JPH07268049A - New phenol resin - Google Patents

Abstract

PURPOSE:To obtain a phenol excellent in resistances to heat and moisture and useful as a curative for an epoxy resin by utilizing an aldehyde formed as a by-product of vanillin production. CONSTITUTION:This new phenol resin is obtd, by treating an aldehyde formed as a by-product of vanillin production together with a phenol at 50 deg.C or higher in the presence of an acidic catalyst and removing volatile components from the resulting product. The resin is used as a curvature for an epoxy resin and, if necessary, mixed with a low-mol.-wt. phenol pref. in an amt. of the resin of 10% or higher. The resin, as the curative, is compounded with an epoxy resin pref. in an equivalent ratio of the phenolic hydroxyl group to the glycidyl group of 0.2-1.5.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the use of aldehyde group-containing by-products obtained in the production of vanillin. More specifically, it relates to a vanillin derivative phenol resin composed of a vanillin derivative and a phenol in a by-product, and these are preferably used as a curing agent for epoxy resins for casting, molding, lamination and the like.

[0002]

PRIOR ART AND PROBLEMS Despite the large amount of aldehyde group-containing by-products obtained during the production of vanillin, its use has not been found so far and it has been used as a fuel. The present invention effectively utilizes a reaction product of this by-product and a phenol as a curing agent for an epoxy resin. Epoxy resins have excellent characteristics such as adhesiveness, processability, and solvent resistance, and are used in a wide range of applications. However, with recent remarkable technological progress, higher performance, especially heat resistance is required in each application field. As a method of improving the heat resistance of the epoxy resin composition, other than improving the epoxy resin itself,
There is a method of changing the curing agent. Examples of the curing agent for the epoxy resin include amine compounds, acid anhydrides and phenol compounds. Generally, when an amine compound is used, it has poor water resistance and has a problem of toxicity. In addition, acid anhydrides have the drawbacks of slow curing and poor water resistance and adhesiveness of the cured products. As a substitute for these, particularly in the field of molding materials, phenol novolac with well-balanced heat resistance and water resistance is used. However, recently, a higher heat resistance than a phenol novolac resin is required for a sealing material for IC electronic parts. Regarding the curing agent for epoxy resin aiming at high heat resistance, for example, JP-A-63-2
Japanese Patent No. 2824 discloses a condensate of phenols and salicylaldehyde. However, also in this condensate, improvement in heat resistance and moisture resistance is desired.

[0003]

[Means for Solving the Problems] The present inventors diligently studied the effective use of a by-product having an aldehyde group, which is obtained when vanillin is produced, and a novel phenol resin containing the by-product and a phenol compound is heat-resistant. The inventors have found that the epoxy resin curing agent is an excellent epoxy resin curing agent that satisfies both moisture resistance and moisture resistance at the same time, and completed the present invention. The present invention treats an aldehyde group-containing by-product obtained when producing vanillin and a phenol at a temperature of 50 ° C. or higher in the presence of an acidic catalyst,
The above problems have been solved by providing a novel phenol resin obtained by removing low-boiling components and a composition comprising a phenol resin and an epoxy resin. The phenol resin of the present invention is a polyhydric phenol obtained from an aromatic aldehyde having a phenolic hydroxyl group and a phenol in a by-product obtained during vanillin production.

The aldehyde group-containing by-product obtained when producing vanillin in the present invention is

[0005]

[Chemical 1]

[0006]

[Chemical 2]

After vanillin was produced by the addition reaction (I) of catechol derivatives containing guaiacol and guetols with glyoxylic acid and the oxidation reaction step (II) of the produced mandelic acid, vanillin was separated with vanillin residue. It is a successive reaction product of addition, condensation, and the like.

The structure of all the components of this by-product is not clear, but it is a compound having an aromatic aldehyde having a phenolic hydroxyl group and an alkoxy group. Structurally confirmed components are isophthalaldehyde (A), a condensate of vanillin (B), and a condensate of vanillin and o-alkoxyphenol (C). These were confirmed by NMR, MS spectrum and IR spectrum. The NMR spectrum of hydroxymethoxyisophthalaldehyde corresponding to (A) is shown in FIG. The NMR spectrum of the trinuclear condensate of vanillin corresponding to (B) is shown in FIG. 2, the IR spectrum is shown in FIG. 3, and the MS (E
I) The spectrum is shown in FIG. Similarly, the trinuclear condensate of guaiacol and vanillin corresponding to (C) is MS
A molecular ion peak 410 was confirmed from the (EI) spectrum. (D) is estimated from the IR absorption spectrum.

[0009]

[Chemical 3]

[0010]

[Chemical 4]

[0011]

[Chemical 5]

[0012]

[Chemical 6]

(A) is a by-product formed by the subsequent reaction of glyoxylic acid with vanillin,
(B) is a compound produced by condensation of vanillin which is a main product, and (C) is a condensation product of vanillin and a raw material o-alkoxyphenol. In addition to this, as a by-product, (D) and the like can be naturally considered.

When the proportion of the condensate such as the components (B), (C) and (D) in the by-product increases, when the novel phenol resin produced therefrom is used as an epoxy curing agent,
The heat resistance of the cured epoxy resin can be increased,
Since the melting temperature of the curing agent rises and its viscosity increases, it is difficult to handle. Therefore, the by-product is selected depending on the purpose of use, and it is necessary to mix another curing agent component instead of the by-product.

At this time, low molecular weight phenol novolacs can be used as a mixture. These are synthesized from phenols and formaldehyde, benzaldehyde, glycols and ether compounds. The blending ratio is preferably that containing at least 10% or more of a phenol resin synthesized from a by-product.

The phenols used in the present invention are compounds having at least one phenolic hydroxyl group in the aromatic ring. Specific examples include unsubstituted phenols such as phenol, resorcinol, and hydroquinone; cresol, ethylphenol, n-propylphenol,
iso-propylphenol, t-butylphenol,
Octylphenol. Monosubstituted phenols such as nonylphenol and phenylphenol; Disubstituted phenols such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol, dibutylphenol, guaiacol and guetol; trisubstituted phenols typified by trimethylphenol Kinds; Naphthol, methylnaphthol, etc.
Naphthols; bisphenols such as biphenol, bisphenol-A, bisphenol-F and the like can be mentioned. In the present invention, the reaction between the by-products and the phenols is carried out by mixing 0.5 mol or more of the phenols with respect to 1 mol of the by-products, and reacting them at a temperature of 50 ° C. or higher in the presence of an organic acid or inorganic acid catalyst for several hours. Is obtained by

As the epoxy resin using the polyhydric phenol of the present invention as a curing agent, known epoxy resins are used. For example, glycidyl ethers of diphenols such as bisphenol A, bisphenol F, bisphenol AD, brominated bisphenol A, resorcin, hydroquinone; phenol novolac, cresol novolac, resorcin novolac, trihydroxyphenyl methane, trihydroxyphenyl propane, tetrahydroxyphenyl Glycidyl ethers such as ethane, polyvinylphenol, and polyisopropenylphenol: glycidyl ethers of polyhydric phenols obtained by condensation reaction of phenols with aromatic carbonyl compounds; glycidylamines such as diaminodiphenylmethane and aminophenol; vinylcyclohexene Dioxide, alicylic diepoxy acetal, alicylic diepoxy carboxylate What alicyclic epoxy resins; hydantoin type epoxy resins, and the like heterocyclic epoxy resins such as triglycidyl isocyanurate.
The amount of the novel phenols of the present invention used as an epoxy resin curing agent is preferably such that the phenolic hydroxyl group becomes 0.2 to 1.5 equivalents relative to the glycidyl group.

In addition, the composition of the curing agent of the present invention and the epoxy resin may be added with known additives such as other curing agents, fillers, curing accelerators, release agents, flame retardants, surface treatment agents and the like, if necessary. Can be added.

In order to resin-encapsulate electronic parts such as semiconductors using the composition of the curing agent of the present invention and an epoxy resin, a transfer mold, a compression mold, an injection mold, etc., and particularly the resin composition is a liquid. In this case, a conventionally known molding method such as a casting method, a dipping method or a dropping method is applied.
Further, in order to use the resin composition for a laminated board, the resin composition is uniformly dissolved using a solvent such as methyl ethyl ketone, toluene, or ethylene glycol monomethyl ether, which is impregnated in glass fiber or organic fiber, and heated. It may be dried to obtain a prepreg, which may be press-molded.

The novel phenol resin of the present invention has a higher heat resistance than the phenol novolac resin which has been widely used as a curing agent for epoxy resins, and it is possible to obtain a cured molded product in which moisture resistance and moldability are well balanced. . If the polyhydric phenol of the present invention is converted into glycidyl ether by a known technique, an epoxy resin having high heat resistance and high humidity resistance can be obtained.

[0021]

INDUSTRIAL APPLICABILITY The present invention can be effectively used by using an aldehyde-containing by-product obtained when producing vanillin as a phenol resin. The novel phenol resin consisting of by-products and phenols is also useful as a curing agent for epoxy resins. Epoxy resin cured products using this exhibit excellent curing characteristics, low water absorption, heat resistance and breaking energy. A resin cured product having a large value is provided. The obtained resin sufficiently satisfies the required characteristics of thermal shock resistance as an IC encapsulant and soldering heat resistance during surface mounting work. Therefore, according to the cured product for semiconductor encapsulating material of the present invention, a high-performance IC encapsulating material is provided.

[0022]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be described below with reference to Examples. Here, the evaluation items and methods of the cured moldings used are as follows. Water absorption rate: The test piece was put in boiling water at 100 ° C., and the weight increase after 24 hours was measured and calculated. Glass transition temperature (Tg): manufactured by Rigaku Denki (TMA814
0) was used to determine the linear expansion change. Flexural strength, flexural modulus, flexural energy: measured using an autograph (Shimadzu AG-5000D) at a crosshead speed of 10 mm / min. The by-product 1 in the examples is a by-product component A + B + C + D, and the by-product 2 is A + B + C obtained by extracting the by-product 1 with chloroform and removing the insoluble component D. The by-product 3 is a component mainly containing A.

Example 1 Phenol 1128 g (12 mol) By-product 1,152 g
Was charged into a 3-liter 3-necked flask, and PTS was used as a catalyst.
(Paratoluene sulfonic acid) (5 g) was added and reacted at 100 ° C. for 3 hours. After that, the reaction solution was heated to 160 ° C. and dehydrated, and unreacted phenol was removed at a reduced pressure of 50 torr. The softening point of this resin was 120 ° C. (Resin A)

Example 2 The synthesis method is the same as in Example 1 except that the by-product 1 of Example 1 is changed to the by-product 2,152 g. The softening point of this resin is 115
It was ℃. (Resin B)

Example 3 The synthesis method is the same as in Example 1 except that the by-product 1 of Example 1 is changed to 3,152 g of by-product. The softening point of this resin is 110 ° C.
Met. (Resin C)

Example 4 After synthesizing the resin A of Example 1, 100 parts of the resin A was mixed with 30 parts of a phenol novolac resin (eg Meiwa Kasei Co., Ltd. H-1 having a softening point of 85 ° C.). The softening point of this resin was 110 ° C. (Resin D)

Comparative Example 1 Phenol 1128 g (12 mol) and 37% formalin 567.6 g (7 mol) were charged into a 3 liter three-necked flask, and 100% oxalic acid 10 g was added as a catalyst to give 100.
The reaction was carried out at ℃ for 3 hours. After that, the reaction solution was heated to 160 ° C. and dehydrated, and unreacted phenol was removed at a reduced pressure of 50 torr. The softening point of this resin was 115 ° C. (Resin E)

Comparative Example 2 Phenol (1128 g (12 mol)) and salicylaldehyde (122 g (1 mol)) were charged into a 3 liter three-necked flask and 5 parts of PTS (paratoluenesulfonic acid) was used as a catalyst.
g and reacted at 100 ° C. for 3 hours. After that, add 10
After dehydration by heating to 0 ° C., unreacted phenol was removed at a reduced pressure of 50 torr. The softening point of this resin is 115 ° C.
Met. (Resin F) Cured Product Evaluation For the cured product evaluation, an epoxidized cresol novolac resin (Nippon Kayaku Co., Ltd. EOCN-1020, softening point 65 ° C.) was used as a representative example of epoxy resin for semiconductors,
Example resins (A to D) of the present invention and comparative example resins (E to D)
F) was blended (Table 1) and triphenylphosphine (TPP) was added and cured as a curing catalyst, and the physical properties were evaluated.

Preparation of test pieces

[Table 1]

The compounding ratio is epoxy equivalent / OH equivalent = 1. Cast epoxy resin, curing agent and curing catalyst are heated and melted at 150.degree. Curing Primary curing 150 ° C 4h + Secondary curing 180 ° C 4h Specimen size a. Water absorption rate 4 mm x 25 mm x 70 mm b. Tg TMA test dimensions c. Bending test piece 4 mm × 6 mm × 75 mm Test method Water absorption rate The test piece was put in boiling water at 100 ° C. and the weight increase after 24 hours was measured. Tg Made by Rigaku Denki (TMA8140) is used. Tg was determined from the change in linear expansion. Flexural strength, flexural modulus, flexural fracture energy Measured using Shimadzu (AG-5000D) autograph Crosshead speed 10 mm / min

[Brief description of drawings]

FIG. 1 is a NMR of hydroxymethoxyisophthalaldehyde corresponding to (A) described in the detailed description of the present invention.
Spectrum.

FIG. 2 is an NMR spectrum of a trinuclear condensate of vanillin corresponding to (B) described in the detailed description of the present invention.

FIG. 3 is an IR spectrum of a trinuclear condensate of vanillin corresponding to (B) described in the detailed description of the present invention.

FIG. 4 is an MS (EI) spectrum of a trinuclear condensate of vanillin corresponding to (B) described in the detailed description of the present invention.

Claims (3)

[Claims] 1. A novel product obtained by treating a by-product containing an aldehyde group, which is obtained when vanillin is produced, and a phenol at a temperature of 50 ° C. or higher in the presence of an acidic catalyst to remove low-boiling components. Phenolic resin. 2. The phenolic resin according to claim 1
Phenolic resin mixture containing at least wt%. 3. A composition comprising the phenolic resin according to claim 1 and an epoxy resin.