1-1: Synthesis of polyfunctional acid anhydride

A flask equipped with a stirrer, a reflux condenser and an agitator was added with 36 g of THF to 23.34 g (108 mmol) of HTAC while purging with nitrogen to obtain a homogeneous solution. The solution was cooled to 5 ° C while stirring, and 10.08 g (127.5 mmol) of pyridine and 54 g of THF were added to 4.44 g (33 mmol) of TMP to uniformly maintain the liquid temperature at 10 ° C. or lower While slowly dropping. After completion of dropwise addition, the mixture was stirred at room temperature for 1 hour, then heated to 50 DEG C, and the reaction was continued for 8 hours. Subsequently, the reaction solution was cooled to 20 占 폚, and the insoluble pyridine hydrochloride was removed by filtration, and then the filtrate was concentrated. The concentrate was dissolved in 120 ml of ethyl acetate, washed with 30 ml of water three times, and then dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated. The resulting concentrate was dissolved in 15 ml of ethyl acetate and recrystallized with toluene to obtain 16.7 g (yield: 75.2%) of the product.

This product was confirmed to be the desired compound by ¹ H-NMR.

¹ H-NMR (chloroform-d 1,? Ppm): 0.90-0.92 (m, 3H), 1.48-2.49 (m, 23H), 3.11-3.41

Example 1-2: Synthesis of polyfunctional acid anhydride

A flask equipped with a stirrer, a reflux condenser and an agitator was added with 7.8 g (36 mmol) of HTAC and 12 g of THF while nitrogen purge was carried out to obtain a homogeneous solution. This solution was cooled to 5 ° C while stirring, and 3.36 g (47.5 mmol) of pyridine and 18 g of acetone were added to 1.40 g (5.5 mmol) of DPE to obtain a homogeneous solution, which was gradually added dropwise did. After completion of dropwise addition, the mixture was stirred at room temperature for 1 hour, then heated to 50 DEG C, and the reaction was continued for 8 hours. Subsequently, the reaction solution was cooled to 20 占 폚, and the insoluble pyridine hydrochloride was removed by filtration, 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 then dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated. The resulting concentrate was dissolved in 5 ml of ethyl acetate and recrystallized from toluene to obtain 5.24 g (yield: 71.3%) of the product.

Examples 1-3 to 1-4

A polyfunctional acid anhydride was synthesized in the same manner as in Example 1-2 except that the polyhydric alcohol was changed to Table 1.

Example 1-5: Synthesis of polyfunctional acid anhydride

A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 78.6 g (363 mmol) of HTAC and 120 g of THF while purging with nitrogen, to obtain a homogeneous solution. This solution was cooled to 5 占 폚 while stirring, and 33.6 g (475 mmol) of pyridine and 180 g of THF were added to 28.5 g (55 mmol) of PE4EO, and the resulting solution was slowly added dropwise while maintaining the liquid temperature at 10 占 폚 or lower. After completion of dropwise addition, the mixture was stirred at room temperature for 1 hour, then heated to 50 DEG C, and the reaction was continued for 8 hours. Subsequently, the reaction solution was cooled to 20 占 폚, and the insoluble pyridine hydrochloride was removed by filtration, and then the filtrate was concentrated. The resulting concentrate was dissolved in 400 ml of ethyl acetate, washed with 100 ml of water three times, and then dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was removed by filtration, and the filtrate was concentrated. The resulting concentrate was dissolved in 40 ml of ethyl acetate and recrystallized with toluene to obtain 74.7 g (yield: 77.1%) of the product.

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

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

The polyfunctional acid anhydride of Example 1-6 was confirmed to be the target compound by ¹ H-NMR. FIG. 2 shows a chart of ¹ H-NMR.

¹ H-NMR (dimethyl sulfoxide -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 Co., Ltd., epoxy equivalent 181), 10 g of an aromatic epoxy resin NC-6300 (manufactured by Nippon Kayaku (Epoxy equivalent: 206, total chlorine content: 550 ppm) was added in an amount of 27 g (manufactured by NIPPON KOGYO KABUSHIKI KOGYO KABUSHIKI KOGYO KABUSHIKI KAISHA) , 23 g of RE-310S (liquid bisphenol A epoxy resin, epoxy equivalent 185, total chlorine amount 500 ppm) manufactured by Nippon Kayaku Co., Ltd., 0.3 g of zinc octyl as other components, 41 g of methyl ethyl ketone as a diluting solvent The resulting mixture was heated to 70 캜 and mixed to obtain a resin composition having a solid content of 70% by mass.

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

Examples 2-2 to 2-14 and 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 polyfunctional acid anhydride and MEK were changed to those shown 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 added and heated to 50 캜, To obtain a resin composition having a solid content of 60% by mass.

Example 2-16: Preparation of resin composition

Except that 35 g of the polyfunctional acid anhydride obtained in Example 1-1 and 41 g of MEK as a diluting solvent were used in place of the methyl ethyl ketone dispersion of colloidal silica (solid content: 30 mass%, Nissan 137 g of ORGANOSILICASOL MEK-ST (hereinafter referred to as MEK-ST, manufactured by Kagaku Kogyo Co., Ltd.) was added to obtain a diluted composition of the resin composition of the present invention having a solid content of 59 mass%.

Comparative Example 2-3: Preparation of resin composition

17 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 23 g of RE-310S (liquid bisphenol A epoxy resin, epoxy equivalent 185, total chlorine content 500 ppm) manufactured by Nippon Kayaku Co., Ltd., , 0.3 g of zinc octylate, and 33 g of acetone as a diluting solvent, to obtain a resin composition diluted composition having a solid content of 70% by mass.

Comparative Example 2-4: Preparation of resin composition

10 g of hydrogenated trimellitic anhydride, 50 g of the glycidyl methacrylate copolymer of Synthesis Example 2, 1 g of triphenylphosphine as a curing catalyst and 40 g of MEK as a solvent were mixed and heated to 50 캜 and mixed to obtain a solid content of 60 Mass%.

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

A shape of 40 mm x 25 mm x 1 mm was formed on a glass substrate with a heat resistant release tape and the thermosetting resin compositions of Example 2 and Comparative Example 2 were each molded to a thickness of about 800 mu m and dried at 80 DEG C for 50 minutes . Vacuum defoaming was performed once during drying to remove the 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.

And then cured in a drier at 140 캜 for 3 hours to obtain a cured product of the present invention. The obtained cured product was measured for glass transition point, toughness and color resistance, and is shown 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 tensile mode at a frequency of 1 Hz in a viscoelasticity measuring system (DMS-6000: Seiko Denshi Kyo Co., Ltd.).

(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 center was pressed was observed. The criteria are as follows.

◎: It does not crack and does not crack even when pressed strongly.

○: Even if pressed lightly, it does not crack, it does not crack, but when pressed strongly, it cracks.

△: When pressed lightly, it cracks, and when pressed hardly, it cracks.

X: Press slightly to divide.

(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 anhydrides of the present invention used in the cured products of Examples 3-1 to 3-5 have an acid anhydride having three or more functional groups and are alcohol aliphatic and have a large molecular weight, It can be considered that the toughness is excellent. On the contrary, the polyfunctional acid anhydride used in the cured product of Comparative Example 3-1 is bifunctional and may be considered to be inferior in heat resistance and toughness in that it is a low molecular weight. The cured product of Comparative Example 3-2 is considered to be inferior in heat resistance and toughness in that the acid anhydride is a monofunctional and low-molecular substance.

Examples 3-6 to 3-14 and Comparative Example 3-3

A cured product of the present invention was obtained in the same manner as in Example 3-1. The obtained cured product was measured for glass transition point, toughness and color resistance, and is shown 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 tensile mode at a frequency of 1 Hz in a viscoelasticity measuring system (DMS-6000: Seiko Denshi Kyo Co., Ltd.). The criteria are as follows.

?: Tg of 200 占 폚 or more

?: Tg of 190 占 폚 or more and 199 占 폚 or less

DELTA: Tg of 185 DEG C or higher and 189 DEG C or lower

X: Tg is 184 DEG C or lower

(2) Yellowing degree: The initial yellowing degree (YI) of the cured film of the cured resin composition and the yellowing degree (YI) after being left at 230 캜 for 20 minutes were measured with a spectrophotometer (U-3900H, manufactured by Hitachi High- (Yellowing degree: JIS K7105 / JIS K7373), and the difference (yellowing degree:? YI) was determined.

?:? YI is 0.4 or less

?:? YI is not less than 0.5 and not more than 0.7

DELTA: DELTA YI is not less than 0.8 and not more than 1.0

X: YI of 1.1 or more

As apparent from the above results, the cured product of the present invention is excellent in heat resistance, toughness and yellowing (coloring resistance). The polyfunctional acid anhydrides of the present invention used in the cured products of Examples 3-6 to 3-14 are superior in heat resistance and toughness in that they have trifunctional or higher acid anhydrides and alcohols as algae are aliphatic and have a large molecular weight . In addition, even though the aromatic ring has a skeleton, it also has excellent color resistance because it has an aliphatic ring. On the other hand, the polyfunctional acid anhydride used in the cured product of Comparative Example 3-3 has high yellowing degree and insufficient coloring resistance because it has aromatic rings only.

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, and 2-16 and Comparative Examples 2-1 to 2-2 to adjust the solid content to 50% by mass, and a commercially available glass cloth (E glass (E glass: about 750 占 퐉 thickness, optical refractive index: 1.560) was impregnated into the glass cloth, and the impregnated glass cloth was impregnated with a glass fiber nonwoven fabric (trade name: IPC106 type: about 30 占 퐉 thickness; plain weave; optical refractive index: 1.561). After raising the glass cloth, it was dried at 120 DEG C for 7 minutes. The sheet after drying was a solid film. It was inserted into a PET film which had been further subjected to releasing treatment, treated at 150 DEG C for 10 minutes while being pressed, and semi-cured to obtain a prepreg. Thereafter, it was cured in a dryer at 150 캜 for 3 hours to obtain a cured product of the present invention. Further, the resin composition of Example 2-16 was obtained in the same manner as in Example 3-1 to obtain a cured product of the present invention. Heat resistance, toughness, yellowing degree and dimensional stability were measured for each of the obtained cured products, and the results are shown in Table 6. The evaluation of heat resistance and yellowing degree is 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 占 폚 / 10 minutes in a viscoelasticity measuring system (DMA / SS-6000: Seiko Denshi Kyo Co., Ltd.). The criteria are as follows.

?: CTE of 25 ppm / K or less

?: CTE of 26 ppm / K or more and 35 ppm / K or less

?: CTE of 36 ppm / K or more and 45 ppm / K or less

X: CTE of 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 proofness and dimensional stability. The multifunctional acid anhydrides of the present invention used in the cured products of Examples 3-15 to 3-20 have trifunctional or higher acid anhydrides and the aliphatic alcohol is aliphatic and has a large molecular weight and is excellent in heat resistance and toughness . In addition, the cured product of the present invention, which contains a large amount of saturated alicyclic rings, has excellent color resistance, glass cross and the like, and is also excellent in dimensional stability. On the other hand, in Comparative Example 3-4, since it does not have a saturated alicyclic ring, the yellowing degree is high and the coloring resistance is insufficient. In addition, the low-molecular acid anhydride used in Comparative Example 3-5 is considered to be inferior in heat resistance and toughness.

Example 4

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

week)

Glass cloth a (IPC106 type, manufactured by Uni-Chika Co., Ltd., thickness: about 30 占 퐉, plain weave, optical refractive index: 1.561)

Glass cross b (IPC3313 type, thickness: about 75 mu m, plain weave, optical refractive index: 1.554, manufactured by Nitto Boseki Co., Ltd.)

As apparent from the above results, the refractive index of the thermosetting resin composition of the present invention was adjusted based on the refractive index of the glass cloth, thereby giving a cured product excellent in transparency without coloring.

The multifunctional acid anhydride and the thermosetting resin composition of the present invention can be used as a coating material for civil engineering construction, an electric and electronic material such as a paint in a FRP, a printed wiring board or a semiconductor field, a resist ink, an adhesive, a sealant, It is mainly suitable for a cured product used for a display device such as a liquid crystal display, a plasma display, an EL display, a portable device, or a solar cell.

Claims (19)

The following formula (1)

^{(Wherein, R 1, R 2, R} 3, R 4, R 5, R 6 are ^{independent, R 1, R 3, R} 4, R 5, R 6 is a hydrogen atom, a hydroxyl group, having a carbon number of 1 to 11, respectively 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 each represent an integer of 1 to 11; (A) containing at least three hydroxyl groups in one molecule and
A polyfunctional acid anhydride obtained by reacting a mixture of trimellitic anhydride halide and nuclear hydrogenated trimellitic acid halide or nuclear hydrogenated trimellitic anhydride halide. A polyhydric alcohol (B) obtained by reacting the polyhydric alcohol (A) according to claim 1 with at least one selected from the group consisting of an alkylene oxide, a cyclic ether and a cyclic ester;
A polyfunctional acid anhydride obtained by reacting a mixture of trimellitic anhydride halide and nuclear hydrogenated trimellitic acid halide or nuclear hydrogenated trimellitic anhydride halide. A process for producing a polyhydric alcohol (A), wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 in the} general formula (1) according to claim 1 are a hydroxyalkyl group having 1 to 4 carbon atoms and a trimellitic anhydride halide And a mixture of nuclear hydrogenated anhydrous trimellitic acid halide or nuclear hydrogenated anhydrous trimellitic acid halide. (B) obtained by reacting the polyhydric alcohol (A) according to claim 3 with at least one member selected from the group consisting of an alkylene oxide, a cyclic ether and a cyclic ester, an anhydride trimellitic acid halide, and an anhydrous anhydride tree A mixture of melitic acid halides or anhydride-treated trimellitic acid halide; and a polyfunctional acid anhydride. The method according to claim 1,
A polyfunctional acid anhydride in which the polyhydric alcohol (A) is trimethylol or dipentaerythritol. 3. The method of claim 2,
Wherein the polyhydric alcohol (B) is a dipentaerythritol ethylene oxide adduct, a dipentaerythritol propylene oxide adduct, a dipentaerythritol tetrahydrofuran adduct, and a dipentaerythritol caprolactone adduct. 3. The method of claim 2,
Polyfunctional acid anhydride wherein the polyhydric alcohol (B) is a pentaerythritol 4 mole ethylene oxide adduct, dipentaerythritol 6 mole ethylene oxide adduct, dipentaerythritol 4 moles 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. 9. The method of claim 8,
Wherein the compound having at least one epoxy group in one molecule is at least one selected from an aliphatic epoxy resin, an aromatic epoxy resin and a copolymerizable epoxy resin. 10. The method of claim 9,
Wherein the compound having at least one epoxy group in one molecule is at least one selected from an aliphatic epoxy resin and an aromatic epoxy resin. 10. The method of claim 9,
Wherein the aliphatic epoxy resin is an epoxy resin having an aliphatic cyclic structure. 10. The method of claim 9,
When the aliphatic epoxy resin is one kind selected from (4- (1,1-bis (p-hydroxyphenyl) -ethyl) -α, α-dimethylbenzyl) phenol type epoxy resin and bisphenol A epoxy resin Lt; / RTI > 9. The method of claim 8,
Wherein the compound having at least one epoxy group in one molecule is a copolymerizable epoxy resin. 9. The method of claim 8,
A thermosetting resin composition further comprising a particle (C-1) or a fiber (C-2) which is not compatible with the polyhydric alcohol (A), trimellitic anhydride halide and nuclear hydrogenated trimellitic acid halide. 15. The method of claim 14,
Wherein the particles (C-1) are inorganic particles. 15. The method of claim 14,
And the fiber (C-2) is a glass fiber. 17. The method of claim 16,
Wherein the fiber (C-2) is a glass cloth produced by spinning a glass fiber and further adding it. A prepreg in which the shape of the thermosetting resin composition according to claim 8 is given in a semi-cured state. A cured product obtained by curing the thermosetting resin composition according to claim 8.

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