JP2001253951A - Laminate sheet formed by using flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate sheet having highly flame-retardant properties together with excellent reliability, even though any halogen compound is not applied. SOLUTION: This laminate sheet is formed using a resin composition which contains (A) a resin comprising an un-halogenated epoxy having at least two epoxy groups in a molecule, (B) a curing agent, and (C) a layered clay mineral containing organic cations between the layers as essential components, wherein the resin composition contains the layered clay mineral in an amount of 0.8-10 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate using a flame-retardant resin composition having excellent flame retardancy without using a halogen-based flame retardant.

[0002]

2. Description of the Related Art Thermosetting resins typified by epoxy resins are widely used in electric and electronic equipment parts due to their excellent properties, and are provided with flame retardancy to ensure fire safety. There are many examples. Conventionally, halogen-containing compounds such as brominated epoxies have generally been used to make these resins flame-retardant.

[0003] Although these halogen-containing compounds have high flame retardancy, aromatic bromine compounds not only separate corrosive bromine and hydrogen bromide by thermal decomposition but also decompose in the presence of oxygen. In some cases, it can form highly toxic polybromodibenzofurans and polybromodibenzooxins. Further, it is extremely difficult to treat aging waste materials and refuse containing bromine.

For these reasons, it is a well-known fact that phosphorus compounds and inorganic flame retardants represented by metal hydrates have been widely studied as flame retardants instead of bromine-containing flame retardants. However, when a phosphate ester or the like is used for the epoxy resin system, the usable range is limited due to bleeding or hydrolyzability. In addition, general phosphoric acid ester compounds having a functional group such as phenolic hydroxyl group generate free phosphoric acid by hydrolysis, which significantly deteriorates the electrical characteristics and reliability, and the metal hydrate. Must be added in a large amount in order to exhibit sufficient flame retardancy, resulting in a disadvantage that the curability and strength of the resin composition are reduced.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made as a result of intensive studies to solve the above-mentioned problems.
An object of the present invention is to provide a laminate having high flame retardancy without adding a halogen compound and not deteriorating the characteristics of a product.

[0006]

That is, the present invention provides:
A resin composition comprising, as essential components, an unhalogenated epoxy resin (A) having at least two epoxy groups in a molecule, a curing agent (B), and a layered clay mineral (C) containing an organic cation between layers. And a laminated board characterized by comprising a flame-retardant resin composition in which the layered clay mineral in the resin composition is at least 0.8% by weight and at most 10% by weight and a base material. It is.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, when a metal hydrate or the like is used in an epoxy resin system, a large amount must be added in order to exhibit sufficient flame retardancy.
A drawback such as a decrease in strength has occurred. In the present invention, in order to solve such a problem, the compatibility with the resin is increased by including an organic cation between the layers of the layered clay mineral, and the decomposition of the resin is suppressed by increasing the interaction with the resin. The technical point is to achieve both flame retardancy and reliability.

The epoxy resin (A) having at least two epoxy groups in one molecule and excluding the halogenated epoxy resin in the present invention includes bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin Resins, phenol novolak type epoxy resins, cresol novolak type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, N-glycidyl compounds from aromatic amines and heterocyclic nitrogen bases, such as N, N-diglycidylaniline, tri Glycidyl isocyanurate, N, N, N ', N'-
Examples thereof include tetraglycidyl-bis (p-aminophenyl) -methane, but are not particularly limited thereto. These can be used in combination of several types.

However, halogen-containing epoxies such as brominated bisphenol A epoxy and brominated novolak epoxy are excluded because the present invention advocates a resin composition not using a halogen-based flame retardant.
Chlorine contained in an ordinary epoxy resin derived from epichlorohydrin is unavoidably mixed. However, the amount is on the order of several hundred ppm of hydrolysable chlorine at levels known to those skilled in the art.

As the curing agent (B) used in the present invention, any of those known to those skilled in the art can be used. In particular, ethylene diamine, trimethylene diamine,
Tetramethylenediamine, linear aliphatic diamines of C ₂ -C _20, such as hexamethylenediamine, meta-phenylenediamine, para-phenylenediamine, para-xylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodicyclohexane, bis (4
Amines such as -aminophenyl) phenylmethane, 1,5-diaminonaphthalene, metaxylylenediamine, paraxylylenediamine, 1,1-bis (4-aminophenyl) cyclohexane, dicyandiamide, phenol novolak resin, and cresol novolak resin , Ter
Novolak-type phenol resins such as t-butylphenol novolak resin and nonylphenol novolak resin;
Resole type phenol resin, polyoxystyrene such as polyparaoxystyrene, phenol aralkyl resin,
Phenolic compounds such as naphthol-based aralkyl resins, in which the hydrogen atom bonded to the benzene ring, naphthalene ring or other aromatic ring is substituted with a hydroxyl group, and a phenolic resin or acid anhydride obtained by co-condensation with a carbonyl compound However, the present invention is not particularly limited to these.

Next, examples of the layered clay mineral (C) containing an organic cation between layers include smectite types such as montmorillonite, saponite, beidellite, hectorite, saponite, and stevensite, vermiculite, illite, and the like. There are sericite and the like, and both natural products and synthetic products can be used. As the layered clay mineral, a smectite-type clay mineral is preferable, and among them, montmorillonite is most preferable.

The organic cation contained between the layers of the layered clay mineral includes an organic ammonium ion, an organic phosphonium ion, an organic sulfonium ion and the like, and an organic ammonium ion or an organic phosphonium ion is preferable.

Among them, an organic ammonium ion is preferable because the interaction with the resin can be controlled by the structure of the organic cation contained between the layers, and the selection of the structure of the organic cation is widened.

The organic ammonium ions include dodecyl ammonium ion, dodecyl trimethyl ammonium ion, myristyl ammonium ion, myristyl trimethyl ammonium ion, stearyl ammonium ion, stearyl trimethyl ammonium ion,
Lauryl ammonium ion, lauryl trimethyl ammonium ion, benzyl ammonium ion, benzyl dimethyl ammonium ion, benzyl tritriethyl ammonium ion, phenyl ammonium ion,
4-methylphenylammonium ion, 3-methylphenylammonium ion, 4,4′-diammonium diphenylmethane, 3,3′-diammonium diphenylmethane, 4,4′-diammonium diphenyl ether, 3.3′-diammonium diphenyl ether,
4,4′-diammonium diphenyl sulfone, 3,
3'-diammonium diphenyl sulfone, 2,2-bis [4- (4-ammoniumphenoxy) phenyl] propane, 2,2-bis [4- (3-ammoniumphenoxy) phenyl] propane, bis [4- (4 -Ammoniumphenoxy) phenyl] sulfone, bis [4- (4
-Ammoniumphenoxy) phenyl] sulfone.

As the organic ammonium ion, when at least one of the groups bonded to the quaternized nitrogen atom is an aromatic group, the interaction with the resin becomes large, so that phenyl ammonium ion, 4-methylphenyl ammonium Ion, 3-methylphenylammonium ion, 4,4′-diammoniumdiphenylmethane, 3,
3′-diammonium diphenylmethane, 4,4′-diammonium diphenyl ether, 3.3′-diammonium diphenyl ether, 4,4′-diammonium diphenyl sulfone, 3,3′-diammonium diphenyl sulfone, 2,2-bis [4- (4-ammoniumphenoxy) phenyl] propane, 2,2-bis [4-
(3-ammoniumphenoxy) phenyl] propane,
Bis [4- (4-ammoniumphenoxy) phenyl]
Sulfone, bis [4- (4-ammoniumphenoxy)
Phenyl] sulfone is preferred.

Preferred examples of the organic phosphonium ion include quaternary phosphonium ions such as tetraphenylphosphonium ion and tetraethylphosphonium ion, but are not particularly limited thereto.

The layered clay mineral containing an organic cation between layers includes an organic cation, a chloride ion, a bromide ion,
It can be produced by using an organic onium salt which is a salt with an anion such as formate ion or acetate ion. As an example, there is a method in which a layered clay mineral containing a metal ion between layers is dispersed in water, and an organic onium salt or a solution thereof is added thereto, followed by stirring and ion exchange.

The mixing ratio of the epoxy resin (A) and the curing agent (B) is set arbitrarily. However, a large excess of any one of the functional groups is not preferred because the moisture resistance, moldability, and electrical properties of the cured product are reduced. The component (C) is contained so that the weight ratio of the layered clay mineral in the resin composition is in the range of 0.8% by weight to 10% by weight. If the proportion is less than 0.8% by weight, the effect of flame retardancy is not obtained, and if it exceeds 10% by weight, heat resistance and moisture resistance are deteriorated and moldability is adversely affected.

The flame-retardant resin composition of the present invention is a thermosetting resin which has high flame retardancy without adding a halogen compound and does not deteriorate the properties of products, and is used for electronic parts and electric parts. It is also suitably used for sealing, coating, insulation, laminates, metal-clad laminates and the like.

In the production of the laminate according to the present invention, a varnish obtained by dissolving a flame-retardant resin composition in a solvent can be used. This varnish is coated and impregnated on a substrate such as paper, glass woven fabric, glass nonwoven fabric, or a cloth having a component other than glass, and dried in a drying oven at 80 to 200 ° C. to form a prepreg. Prepare. This is heated and pressed to produce a laminate or a metal-clad laminate for a printed wiring board.

A common solvent is used for preparing a varnish of the flame-retardant resin composition according to the present invention. The solvent used must have good solubility in part or all of the composition, but a poor solvent can be used as long as it has no adverse effect. Examples of the solvent used include acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, toluene,
Aromatic hydrocarbon solvents such as xylene and mesitylene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, isobutyl cellosolve, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, Various glycol ether solvents such as dipropylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ester solvents such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and ethyl acetate; Dialkyl glycol ether solvents such as toluene dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, amide solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, methanol, ethanol, etc. Alcohol-based solvents, and some of them can be used in combination.

[0022]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the present invention. First, Synthesis Examples 1 to 3 of the layered clay mineral containing an organic cation between the layers as the component (C) will be described. Next, a layered clay mineral containing an organic cation will be blended between the layers to form a laminate. Examples 1 to 4 for preparing a board are described.

(Synthesis Example 1) 110 g of Kunipia F (montmorillonite manufactured by Kunimine Kogyo KK) was swelled and dispersed in 2200 ml of water at 80 ° C., and 9.3 g of aniline and 10.4 ml of hydrochloric acid (35%) were added to 100 ml of water. The added solution was added dropwise and stirred at 80 ° C. for 1 hour. Since montmorillonite aggregates, filtration and washing are repeated to remove the ion-exchanged sodium chloride, followed by drying to obtain montmorillonite [clay mineral (a)] containing phenylammonium ions between layers. The yield was 60%.

(Synthesis Example 2) 110 g of Kunipia F (montmorillonite manufactured by Kunimine Industries Co., Ltd.) was swelled and dispersed in 2200 ml of water at 80 ° C., and mixed with 150 ml of water and 50 ml.
20.5 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and hydrochloric acid (3
5%) A solution to which 10.4 ml was added was added dropwise.
Stirred for hours. Since montmorillonite aggregates, filtration and washing are repeated to remove the ion-exchanged sodium chloride, and dried, and montmorillonite [clay containing ammonium ion of 2,2-bis [4- (4-aminophenoxy) phenyl] propane between layers is used. Mineral (b)] was obtained.
The yield was 88%.

(Synthesis Example 3) 110 g of Kunipia F (Montmorillonite manufactured by Kunimine Industries Co., Ltd.) was swelled and dispersed in 2200 ml of water at 80 ° C., and a solution obtained by adding 41.9 g of tetraphenylphosphonium bromide to 200 ml of methanol was added dropwise. And stirred at 80 ° C. for 1 hour. Since montmorillonite aggregates, filtration and washing are repeated to remove the ion-exchanged sodium bromide and dried to obtain montmorillonite [clay mineral (c)] containing tetraphenylphosphonium ions between layers. The yield was 85%.

(Example 1) 87.3 parts by weight of phenol novolak epoxy resin ("Epiclon" N-770, epoxy equivalent 190 g / eq, manufactured by Dainippon Ink) and 9.7 parts by weight of dicyandiamide were obtained according to Synthesis Example 1. 3.0 parts by weight of the obtained clay mineral (a) was added to methyl cellosolve /
A mixed solvent of methyl ethyl ketone = 1/1 was added, and the varnish was adjusted to a non-volatile content concentration of 50%. Using this varnish, 100 parts of glass cloth (0.18 mm thick, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts of varnish solids, dried in a dryer oven at 150 ° C. for 4 minutes, and resin content was measured. A 44.4% prepreg was prepared. Eight pieces of the obtained prepregs were stacked, and an electrolytic copper foil having a thickness of 35 μm was stacked on the upper and lower sides of the prepregs, and heated and pressed at a pressure of 3.9 MPa (40 kgf / cm ² ) at a temperature of 170 ° C. for 120 minutes to form .6
mm double-sided copper-clad laminate was obtained. The obtained laminate was evaluated for flame retardancy, solder heat resistance, peel strength, and glass transition temperature.

The flame retardancy was evaluated by the vertical method according to the UL-94 standard. Solder heat resistance and peel strength are JIS C
The heat resistance was measured in accordance with Example 6481, and the solder heat resistance was determined by performing a moisture absorption treatment for 2 hours after boiling and then floating in a solder bath at 260 ° C. for 180 seconds to check for abnormal appearance. The glass transition temperature was determined from the peak temperature of tan δ by a viscoelastic method.

Examples 2 to 4 Phenol novolak epoxy resin ("Epiclone" N-770), dicyandiamide, clay mineral (a) obtained according to Synthesis Example 1, and clay mineral (b) obtained according to Synthesis Example 2 A laminate was prepared in the same manner as in Example 1 except that the clay mineral (c) obtained in Synthesis Example 3 was blended in accordance with Table 1 to obtain a flame retardant, solder heat resistant, peel strength, and glass. The transition temperature was evaluated.

[0029]

[Table 1]

(Comparative Examples 1 to 4) A laminate was prepared in the same manner as in Example 1 except that the respective components were blended according to Table 2, and flame retardancy, solder heat resistance, peel strength, and glass transition temperature were measured. Was evaluated.

[0031]

[Table 2]

In Comparative Example 3 using the conventional flame retardant, although the flame retardancy achieved V-0, since a large amount of the flame retardant was added, blisters were generated in the solder heat resistance test. Low peel strength. In Comparative Example 4, since the curability was poor, the glass transition temperature was low, the peel strength was low, and blisters were generated in the soldering heat test. In Examples 1 to 4 and Comparative Example 1 using a layered clay mineral containing an organic cation between layers according to the present invention, the solder heat resistance, peel strength, and glass transition temperature all showed good results. Comparative Example 1 with a small amount of addition of the layered clay mineral containing an organic cation between the layers caused by the above-mentioned method has insufficient flame retardancy, and the compounding amount of the layered clay mineral containing an organic cation between the layers is small. In Comparative Example 2 having a large number, the solder heat resistance was reduced.

[0033]

According to the present invention, a resin composition using a layered clay mineral containing an organic cation between layers has high flame retardancy without adding a halogen compound and has excellent reliability. And flame retardant resin composition suitably used for non-halogen material applications required in the future, and,
A laminated board using the same is provided, and its industrial utility value is extremely high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 9/04 C08K 9/04 C08L 63/00 C08L 63/00 C // H05K 1/03 610 H05K 1 / 03 610L 610S F-term (reference) 4F072 AA01 AA04 AA06 AA07 AB09 AB27 AD23 AE07 AF30 AG03 AG14 AG19 AH02 AH22 AJ04 AK14 AL13 4F100 AA01A AB17 AB33 AC03A AG00 AK53A AL05A AL06A AT00B BA02A02 CD02 002 CD07W CD14W DM007 EN036 EN076 EN126 FB087 FD137 FD14X FD146 GQ00

Claims (4)

[Claims] An essential component is an unhalogenated epoxy resin (A) having at least two epoxy groups in one molecule, a curing agent (B), and a layered clay mineral (C) containing an organic cation between layers. A flame retardant resin composition in which the layered clay mineral in the resin composition is 0.8% by weight or more and 10% by weight or less and a base material. A laminated plate characterized by the above. 2. The laminate according to claim 1, wherein the organic cation contained between the layers of the layered clay mineral (C) is a quaternary ammonium ion. 3. The laminate according to claim 2, wherein at least one of the quaternary ammonium ions bonded to the quaternized nitrogen atom is an aromatic group. 4. The laminate according to claim 1, wherein the organic cation contained between the layers of the layered clay mineral (C) is a quaternary phosphonium ion.