JPS61197240A - Laminated board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Background) The present invention relates to a laminate made of an epoxy resin with excellent heat resistance.

(Prior Art) Laminated plates made of epoxy resin are widely used as structural materials because of their excellent mechanical strength, dimensional stability, chemical resistance, and the like. In the field of electronics, in addition to the above properties, electrical insulation, moisture resistance, and Due to its good physical properties, it is often used as a printed circuit board.

(Problems to be solved by the invention) However, the miniaturization of electrical products, the miniaturization of printed circuits,
Nowadays, as heat treatment temperatures in mounting processes continue to rise, there is a strong demand for improvements in the heat resistance, tracking resistance, and arc resistance of laminates, and for lower metal corrosion resistance by reducing impurities such as chlorine.

In view of this situation, Reihatsu Co., Ltd. conducted research on Eikura, and by using an epoxy resin represented by formula (I),
The present inventors have discovered that a laminate plate with excellent heat resistance, tracking resistance, arc resistance, etc. and low levels of impurities such as chlorine has been produced, and the present invention has been achieved.

(Structure of the Invention) That is, the present invention is "a laminate comprising an epoxy resin represented by the following formula (I) and a curing agent".

However, R1 is an organic compound residue having active hydrogen.

nl-R2...nl is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100.

j represents an integer from 1 to 100.

A is an oxycyclohexane skeleton having a substituent and is represented by the following formula.

One or more of these are contained in the resin.

In the epoxy resin prepared by the formula (I) of the present invention, RI/fi is an organic residue having active hydrogen, and examples of the organic substance having active hydrogen, which is a precursor thereof, include alcohols, phenols, carboxylic acids, etc. , amines, thiols, etc.

The alcohol may be a monohydric alcohol or a polyhydric alcohol.

For example, aliphatic alcohols such as methanol, ethanol, proponol, butanol, pentanol, hexanol, octyl alcohol, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, Pyrene gelicol, cyfurobi1/nglycol, 1,3 butanediol, 1,4 butanediol, bentanediol, 1,6 hexanediol, neopentyl glycol, oxypivalic acid neopentyl glycol ester, cyclohexane dimetatool, glycerin,
Examples include polyhydric alcohols such as diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol.

゛ Phenols include phenol, cresol,
Examples include catechol, hyrogallol, nohydroquinone, hydroquinone monomethyl ether, bisphenol A1 bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S1 phenolic resin, and cresol novolak resin.

Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanoic acid, trimellitic acid, pyromellitic acid,
Examples include polyacrylic acid, phthalic acid, isophthalic acid, and terephthalic acid. Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid.

Examples of abans include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, inphorondiamine, toluenediamine, hexamethylenediamine, Examples include xylene diamine, diethylenetriamine, triethylenetetramine, and ethanolamine.

Examples of thiols include mercapto compounds such as methyl mercaptan, ethyl mercaptan, probyl mercaptan, and phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol esters of mercaptopropionic acid, such as ethyl-17 glycol dimercabutopropionic acid ester, and mercaptopropionic acid. Examples include methylolpropane trimercaptopropionic acid ester, pentaerythritol benthamercaftpropionic acid ester, and the like.

In addition, as compounds having active hydrogen, hapolyvinyl alcohol, polyvinyl acetate partial hydrolyzate, f
Starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, allyl alcohol resin, styrene allyl alcohol copolymer resin, styrene-ma-twin acid copolymer resin, alkyd resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin ,
Examples include polypropylene polyol, polyetramethylene glycol, etc.

In addition, compounds with active hydrogen have unsaturated 2 atoms in their skeleton.
It may have a double bond, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, and tetrahydrophthalic acid. The unsaturated double bonds of these compounds may also have an epoxidized structure.

n in general formula (L), , n2...nl
is 0 or an integer from 1 to 100, and the sum is 1 to 100
However, if it is more than 100, it becomes a resin with a high melting point and is difficult to handle, making it practically unusable.

l is an integer from 1 to 100.

Among the substituents X of A in formula (I) OHOR2 That's more preferable.

That is, in the present invention, it is preferable for the substituent X to be an overlying one, since this increases the crosslinking density when cured.

Specifically, the epoxy resin represented by formula (I) of the present invention is a polyether resin obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide using an organic compound having active hydrogen as an initiator, i.e. , can be produced by epoxidizing a polycyclohexene oxide polymer having a vinyl group side chain with an oxidizing agent such as a peracid.

4-Vinylcyclohexene-1-oxide is obtained by partially epoxidizing vinylcyclohexene obtained by a dimerization reaction of butadiene with peracetic acid.

When 4-vinylcyclohexene-1-oxide is polymerized in the presence of active hydrogen, it is preferable to use a catalyst.

Examples of catalysts include amines such as methylamine, ethylamine, propylamine and piperazine, organic basic acids such as pyridines and imidazoles, and formic acid.

Organic acids such as acetic acid and propionic acid, inorganic acids such as sulfuric acid and hydrochloric acid, alkali metal alcolades such as sodium methylate, alkalis such as KOH and NaOH, BF
3. ZnCl2. Examples include Lewis acids such as AlCl3.5nC14 or complexes thereof, and organometallic compounds such as triethylaluminum and diethylzinc.

These catalysts can be used in an amount of 0.01 to 10%, preferably 0.1 to 5%, based on the reactants. The reaction temperature is preferably -70 to 200°C, and the reaction can also be carried out using a solvent. The temperature of the solvent is -30°C to 100°C.

However, it cannot be used unless it has active hydrogen.

That is, acetone, methyl ethyl ketone, methyl isobutyl ketone and other ketones, penzene, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters, etc. can be used.

Now, in order to epoxidize the thus synthesized polycyclohexene oxide polymer having vinyl group side chains to produce the epoxy resin of formula (1) for the laminate of the present invention, peracids, nohydrocarbons, etc. Either oxides can be used.

Peracids include performic acid, peracetic acid, and perbenzoic acid.

Trifluoroperacetic acid and the like can be used.

Among these, peracetic acid is a particularly preferred epoxidizing agent because it is industrially available at low cost and has high stability.

Hydrogen peroxide is a hydroperoxide.

Tertiary butyl, hydroperoxide, cumene peroxide, etc. can be used.

A catalyst can be used during epoxidation if necessary. For example, in the case of a peracid, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst. In the case of hydroperoxides, the catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tert-butyl hydroperoxide. can.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and physical properties of the raw materials.

Depending on the conditions of the epoxidation reaction, substituents in the raw materials may undergo a side reaction with the oxidizing agent, etc. at the same time as the olefin bond is epoxidized, resulting in modified substituents that may be contained in the target compound. come. The ratio of the three substituents in the target compound is determined by the Class 81 epoxidizing agent, the molar ratio of the epoxidizing agent to the olefin bond, and the reaction conditions.

For example, when the epoxidizing agent is peracetic acid, the modified substituents are mainly those like Q'11 below, and are generated from the produced epoxy group and the by-produced acetic acid.

The target compound can be taken out from the reaction crude liquid by ordinary chemical industrial means such as concentration.

The epoxy resin represented by formula (I) may be used alone, but it can also be used in combination with other epoxy resins such as hydrogenated epoxy resins and novolak epoxy resins.

The curing agent used in the present invention includes amine compounds such as diaminodiphenylmethane and dicyandiamide;
acid anhydride compounds such as hexahydroheptalic anhydride;
Compounds known to react with epoxy groups, such as phenolic compounds such as phenol novolacs and thiol compounds, can be used. The amount used is preferably 0.3 to 2 equivalents based on the epoxy resin.

The laminate of the present invention is produced by dissolving the above-mentioned epoxy resin, curing agent, and curing accelerator in an organic solvent to form a face, and then impregnating the base sheet with prepreg, which is then layered and integrally molded under heat and pressure. In particular, it can be manufactured.

Triethylamine DBU is used as a curing accelerator.

Amine compounds such as benzyldimethylamine.

Imidazoles such as 2-1-ndecyl imidazole and 2-ethyl-4-methylimidazole, F3 complexes such as BF3/piperidine complex, etc. can be used.

The amount used per 100 parts by weight of the epoxy resin and curing agent mixture is determined by the balance between curability and the physical properties of the laminate.
For example, benzyldimethylamine, 2-undecylimidazole.

In the case of 2-ethyl-4-methylimizodal, it is preferable to use 0.1 to 5 parts by weight.

As the organic solvent, acetone, methyl ethyl ketone, methanol, dimethyl formamide, methyl cellosolve, etc. can be used. It is preferable that the nonvolatile content of the festival be 20 to 95%.

The base materials are paper, glass cloth, and glass benecou.

Mica, polyester fiber, etc. can be used.

The base material is immersed in the above festival and heated at 100 to 200°C for 1 minute or more.
A prepreg can be produced by heating and drying for 1 hour.

In addition, the prepreg was heated under a pressure of 10 to 100 Ky for 13
A laminate can be obtained under conditions of 0 to 180°C and 30 to 240 minutes.

During production, changes such as adding components such as fillers and omitting the use of organic solvents may be made as necessary.

Curing agent, curing accelerator, organic solvent, base sheet.

Fillers and the like may be used singly or in combination.

(Effects of the present invention) As shown in Tables 1 and 2 below, the laminate of the present invention has excellent heat resistance, tracking resistance, and arc resistance, and also has low chlorine impurities and metal It has the characteristic of being less corrosive to other people, making it particularly suitable as a printed circuit substrate.

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

Synthesis Example-1 Allyl alcohol 589 (1 mol), 4-vinylcyclohexene-1-oxide 8689 (7 mol) and B
4.7 g of F3 etherate was mixed at 60°C, and gas chromatography analysis revealed that 4-vinylcyclohexene-1-
The reaction was continued until the oxide conversion rate reached 98 coefficients or higher. Ethyl acetate was added to the obtained reaction crude liquid and washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid.

In the infrared absorption spectrum of the product, the absorption due to the epoxy group of 810,850(!II) observed in the raw material has disappeared, and 1080.1150cIL-'
Gas chromatography analysis showed that there was absorption due to ether bonds in the product, and although there was only a trace amount of allyl alcohol in the product, the infrared absorption spectrum showed that it was 3450 C.
Since there is absorption of OH group at m-', it was confirmed that this compound has the structure shown by the following formula.

Ta.

This compound 40.2,! was dissolved in ethyl acetate and charged into a reactor, and peracetic acid 3959 as an ethyl acetate solution was added dropwise thereto over 2 hours. During this time, the reaction temperature was 40
It was kept at ℃. After adding peracetic acid, heat at 40°C for another 6 hours.
Time aged.

Ethyl acetate was added to the reaction crude solution, and the mixture was washed with alkaline water containing sodium carbonate, and then thoroughly washed with distilled water.

The ethyl acetate layer was concentrated to obtain a viscous clear liquid.

This compound has an oxirane oxygen content of 9.27%, and a characteristic absorption due to the epoxy group is seen at 1260 cm in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups is observed at 1640'♂, and O at 3450'♂.
Since absorption by the -50- group is observed in the H group, 1730tyR'', this compound has the structure of general formula (I) (R1 nigericidyl group is an allyl group, n = average 7. Acetic acid is added to the epoxy group. It was confirmed that the compound contains some groups.

Reference Example-1゜The total amount of chlorine in the epoxy resin synthesized in Synthesis Example 1 was measured.

The measurement was carried out by weighing the sample 2f. The total amount of chlorine was measured by combustion in an oxygen cylinder for 1,000 s ppm. Considering that in ordinary epoxy resins made from epichlorohydrin as a starting material, the total chlorine is usually about several hundred ppm, it can be seen that the total chlorine in 1° of the resin of the present invention is extremely small. .

Reference Example 2 The product of Synthesis Example 1 was cured using 4-methylhexahydro anhydride 7-tal cR (Ricazid MH-700, Shin Nippon Rika Co., Ltd.) as a curing agent and benzyldimethylamine as a curing catalyst. As a comparison resin, bisphenol A and diglycidyl ether (Epicote 828. Yuka shell epoxy) were used and compounded according to the following formulation, melted and mixed at 80C for about 5 minutes, and then deflated under reduced pressure. Then, curing was performed four times by casting to obtain a cured product. For curing, pre-curing was performed at 100°C for 1 hour in O-Lan, and further curing was performed at 160°C.
Post-curing was carried out for 2 hours at °C.

The obtained cured product was cut into test pieces, and JIS
- Measurements of heat distortion temperature, etc. were carried out using -6911, and the results shown in Table 1 were obtained.

Mixing prescription Epoxy resin 1.0 Shodo MH-700
1.0 equivalent benzyldimethylamine (relative to formulation) 0.51 amount T Table 1 Physical properties of cured product It is clear that by using the epoxy resin of formula (I), excellent physical properties of the hardened product can be obtained.

Example-1゜5011r parts of the product of Synthesis Example-1 (hereinafter referred to as parts-f)
') and 50 parts of brominated epoxy resin for laminates (Ciba Geigy, trade name Ar8011), 30 parts of methyl ethyl ketone was added to make a homogeneous solution, and 5.7 parts of dicyandiamide as a KN-forming agent was dissolved in 40 parts of methyl cellosolve. In addition, 0.25 parts of 2-ethyl-4-methylimidazole was added as a curing accelerator to obtain a festival.

This face was impregnated with glass cloth (Nittobo trade name WE-18W epoxy silane treated) and dried by heating at 140° C. for 3 minutes to obtain a 1-rib leg with a resin content of 38-40%.

Next, a 1.6-inch copper-clad laminate was produced from eight fibre-regs under the conditions of 40°C/9/cd pressure, heating temperature of 165°C, and heating time of 60 minutes.

After removing the plane foil by etching this copper-clad laminate, 50 w x x 5 Q. Test piece for the basket? Prepared and processed in a Houlescher cooker (121°C > 260°C)
A soldering heat resistance test was conducted for 30 seconds. The results are shown in Table 2.

Comparative Example - 1゜100 parts of brominated epoxy resin for laminates (Ciba Gaiki Co., Ltd., trade name Ar8011) was used as the epoxy resin...
A laminate was produced and tested in the same manner as in Example 1 except for the following. The results are shown in Table 2.

Table 2. Physical properties of dermal plate ○;No abnormality X: Measling or blistering patent author Daicel Chemical Industries, Ltd.

Claims (1)

[Claims] A laminate characterized by comprising an epoxy resin and a curing agent represented by the following formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) However, R_1 is 1 active hydrogen. organic compound residues. n_1, n_2...n_l is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100. l represents an integer from 1 to 100. A is an oxycyclohexane skeleton having a substituent and is represented by the following formula. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ group, carboalkyl group, or carboaryl group), but there are mathematical formulas, chemical formulas, tables, etc., and at least one or more ▼ is contained in the resin represented by formula (I).