TWI502015B - Resin composition and cured product thereof - Google Patents

Description

Resin composition and cured product thereof

The present invention relates to a resin composition excellent in ultraviolet (UV) absorption characteristics and a cured product thereof (Resin Composition and Cured Product thereof).

The phenol glyoxal resin obtained from phenol and glyoxal (dialdehyde) is effective as an insulating material such as a highly reliable semiconductor sealing material, a laminate (printed wiring board), and the like because of its UV absorption property. Wide range of applications such as Carbon-Fiber-Reinforced Plastic (CFRP), such as various electrical-electronic materials, molding materials, casting materials, laminate materials, coatings, adhesives, resists, and optical materials. A mixed component of the epoxy resin composition or an epoxy modified material used. In particular, the phenol glyoxal resin is useful as a constituent material of a laminate such as a packaged printed circuit board that has been subjected to quality management by automatic optical inspection (AOI) based on optical characteristics.

For example, as an example of an epoxy resin composition for AOI suitability, there is disclosed a phenol glyoxal resin (Fluorescent Phenol-glyoxal Condensation Product) which is produced under specific conditions, A composition with an epoxy resin having a specific epoxy value and a curing agent thereof. Here, examples of the curing agent include aromatic amines, polyamines, and polyfluorenes. An amine, a dicyandiamide, a phenol novolak resin, a melamine-formaldehyde resin, etc. (refer patent document 1).

Prior art literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2002-542389

In the above AOI, fluorescence measurement of a wavelength of about 450 nm to about 650 nm (especially an excitation wavelength of about 442 nm) and/or measurement of a UV absorbance of a wavelength of about 350 nm to about 365 nm are usually performed. As an AOI suitability, more excellent UV absorption characteristics are also required for previously known epoxy compositions.

As a person who can solve such a problem, the present invention as follows is provided.

The present invention provides a resin composition comprising: (A) a substituted phenol glyoxal resin obtained by reacting cresols and/or xylenols with glyoxal under an acid catalyst; (B) At least one selected from the group consisting of biphenyltetracarboxylic acid and its anhydride; and (C) an epoxy resin.

The above (B) is preferably selected from the group consisting of the compounds (1) to (4) shown below: [Chemical Formula 1]

The resin composition of the present invention usually contains 0.5% by mass to 30% by mass of the above (A) and 0.5% by mass to 30% by mass of the above (B) and 40% by mass to 98% by mass of the above (C).

The resin composition of the present invention preferably further contains (D) an epoxy resin hardener in an amount of 0.5% by mass to 50% by mass.

The above cresols are preferably selected from the group consisting of p-cresol, m-cresol and o-cresol. At least one of the group formed.

The above xylenol is preferably selected from the group consisting of 2,6-xylenol, 3,5-xylenol, 2,3-xylenol, 2,5-xylenol, 2,4-xylenol and At least one of the group consisting of 3,4-xylenol.

The glyoxal is preferably at least one selected from the group consisting of a monomeric glyoxal, an aqueous solution of a polymerized glyoxal and glyoxal.

The acid catalyst is preferably at least one selected from the group consisting of sulfuric acid, p-toluenesulfonic acid and oxalic acid.

The above epoxy resin is preferably a thermosetting epoxy resin.

The epoxy resin curing agent is preferably at least one selected from the group consisting of an aliphatic amine compound, an aromatic amine compound, a phenol novolac resin, an imidazole compound, and an acid anhydride compound.

In the present application, a cured product of the resin composition as described above is also provided.

The cured product of the resin composition of the present invention exhibits high UV absorption intensity and high fluorescence intensity. The product obtained by the resin composition of the present invention and the cured product thereof can improve the accuracy in the AOI and shorten the inspection time, and therefore is particularly effective for applications such as substrates for quality management by AOI.

Hereinafter, the present invention will be described in more detail.

The (A) substituted phenol glyoxal resin of the present invention is a cresol and/or a xylenol (hereinafter sometimes referred to as a substituted phenol), and a glyoxal in an acid catalyst. Get the reaction.

Examples of the cresols include p-cresol, m-cresol and o-cresol, and examples of the xylenol include 2,6-xylenol, 3,5-xylenol, and 2,3-. Xylenol, 2,5-xylenol, 2,4-xylenol, 3,4-xylenol, and the like.

In the present invention, at least one selected from the above-listed cresols and/or xylenols may be used as the substituted phenol, and one or two or more kinds of cresols may be used, and xylenol may be used. One or more of the classes, and a suitable mixture of these.

Among these, in terms of excellent UV absorption characteristics, p-cresol, a mixture of p-cresol and other cresols, or a mixture of xylenols can be preferably used.

Glyoxal (dialdehyde) can be used in various forms, and for example, a monomer having a relatively high purity of glyoxal, a polymerized glyoxal, an aqueous solution of glyoxal, or the like can be used. Among these, an aqueous solution of glyoxal of about 40% is preferable in terms of easiness of obtaining.

Examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid, and oxalic acid. Among them, p-toluenesulfonic acid is preferred because it is excellent in reactivity.

As a reaction of the substituted phenol and glyoxal carried out in the presence of the above acid catalyst, for example, a substituted phenol having a molar excess relative to glyoxal may be mixed in the presence or absence of a solvent, And usually carried out under heating. More specifically, it is usually heated at a temperature of 40 ° C to 250 ° C, preferably 60 ° C to 200 ° C, for example, for 1 hour to 12 hours, preferably for 3 hours to 9 hours.

After the reaction is completed, the catalyst is neutralized. The basic compound used for neutralization is not Particularly, generally, sodium hydroxide, potassium hydroxide or sodium hydrogencarbonate can be used, and among them, sodium hydroxide or sodium hydrogencarbonate is preferred. The basic compound can also be used in the form of an aqueous solution.

Next, the obtained reactant is dissolved in, for example, acetone or the like and separated by filtration. Here, the substituted phenol glyoxal resin is recovered as a soluble matter (filtrate). Further, the insoluble matter is a crystalline tetraphenol (monomer).

The substituted phenol glyoxal resin is obtained by removing excess substituted phenol and a solvent to be used by atmospheric distillation, vacuum distillation, steam distillation or the like.

The (B) biphenyltetracarboxylic acid and its anhydride (hereinafter also referred to as biphenyltetracarboxylic acid) contained in the resin composition of the present invention are usually preferably a biphenyltetracarboxylic acid skeleton. It is a form in which an adjacent acid anhydride is formed on one phenyl ring, that is, an acid anhydride can be formed. At this time, there are three isomers in the four carboxylic acids, that is, 1,1'-, 2,3,2',3'-body, 2,3,3',4 with respect to the biphenyl linkage position. '-body and 3,4,3',4'-body. Further, a substituent such as an alkyl group, an alkoxy group or a halogen may be present on the ring. Such a biphenyltetracarboxylic acid can be obtained as a commercially available product, and can be produced, for example, according to a production method disclosed in Japanese Laid-Open Patent Publication No. 2006-290836.

The biphenyltetracarboxylic acid may be any one of these isomers, and may be a combination of two or more.

In the above, a compound represented by the above chemical formula, that is, 3,3',4,4'-biphenyltetracarboxylic acid represented by the compound (1) and a compound represented by the compound (3) can be preferably used. An acid anhydride, 2,3,3',4'-biphenyltetracarboxylic acid represented by the compound (2), an acid anhydride thereof as the compound (4), a mixture thereof, and the like Those who have the above substituents.

Among these, a biphenyltetracarboxylic anhydride (compound (3) and a compound (4)) which is excellent in reactivity with an epoxy resin and has a high curing rate is particularly preferable.

When the (C) epoxy resin used in the present invention is a usual thermosetting epoxy resin, any of them may be used. Specifically, glycidyl ether of bisphenol A, glycidyl ether of phenol novolak resin, glycidyl ether of cresol novolak resin, glycidyl ether of bisphenol F, dicyclopentadiene can be preferably used. a glycidyl ether of a phenol condensate, a glycidyl ether of a phenol/salicylaldehyde condensate, a 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and a glycidyl glycoside of the bromide Ether, etc.

Among these, glycidyl ether of bisphenol A, glycidyl ether of phenol novolak resin, 3,4-epoxycyclohexyl methyl 3,4-epoxycyclohexanecarboxylic acid, and the like can be preferably used.

The resin composition of the present invention preferably contains (D) an epoxy resin hardener. (D) If the curing agent is a curing agent used in a usual epoxy resin, any of them may be used. For example, an aliphatic amine compound, an aromatic amine compound, a phenol novolak resin, an imidazole compound, and an acid anhydride compound other than (B) are mentioned.

Specific examples of the aliphatic amine compound include diethylenetriamine and triethylenetetramine. Examples of the aromatic amine compound include m-phenylenediamine and diaminodiphenylmethane. Examples of the acid anhydride compound include phthalic anhydride and 4-methylcyclohexane-1,2-dicarboxylic anhydride, and the exemplified compounds can be preferably used. .

The amount of each component in the present invention is not particularly limited, and it is preferably (A) The substituted phenol glyoxal resin is 0.5% by mass to 30% by mass. If it is in this range, the strength of the cured product of the resin composition is not lowered, and excellent UV absorption strength can be exhibited, but more preferably 1 mass. %~15% by mass, particularly preferably 3% by mass to 15% by mass.

(B) The blending amount of the biphenyltetracarboxylic acid is preferably 0.5% by mass to 30% by mass. If the ratio is in this range, the strength of the cured product is not lowered, but more preferably 1% by mass to 15% by mass, particularly preferably It is 5 mass% to 15 mass%.

(C) When the amount of the epoxy resin is too large, the UV absorption property is lowered. If the amount of the cured product is too small, the strength of the cured product is lowered. Therefore, it is preferably 40% by mass to 98% by mass, and more preferably 70% by mass to 97% by mass. More preferably, it is 70% by mass to 91% by mass.

Further, when the blending ratio of each component is within the above range, there is no particular problem, and it is preferred that the epoxy equivalent of the (C) epoxy resin be equal to the acid value, amine value, and hydroxyl group equivalent of the curing agent. The (D) epoxy resin hardener is formulated in an amount of usually 0.5% by mass to 50% by mass, and can be blended in an amount of preferably 1% by mass to 50% by mass, particularly preferably 3% by mass to 15% by mass ( D) Epoxy resin hardener.

In the resin composition of the present invention, various additives may be added to the extent that the properties are not impaired. Examples of such additives include a flame retardant, a curing accelerator, an antioxidant, a plasticizer, an inorganic compound, and the like. As the flame retardant, a bromine compound such as brominated biphenyl, a phosphorus compound or a ruthenium compound such as antimony trioxide or the like can be preferably used. Further, as the hardening accelerator, a phosphorus compound such as triphenylphosphine, a phenol compound, an imidazole such as methylimidazole or phenylimidazole, or a guanamine compound can be preferably used. Further, as the antioxidant, a hindered phenol compound, a phosphorus compound or the like can be preferably used.

The method for producing the resin composition of the present invention is not particularly limited. For example, it is preferred to use: (A) substituted phenol glyoxal resin, (B) biphenyltetracarboxylic acid, (C) epoxy resin, and (D) epoxy resin hardener as needed Thereafter, the mixture is heated and melted at 50 to 150 ° C, preferably 70 to 120 ° C, and melt-mixed; a method in which each raw material is dissolved in a solvent such as acetone, and the solvent is distilled off. Among these methods, the method of performing melt mixing after preliminary mixing is simple and preferable.

The resin composition of the present invention can be cured by heat to obtain a cured product. The temperature and hardening time during heat curing are not particularly limited, but are preferably from 120 ° C to 250 ° C, more preferably from 135 ° C to 170 ° C, and the curing time is from 1 minute to 60 minutes, preferably from 5 minutes to 30 minutes.

This cured product has excellent performance as an electronic component and exhibits excellent UV absorption characteristics in AOI inspection, so that accuracy in quality inspection of a substrate or the like can be improved, and inspection time can be shortened.

Example 1

The following is a more specific embodiment of the present invention, but the following examples are intended to illustrate the present application, and the scope of the present invention is not limited to the embodiments.

(Example 1)

<Synthesis of substituted phenol glyoxal resin>

In a 1 liter separable flask equipped with a thermometer and a cooling tube, 216 g of p-cresol (made by Wako Pure Chemical Industries Co., Ltd.) and 40% aqueous solution of glyoxal (and pure light) were added. Manufactured by the pharmaceutical industry, 36.3 g of p-toluenesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was heated to 100 ° C under a nitrogen stream, and the reaction was carried out for 2 hours. Then, the water was distilled off, and then the temperature was raised to 200 ° C, and the reaction was carried out for 3 hours.

After completion of the reaction, the reaction liquid was cooled, and the mixture was neutralized with an aqueous sodium hydroxide solution and filtered, and 200 ml of acetone was added. Further, acetone in the filtrate was removed by an evaporator to obtain 188.1 g of a solid resinous product (substituted phenol glyoxal resin).

<hardening>

15 g of the resinous product, biphenyltetracarboxylic anhydride of the formula (3) (manufactured by JFE Chemical Co., Ltd.), 15 g, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl Ester (manufactured by Wako Pure Chemical Industries, Ltd.) 63g, 4-methylcyclohexane-1,2-dicarboxylic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 84g, and triphenylphosphine (Wako Pure Chemical Industries, Ltd.) (manufacturing) 0.2 g of the mixture was heated at 140 ° C for 5 minutes on a hot plate, and melt-mixed to obtain a cured product. The cured product is considered to contain a portion which is insufficiently hardened and exhibits solubility in tetrahydrofuran.

<Measurement>

0.5 g of the cured product obtained above was dissolved in 99.5 g of tetrahydrofuran, and the UV spectrum and the fluorescence spectrum were measured. The results are shown in Table 1.

The UV absorption intensity was measured by using UV1650PC manufactured by Shimadzu at a wavelength of 350 nm and 365 nm.

The fluorescence intensity was obtained by measuring the maximum count number of the excitation wavelength of 442 nm using RF5300PC manufactured by Shimadzu.

(Example 2)

A cured product was obtained in the same manner as in the <hardening> of Example 1, except that the amount of the resin-form product was changed to 5 g and the amount of the biphenyltetracarboxylic anhydride used was changed to 5 g.

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Example 3)

A cured product was obtained in the same manner as in the <hardening> of Example 1, except that the amount of the resin-form product was changed to 20 g and the amount of the biphenyltetracarboxylic anhydride used was changed to 20 g.

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Example 4)

A resinous product was synthesized in the same manner as in the "synthesis of the substituted phenol glyoxal resin of Example 1" except that o-cresol (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of p-cresol. Then, a cured product was obtained in the same manner as in Example 1.

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Example 5)

Hardness was obtained in the same manner as in the <hardening> of Example 1, except that the biphenyltetracarboxylic anhydride was replaced with the biphenyltetracarboxylic anhydride of the formula (4) (manufactured by JFE Chemical Co., Ltd.). Compound.

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Example 6)

A cured product was obtained in the same manner as in the <hardening> of Example 1, except that the biphenyltetracarboxylic anhydride was replaced with the biphenyltetracarboxylic acid of the formula (1) (manufactured by JFE Chemical Co., Ltd.).

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Example 7)

A cured product was obtained in the same manner as in the <hardening> of Example 1, except that the biphenyltetracarboxylic anhydride was replaced with the biphenyltetracarboxylic acid of the formula (2) (manufactured by JFE Chemical Co., Ltd.).

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Comparative Example 1)

A resinous product was synthesized in the same manner as in the "synthesis of the substituted phenol glyoxal resin of Example 1" except that p-cresol was replaced with phenol, and then hardened in the same manner as in Example 1. Things.

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Comparative Example 2)

A cured product was obtained in the same manner as in the <hardening> of Example 1, except that the biphenyltetracarboxylic anhydride was not used.

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Comparative Example 3)

In the "hardening" of Example 1, a cured product was obtained in the same manner except that the resinous product and the biphenyltetracarboxylic anhydride were not used.

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

(Comparative Example 4)

A cured product was obtained in the same manner as in the <hardening> of Example 1, except that the biphenyltetracarboxylic anhydride was replaced with a novolac type phenol resin (manufactured by Kyoei Chemical Co., Ltd.).

The UV absorption intensity and the fluorescence intensity measured for the cured product in the same manner as in Example 1 are shown in Table 1.

As described above, the cured product obtained in the examples of the present invention is more excellent in UV absorption intensity and fluorescence intensity than the cured product of the comparative example. Such a resin composition of the present invention is particularly effective for use in a substrate or the like which is quality-managed by AOI, and can improve the accuracy in the quality inspection and shorten the inspection time.

Claims (10)

A resin composition comprising: (A) a substituted phenol glyoxal resin obtained by reacting cresols and/or xylenols with glyoxal under an acid catalyst; (B) selected from the group consisting of At least one of the group consisting of benzenetetracarboxylic acid and an acid anhydride thereof; and (C) an epoxy resin; wherein the resin composition contains 0.5% by mass to 30% by mass of the above (A) and 0.5% by mass. 30% by mass of the above (B), 40% by mass to 98% by mass of the above (C). The resin composition according to claim 1, wherein the above (B) is a group selected from the group consisting of the compounds (1) to (4) shown below: [Chemical Formula 1] The resin composition according to claim 1 or 2, further comprising 0.5% by mass to 50% by mass of the (D) epoxy resin hardener. The resin composition according to claim 1, wherein the cresol is at least one selected from the group consisting of p-cresol, m-cresol and o-cresol. The resin composition according to claim 1, wherein the xylenol is selected from the group consisting of 2,6-xylenol, 3,5-xylenol, 2,3-xylenol, 2,5 At least one selected from the group consisting of xylenol, 2,4-xylenol and 3,4-xylenol. The resin composition according to claim 1, wherein the glyoxal is at least one selected from the group consisting of a monomeric glyoxal, an aqueous solution of a polymerized glyoxal and glyoxal. . The resin composition according to claim 1, wherein the acid catalyst is at least one selected from the group consisting of sulfuric acid, p-toluenesulfonic acid and oxalic acid. The resin composition according to claim 1, wherein the epoxy resin is a thermosetting epoxy resin. The resin composition according to claim 3, wherein the epoxy resin hardener is selected from the group consisting of an aliphatic amine compound, an aromatic amine compound, a phenol novolak resin, an imidazole compound, and an acid anhydride compound. At least one of them. A cured product which is a cured product of the resin composition according to any one of claims 1 to 9.