JPS62167318A - Curing of epoxy resin - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin having improved storage stability and curing characteristic, by using a specific naphthol derivative as an epoxy resin curing agent. CONSTITUTION:An epoxy compound having >=2 epoxy groups in one molecule is cured. In the process, a naphthol derivtive having at least 2 hydroxyl groups linked to the naphthalene uncleus, preferably monohydric naphthol in the molecule, preferably a fusible and soluble compound, obtained by linking >=2 monohydric naphthols (alpha-naphthol or beta-naphthol) and/or a dihydric naphthols through linking chains, having normally <=5,000 molecular weight and expressed by the formula (p is 1-2; R' is substituent group on the naphthalene uncleus; n is 0-2; R is bi- - tetrafunctional linking group of the naphthalene uncleus; m is a number for keeping the molecular weight at <=5,000 and further fusibility in relation to R), etc., is used as an epoxy resin curing agent.

Description

Detailed Description of the Invention: a. Industrial Application Field The present invention relates to a method for curing epoxy resin, and in particular to curing of epoxy resin using a specific naphthol derivative as a curing agent, which has not been conventionally used as an epoxy resin curing agent. Regarding the method.

b. Conventional technology Epoxy resins have traditionally been developed to suit various uses by using various curing agents such as amine curing agents, acid anhydride curing agents, polyphenol curing agents, and anionic curing agents. It is possible to obtain cured products with a wide range of curing properties9 mechanical properties and mechanical properties, making it suitable for various paints and adhesives.

Resin for fiber reinforced composite materials (for printed circuit boards).

It is used in a wide range of applications, including (for aviation and space), sealing resins (especially for electronic parts), and resins for molds.

In particular, products cured with polyphenol curing agents generally achieve a lower crosslinking density than those cured with amine curing agents, so the short-term heat resistance represented by Tg is lower than that of products cured with anionic curing agents. However, it has low moisture absorption and excellent electrical properties, and has other characteristics such as storage stability and fast curing speed in the B stage, and is mainly used as a sealing resin for semiconductor transfer molding. It is reported that there has been significant growth in the electrical field. However, with the increasing density of semiconductors and the like, there has been a demand for cured products that have even lower hygroscopicity and excellent electrical properties and heat resistance.

C0 Object of the Invention The object of the present invention is to provide an epoxy resin that has both good storage stability and good curing properties, and the cured product thereof has excellent dimensional stability and electrical properties, and furthermore, has low moisture absorption, Heat-resistant,
&I It is an object of the present invention to provide a method for curing an epoxy resin which provides a cured epoxy resin with improved flammability.

d1 Structure of the Invention The object of the present invention is to use a naphthol derivative having at least two hydroxyl groups in one molecule that binds to a naphthalene nucleus when curing an epoxy compound having two or more epoxy groups in one molecule. Especially achieved. In the present invention, a curing accelerator may be used in addition to the above naphthol derivative.

In the present invention, naphthol derivatives having at least two hydroxyl groups bonded to a naphthalene nucleus in one molecule generally preferably include the following.

(1) Two or more monohydric naphthols (α-naphthol or β-naphthol) and/or dihydric naphthols linked by a linking chain, generally with a molecular weight of 50
Fusible and/or soluble compounds as represented by the following formula below.

ts and R/ are hydrocarbon groups having 10 or less carbon atoms.

halogen atom, carboxyl group, carboxylic acid anhydride group,
Examples include carboxylic acid ester groups. However, the hydrocarbon group may contain an active group for epoxy groups, such as an alcoholic hydroxyl group or a carboxyl group.

R is generally an organic group having 10 or less carbon atoms,
It has a divalent to tetravalent bonding chain. This bonding group may contain an active group for an epoxy group such as a carboxyl group, a carboxylic acid anhydride group, or a phenolic hydroxyl group.

A more specific example is as follows.

*-G-naphthol formaldehyde condensate rice methyl-
α-naphthol is 7 toll formaldehyde (β-naphthol is 2
β-
Most of the naphthol novolacs will be exhibited in 2F format.

) Dihydroxnaphthalene formaldehyde condensates, etc., and nuclear halogen-substituted products thereof, such as brominated products, and preferably not more than 50 mol of these tols, etc., are mixed with phenol, cresol, xylenol, fromphenol, resorcinol, etc. Novolak type compounds substituted with phenols can be used very preferably.

In addition to formaldehyde, condensates with other monoaldehydes and monoketones can also be suitably used. In this case, a two-body type is particularly preferably used since the reactivity toward formaldehyde is reduced. Of course, depending on the reaction conditions, products with even more advanced condensation can be obtained and can be used in the same way.

Monoaldehydes used in such condensations.

benzaldehyde, p-hydroxybenzaldehyde,
Examples include naphthaldehyde, acetone, cyclohexanone, cyclopentanone, and methyl ethyl ketone.

Furthermore, by using dialdehydes such as glyoxal, glutaraldehyde, tele-7-taraldehyde, and in-7-taraldehyde, the basic binding group can be
Depending on the individual, a polynaphthol compound having four naphthalene nuclei can also be suitably used.

For example, when glutaraldehyde is used, a gelinaphthol compound as shown in the following formula is obtained, and bonding groups other than those formed from aldehydes and ketones, such as sulfonyl groups and carbonyl groups, can also be used. For example, in the case of a sulfonyl group, this is dioxycin-7-tylsulfone, which corresponds to suphenol S in the case of phenol.

Furthermore, polyvinylnaphthol, which corresponds to polyvinylphenol in the case of phenol, can also be used.

Generally, such naphthol derivatives have a number of naphthalene nuclei of from 2 to 20, more preferably from 2 to 12, more preferably from 2 to 10. Particularly preferably, those in the range of 2 to 7 are used.

Among the above-mentioned naphthol derivatives of the present invention, a particularly preferred method for producing the novolak type curing agent is a method in which a naphthol component and an aldehyde component are subjected to a condensation reaction in the presence of an acidic catalyst. Here, the ratio of the aldehyde component to the naphthol component is adjusted depending on the desired degree of polymerization of the novolak.

Specific examples of acidic catalysts include protonic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, methanesulfonic acid, toluenesulfonic acid, boron trifluoride, boron trifluoride ether complex,
Lewis acids such as aluminum chloride, tin chloride, zinc chloride, iron chloride, titanium chloride, oxalic acid, and the like can be used.

Among these, it is preferable to use protonic acids,
In particular, hydrochloric acid, sulfuric acid, methanesulfonic acid, toluenesulfonic acid, etc. are preferably used.

The amount of these catalysts to be used is selected between 0.001 and 0.05 mole times the raw material naphthol component (T).

The reaction temperature is usually 80 to 250°C, but the initial stage is carried out at 80 to 150°C, and the reaction temperature is further raised as necessary. The reaction time is 1 hour to 1 hour.
It can be selected within the range of 0 hours.

When the above-mentioned reaction of the present invention is carried out without a solvent, it is desirable to raise the temperature because the melting point of the novolak-type Nuttall resin increases as the degree of polymerization increases.

Also, the above reaction positions are toluene and chlorobenzene.

Aromatic hydrocarbons such as dichlorobenzene, nitrobenzene and diphenyl ether, ethers such as ethylene glycol and dimethyl ether of diethylene glycol, etc. can also be used as the solvent.

Although the preferred synthesis method for the novolac type epoxy resin curing agent of the present invention has been described above, the synthesis method is not necessarily limited to this.

+21dl Hydroxynaphthalene Specifically, the polyhydroxynaphthalene described in the present invention is 1,6-dihydroxynaphthalene/, 2,7-dihydroxynaphthalene/, 1,5-dihydroxynaphthalene, S3
-dihydroxynaphthalene.

1.7-dihydroxynaphthalene, 2.6-dihydroxynaphthalene, 1.8-dihydroxynaphthalene, 1.
2-dihydroxynaphthalene.

1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,2,3-naphthalenetriol, 1
, 2.4-s7 talent trio.

1,2.5-naphthalene triol 11λ6-su7
Talent triol, 1,2.7-s7talent triol, 1,2.8-naphthalene triol.

1. Turtle 5-7 talent trio; 1. &6-naphthalenetriol, 1,3.7-naphthalenetriol, 1
, 3.8-s7 talent trio.

1,4.5-7-naphthalenetriol, 1.46-naphthalenetriol, 1.6.7-naphthalenetriol+2-3=6-naphthalenetriol τ, preferably 1,6-dihydroxynaphthalene, 2. 7-dihydroxynaphthalene.

By the way, an epoxy resin containing a predetermined amount of an epoxy resin curing agent mainly composed of a naphthol derivative as described above has good storage stability, and has a temperature of 80°C to 24°C.
It cures at a temperature of 0°C, yielding a cured product with excellent properties.

The amount of the epoxy resin curing agent containing the naphthol derivative of the present invention as a main component is 0.4 to 1.6 as active hydrogen equivalent of the curing agent per 1 equivalent of epoxy group of the epoxy resin.
, preferably 0.6 to 1.4, particularly preferably 0.7 to
The range is 1.2.

Epoxy compounds to be applied to the curing agent containing a naphthol derivative as a main component of the present invention include various well-known epoxy compounds in which at least one type of epoxy group having two or more epoxy groups in one molecule is used as the main ingredient. However, for example, glycidyl ethers of polyhydric phenols and polyhydric naphthols, especially glycidyl ethers of bisphenol A type, glycidyl ethers of bisphenol F type, phenol formaldehyde, 7-toll formaldehyde, polyglycidyl ethers of resins, and phenol. Polyglycidyl ethers of novolak-type resins of esters and naphthol with other aldehydes, phenylolmethane triglydyl ether, phenylglycidyl esters from aromatic carboxylic acids, epoxy compounds from alicyclic compounds, etc. Sidyl isocyanurate, triglylyl-p-amine phenol, tetraglycidyldiaminodiphenylmethane, and nitrogen-containing epoxy compounds can also be used.

In addition, instead of some of these polyepoxy compounds, monoepoxy compounds such as phenylcricidyl ether, nonylphenylcricidyl ether, yl-=y' tylcidyl ether, etc. can be used as a viscosity modifier. .

Considering the characteristics of the curing agent of the present invention, phenol and/or cresol novolac glycidyl ethers,
α-Naphthol novolak glycidyl ethers and bisphenol-A-diglycidyl ethers are particularly suitable.

Further, other curing agents, curing accelerators, fillers, etc. may be added to the epoxy resin composition of the present invention, if necessary. In particular, by adding a curing accelerator to the novolak type epoxy resin curing agent of the present invention immediately before use, the low-temperature curing properties can be further improved dramatically. Preferred curing accelerators include tertiary amines such as N,N-dimethylbenzylamine, α-methylbenzyldimethylamine, 2.4.6-tris(dimethylaminomethyl)phenol hexamethoxymethylmelamine, N,N -Amine oxides such as dimethylbenzylamine oxide, BF3-
Piperidine, boron amine complexes such as triethanolamine porate, polyacid ester derivatives.

Aniline-formaldehyde resins, particularly preferably N,N-dimethylbenzylamine and a-methylbenzyldimethylamine.

These are tertiary amines such as 2,4,6-tris(dimethylaminomethyl)7enol. The amount of curing accelerator added is 0.05 to 5%, preferably 0.1 to 1%, particularly preferably 0.2 to 0.8%.

The above-mentioned naphthol derivative, polyepoxy compound, and if necessary, the above-mentioned curing accelerator are mixed, and the curing reaction is proceeded at the time of shaping as a so-called B-stage resin, either as it is or by causing a partial reaction. You will get a cured product.

In addition to the above ingredients, some of the curing agents may be replaced with other curing agents, such as polyphenols such as phenol novolac, cresol novolak, polyvinylphenol, and anhydride curing agents such as trimellidic acid and phthalic anhydride. It is possible.

In addition, other additives such as alumina powder, inorganic powders such as stonite, metal powders such as aluminum, copper, and silver, dyes, and pigments can be added in appropriate amounts depending on the functions required of the cured product.

The resin mixture before curing can be used in powder or lake form by transfer molding or compression molding.

It can also be used as a paint or adhesive by applying it to a surface in the form of a solution such as wax, drying, and hardening.

Further, it is possible to prepare a so-called prepreg by impregnating such a varnish into a glass woven fabric, carbon fiber, aramid fiber, etc., and mold the prepreg into a structure by press molding or autoclave molding.

The cured epoxy resin using the curing agent of the present invention has low moisture absorption, excellent electrical properties, and heat resistance, and is suitable for advanced technology fields such as electrical and electronic applications such as semiconductor encapsulants, and aerospace applications. It can be used for.

The present invention will be explained in detail with reference to Examples below.

The examples are illustrative and not limiting.

Measurement of physical properties in Examples Molecular weight Measured by freezing point depression method using dioxane.

Melting: MICROMEL by YANAGIMOTO MFG Co
Measurement was performed using TING POINT APPARATUS at a temperature increase rate of 2°C/-.

Measured using a thermomechanical analyzer (Du Pant 101090) D at a heating rate of 10°C/min.

Measured using a thermomechanical analyzer (Du Pont 1090) TGA at a heating rate of 20°C/min.

Thermomechanical analyzer (Du Pont 1090) D
Measured in SC at a heating rate of 10°C/min.

Curing temperature: Temperature at which it cures within 8 minutes when heated on a hot plate.

Water absorption rate: A molded piece cut to a size of 12 ws x 50 ws x 5 xx was immersed in boiling water for one week, and the water absorption rate was determined according to the following formula.

d Synthesis Example 1 Synthesis of alpha-su7thol-formaldehyde novolac resin> A solution of 40 parts of alpha-naphthol, 19 parts of a 35% formaldehyde aqueous solution, and 0.1 part of oxalic acid in 4 parts of water was stirred for 1 hour. Reflux, add 1.4 parts of 36% hydrochloric acid,
Continue the reaction for an additional 35 minutes. Thereafter, the heating was stopped, a large amount of water was added to the reaction mixture, and stirring was continued for an additional 30 minutes. The water was then removed by decantation, and the remaining resin was dried under reduced pressure. The resulting novolak-based 7-tall resin was 39
The melting point is 130-145°C, the molecular weight is 521 (the molecule contains an average of 3.4 naphthol components, an average of 24 formaldehyde components, and 3 hydroxyl groups in the molecule).
．． (including 4 pieces).

Synthesis Example 2 <Synthesis of β-naphthol-formaldehyde novolac resin> A solution of 284 parts of β-naphthol, 154 parts of toluene, and 22 parts of oxalic acid dissolved in 22 parts of water was heated to 120°C and melted, and 35q6 formaldehyde aqueous solution was added thereto. 84 parts were added dropwise at 105° C. over 1.5 hours while stirring, and the reaction was continued for an additional 25 hours. After distilling off the water from the reaction mixture, heat it! Filter it! The separated solids are washed with hot water and dried under reduced pressure. The resulting naphthol resin was 280 parts with a melting point of 199~
The molecular weight at 202°C is 300 (2 naphthol components in the molecule.

(contains one formaldehyde component and two hydroxyl groups in the molecule).

Synthesis Example 3 (Synthesis of 1,1,5,5-tetrakis(1-hydroxynaphthyl)pentane (TONP)) 288 parts of α-naphthol was added to 25% of glutaraldehyde.
After heating and dissolving 200 parts of an aqueous solution at KIIO°C, 0.4 part of salt fi and 0.6 part of p-)luenesulfonic acid were added to the solution and reacted for 1 hour with stirring, and the temperature was further raised to 160°C for 2 hours. The reaction continued. The reaction mixture was dehydrated at 160°C, and unreacted α-7 torr was distilled off under reduced pressure. The obtained compound was 260 parts with a melting point of 160~
175℃2 molecular weight is 651 (4 naphthol components in the molecule.

(contains one dialdehyde component and four hydroxyl groups in the molecule).

Synthesis Example 4 144 parts of G-naphthol 82 parts of I P-oxybenzaldehyde were heated and melted at 130°C, and the IC in O was 36%.
0.2 parts of hydrochloric acid and p-) luenesulfone l! ! ! 0.3 part was added thereto, and the reaction was heated at 100°C for 1 hour, and then heated at 190 to 200°C for 8 hours while distilling water produced by the reaction out of the reaction system.

The reaction product was crushed, washed with hot water, and then dried.

The resulting resin weighed 209 parts, had a melting point of 300°C or higher, and a molecular weight of 529. It contains an average of 25 naphthol components and an average of 1.5 p-hydroxybenzaldehyde components in the molecule, and 4.0 hydroxyl groups in the molecule.
It is a novolac-type 7-tall resin (ONB) containing

Example 1 100 parts of epoxy resin (Epifuto 154).

α-naphthol formalyynovo2tsuku86 as a curing agent
0.35 parts, benzyldimethylamine as curing accelerator
Dissolve 1 part in 300 parts of acetone and mix uniformly at 35°C.
Acetone was removed under reduced pressure. The curing initiation temperature of the obtained composition was 99°C, and the temperature at which it was cured within 8 minutes using a hot grate was 185°C. Next, the composition was heat-treated in a metal mold at 150°C for 1 hour and then at 180-220°C for 4 hours while gradually increasing the temperature to obtain a hardened molded piece. The Tg of the molded product is 185°C, and the Td
The temperature was 330°C, and the water absorption rate was 1.8°C.

Examples 2 to 7 and Comparative Examples 1 to 4 In Example 1, epoxy resin (Epicoat 154) 10
The curability and physical properties of the cured molded product were measured in the same manner as in Example 1 except that the predetermined amounts of the epoxy resin and curing agent shown in the table below were used for 86 parts of α-naphthol formalin novolak). The results are summarized in the table below.

For comparison, examples are shown in which phenol-formalin novolac is used as a curing agent (Comparative Example 1.2) and when diaminodiphenylsulfone is used as a curing agent and no curing accelerator is used (Comparative Example 3.4). Indicated.

Products using the curing agent of the present invention have a lower water absorption rate and superior curing properties than those using other types of curing agents.

It was found that it has heat resistance.

Procedural amendment Written March 9, 1986 by Tokihiro Tomi, Director General of the Tokugawa Bureau 1, Indication of φ No. 61-7872 2, Name of the invention Method for curing epoxy resin 3, Person making the amendment φ Related: Patent applicant: 1-11 Minamihonmachi, Higashi-ku, Osaka (300), Teijin Co., Ltd., Okamoto Sashibe 4, Daigoi Ministry, Agent: No. 1, 2-1, Uchisaiwai-cho, Chiyoda-ku, Tokyo (Iino Building), Jojin Co., Ltd. Uchimei II [Understanding 14 "Detailed Description of the Invention" + 1) The formula in line 7 of page 4 of the specification is corrected as follows.

(2) Page 5, line 11 to the last line of the specification are corrected as follows.

*Naphthol formaldehyde condensate *Methylnaphthol formaldehyde condensate (among the above, α-naphthol is preferred.β-su7
In the case of tall disks, the diphthalmium substances tend to crystallize and are easily fixed, so β-su7'' (3) Change the ``monizing agent, anionic type'' in the first line of page 2 of Specification-V to ``monizing agent, cationic curing agent''. I corrected it to ``agent, anitan type''.

(4) Details im? 1 monoaldehyde on page 'd line 44, 1 +- heptanoaldehyde, as monoketones,
"Acetaldehyde, propionaldehyde," 4 Correct.

(5) In page 9, line 8 of the specification, "it is preferable to use a protonic acid" is corrected to "it is preferable to use oxalic acid or a protonic acid, and the protonic acid is used at °C."

(6) Specification %12 Sadasuetake's "aldehyde, resin"
is corrected to "aldehyde resin".

that's all

Claims (1)

[Claims] When curing an epoxy compound having two or more epoxy groups in one molecule, a naphthol derivative having at least two hydroxyl groups in one molecule bonded to a naphthalene nucleus is used. How to cure epoxy resin.