JPH03287678A - Flame-retardant adhesive composition and filmy adhesive - 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 (Field of Industrial Application) The present invention relates to a flame-retardant adhesive composition and a film-like adhesive obtained by forming the flame-retardant adhesive composition into a film.

More specifically, the present invention has excellent flame retardancy and peel adhesion, and can be used as an adhesive (particularly for bonding a honeycomb core to a surface material constituting a honeycomb sandwich panel), or as an electronic component sealant. The present invention relates to the composition suitably used for insulating materials and the like, and a film adhesive made from the composition.

(Conventional Technique 1) In recent years, as shown in Japanese Unexamined Patent Publication No. 58-201840, in order to improve high adhesiveness and excellent flame retardancy, epoxy resin is added to both ends of the adhesive. Attempts have been made to blend reactants of butadiene-acrylonitrile copolymers having carboxyl groups, nitrile rubber, brominated epoxy resins, and the like.

(Problem B to be Solved by the Invention) However, the above composition has the disadvantage that flame retardancy and adhesiveness are not necessarily sufficient.

(Means for Solving the Problems) In response to the current situation, the present inventors have improved flame retardancy by incorporating wollastonite, antimony trioxide, and bromine into the composition, and further, It was discovered that wollastonite improves the cohesive force of the cured product, thereby improving the adhesiveness, and the present invention was completed.

That is, the present invention consists of; The present invention relates to a flame-retardant adhesive M composition containing 15 to 40% by weight of bromine, and further relates to (1) a film-like adhesive comprising the above flame-retardant adhesive composition.

The epoxy resin used in the present invention is an epoxy resin that does not contain silicon atoms or titanium atoms, and specifically includes glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, cycloaliphatic Examples include group epoxy resins, linear aliphatic epoxy resins, rubber-modified epoxy resins, urethane-modified epoxy resins, and halogen-containing epoxy resins.

The above halogen-containing epoxy resin used in the present invention is
Epoxy resin is halogenated with chlorine, bromine, etc.

When imparting plasticity to the cured product of the composition of the present invention,
Rubber-modified epoxy is preferably used.

The rubber-modified epoxy resin used in the present invention is a reaction product of an epoxy resin and a rubber having a terminal or pendant carboxyl group. In the present invention, rubber includes polybutylene, polybutadiene (PBR), butadiene-acrylonitrile rubber (NBR), silicone rubber, and the like.

In particular, liquid butadiene-acrylonitrile rubber, which has carboxyl groups at both ends, is preferably used as the rubber-modified epoxy resin because it has good compatibility with other epoxy resins and gives the cured product good flexibility. .

Examples of the curing agent used in the present invention include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, polyamide polyamines, acid anhydrides, imidazoles, and polymercaptans.

Specifically, diethylenetriamine (DETA), triethylenetetramine (TETA), veridine, pyridine, iminobispropylamine (dipropylenetriamine) (DPTA), bis(hexamethylene)triamine, 1,3.6-trisaminomethyl Hexane (TMAR
), polyether diamine, tetraethylene pentamine (TEPA), dipropylene diamine (DPDA),
Dimethylaminepropylamine (DMAPA), diethylaminopropylamine (DEAPA), AMIN
E 24B, N-aminoethylpiperazine (N-AR
P), Ramiron C-260, Picoline, Menthendiamine (MDA), Influorondiamine 7 (IPDA)
, S Cure211.212, Wondermin HM, 1
．． 38AC, m-xylene diamine (m-XDA), Shawamine χ, amine black, Schilleramine black, Shawamine N, Shawamine 1001.1010,
Metaphenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), ketimine, tetramethylguanidine, benzyldimethylamine, 2,4.6-tris(dimethylaminomethyl)phenol (DMP-30), anhydrous Phthalic acid (PA), trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate) (TME), glycerol tris(anhydrotrimellitate) ) (TMG), maleic anhydride (MA), succinic anhydride (SA), tetrahydrophthalic anhydride (THPA), methyltetrahydrophthalic anhydride (Me-THPA), methylnadic anhydride (N
MA), alkenyl succinic anhydride, hexahydrophthalic anhydride (HHPA), methylhexahydrophthalic anhydride (Me-HHPA), 2-methylimidazole, 2
-Ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, l-benzyl-2-methylimidazole, 1-cyanoethyl-2-methyl-4-methylimidazole, 1-cyanoethyl -2-Undecylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate), 2,4-diamino-6- (
2-Methylimidazolyl-(1))-ethyl-5-)riazine, 2,4-diamino-6-(2-ethyl-4-methylimidazolyl-(1)]-]ethyl-3-triazine2,4-diamino -6[2-undecylimidazolyl-(1)]-]ethyl-5-riazine, 2-phenyl-
4,5-dihydroxymethylimidazole, 2-phenyl4-methyl-5-hydroxymethylimidazole, 1
-cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, dicyandiamide (DICY), organic acid hydrazide, diaminomaleonitrile ( DAMN), dichlorophenyldimethylurea (DCMU), etc. can be used.

The amount of curing agent blended into the epoxy resin in the present invention is preferably about 0.5 to 1.5 equivalents per equivalent of epoxy group, and in the present composition, by containing it in the range of 1 to 15% by weight, A cured product with good adhesive properties can be obtained.

If the amount is less than 1% by weight, sufficient curing of the epoxy resin will not occur, and if it exceeds 15% by weight, the amount of curing agent will be excessive, resulting in unreacted curing agent remaining and decreasing the cohesive strength of the cured product. decreases rapidly.

The flame retardant used in the present invention is a flame retardant that does not have an epoxy group, and examples include phosphorus flame retardants, halogen flame retardants, and inorganic flame retardants.

Specifically, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tris(halopropyl) phosphate, tris(halothyl)
Phosphate, chlorinated paraffin, chlorinated polyethylene perchloropentacyclodecane, hexabromobenzene, decadibromodiphenyl oxide, tetrabromobisphenol A, hexabromocyclododecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl Ether, pentabromotoluene, ammonium bromide, red phosphorus, tin oxide, tin hydroxide, molybdenum oxide, ammonium molybdate, zirconium oxide, zirconium hydroxide,
Barium metabolate, zinc oxalate, aluminum hydroxide, dawsonite, magnesium hydroxide, calcium aluminate, more preferably decabromodiphenyl oxide, tetrabromobisphenol A, hexabromocyclododecane, decabromodiphenyl ether, hydroxide Aluminum, magnesium hydroxide, etc., the product name is Pyro-Chek77B (Ferro Cor
(manufactured by Sayteck), 5aytex BT-93 (manufactured by Sayteck), etc. can be used alone or as a mixture.

As the flame retardant, antimony trioxide, and wollastonite of the present invention, those that have been surface-treated according to the coupling rule etc. are preferably used in order to keep the viscosity of the composition of the present invention low (film formation), and Lower viscosity (filming)
And for the purpose of improving the cohesive force of the cured product, the average particle size is 0.5~
A thickness of 50 μm is preferably used. In the present invention, the average particle diameter is a value measured by a sinking balance method.

In the present invention, (i) bromine is 15 to 40% by weight, preferably 20 to 30% by weight, and (b) antimony trioxide is 3% by weight.
-10% by weight, preferably 4-8% by weight, (c) wollastonite 5-30% by weight, preferably 6-20% by weight
By containing it, flame retardancy is improved, and wollastonite also has the effect of improving the cohesive force of the cured product.

In the adhesive composition of the present invention, containing a specific amount of bromine in the composition means that the additive components constituting the composition, such as the epoxy resin, curing agent, flame retardant, etc., contain bromine. It is present as a containing compound, meaning that the composition as a whole contains bromine in the above specified amount, and the component may contain bromine bonded to a plurality of additives or compounds.

In the present invention, wollastonite is generally used as a flame retardant in combination with predetermined amounts of bromine and antimony trioxide. By adding the same amount of aluminum hydroxide or magnesium hydroxide, the same degree of flame retardant effect can be obtained in the cured product of the composition, and the adhesive strength (
It was found that the material has a cohesive force).

If even one of the three conditions (a) to (c) above is less than the lower limit, sufficient flame retardancy cannot be exhibited.
Moreover, even if the upper limit is exceeded, the flame retardance will not be improved and the viscosity will increase rapidly, which will cause problems when mixing the composition and when molding the composition into a film.

Furthermore, if the amount of wollastonite is less than 5 parts by weight, the cohesive force after curing the composition will decrease rapidly.

If the cured product of the composition of the present invention is to have durability against moisture, salt, temperature changes, etc., this can be improved by adding a coupling agent (especially epoxy silane).

The composition of the present invention can be produced by mixing desired amounts of each essential component and, if necessary, each optional component (including a solvent and known additives for adhesives) at room temperature or under heating. This is done by

In addition, the composition of the present invention has appropriate viscosity and adhesiveness due to the addition of wollastonite, antimony trioxide, etc., so it is easy to form into a film (and when used as a film adhesive). It has good handling properties because it is less sticky.

Further, for the purpose of imparting thixotropy, talc, asbestos, silica (fine powder), etc. are preferably used alone or as a mixture.

(Function) The flame retardant adhesive composition of the present invention and the film adhesive formed from the flame retardant adhesive composition contain 15 to 40 bromine.
By containing 3-10% by weight of antimony trioxide and 5-30% by weight of wollastonite, the mutual flame retardant effects are promoted, higher flame retardance can be obtained, and Lastonite was able to improve the cohesive force of the cured product.

[Method of Measuring Properties and Evaluating Effects] (1) Peel Adhesion: (Method of Preparing Test Body and Method of Evaluation) It was conducted in accordance with the T-peel test of JIS-6854.

The test piece material is 5US430 (thickness 0.15m
), a film adhesive of about 80 g/nf was used, and the adhesive was pressed and cured at 130'C for 11 hours.

The moving speed of the grip during strength measurement was 200 stitches per minute.

(Evaluation) Average value of measured values; 3.0 kg or more/25 units...0 3, less than 0 kg/25 units...× ■ Flame retardance: (Method for preparing test specimen for base material test) 40X40- 5US430 (thickness 0°15cm) cut into
) and aluminum honeycomb core (foil thickness 76μm, core thickness 50■
, cell size 0.25 inch) through a film adhesive (basis weight: approximately 80 g/po) as shown in Figure 1.
It was pressed and cured at 130° C. for 1 hour to obtain a test specimen.

(Evaluation method) The base material test was conducted according to the base material test shown in JIS A1321, and the number of test pieces was three.

(Evaluation) If all three specimens for base material testing pass the base material test...
...O If even one out of three test specimens for the base material test did not pass the base material test...x, and the film adhesive was evaluated by the method described above.

(Example) - A uniform composition was prepared by heating and stirring at the mixing ratio shown in Table 1.

This composition was placed on a release paper to give a basis weight of about 80 g/bot to produce a uniform film adhesive (effects of the invention) As explained above, the flame retardant adhesive composition of the present invention, A film-like adhesive obtained by forming a flame-retardant adhesive composition into a film contains 15 to 40% by weight of bromine, 3 to 10% by weight of antimony trioxide, and 5 to 30% by weight of wollastonite. The mutual flame retardant effects were promoted, and higher flame retardancy could be obtained, and the cohesive force of the cured product could be improved by wollastonite.

[Brief explanation of the drawing]

FIG. 1 is a side view showing a test specimen for evaluating flame retardancy using a film adhesive made from a flame retardant adhesive composition that is an effect of the present invention. 1...Film adhesive (cured product) 2...Test piece (SUS430) 3...Aluminum honeycomb core 4...Test specimen for flame retardancy evaluation ¥1 diagram

Claims (2)

[Claims] (1) Consists of 40-85% by weight of epoxy resin, 1-15% by weight of curing agent, 0-30% by weight of flame retardant, 3-10% by weight of antimony trioxide, 5-30% by weight of wollastonite, and further contains bromine in the composition. A flame-retardant adhesive composition characterized by containing 15 to 40% by weight. (2) Consists of 40-85% by weight of epoxy resin, 1-15% by weight of curing agent, 0-30% by weight of flame retardant, 3-10% by weight of antimony trioxide, 5-30% by weight of wollastonite, and further contains bromine in the composition. A film-like adhesive comprising a flame-retardant adhesive composition, characterized in that it contains 15 to 40% by weight.