JPH0647881A - Fire retardant laminate sheet - Google Patents

Abstract

PURPOSE:To obtain a laminated sheet excellent in heat resistance and electric characteristics and having fire retardancy by preparing varnish by resolving an epoxy resin, a curing agent and a curing accelerator to impregnate a base sheet with this varnish to obtain a prepreg and superposing the prepregs one upon another to integrally mold them under heating and pressure. CONSTITUTION:One kind of a substance selected from a compd. having one or more vinyl group and one epoxy group in its molecule, a polybasic acid anhydride, polybasic acid, an acid polymer and a polymer containing one or move active hydrogen is used. A resin having a vinyl group obtained by reacting one compd. selected from compds. each having one or more active hydrogen with this substance is epoxidized to obtain an epoxy resin which is, in turn, used in an amt. of 20-80wt.%. In addn. thereto, 80-20 pts.wt. of a halogenated epoxy resin respresented by formula I (wherein n is an integer of 0 or more and X is a bromine atom or a chlorine atom) and a curing agent for an epoxy resin are together used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated plate made of an epoxy resin having excellent heat resistance and flame retardancy.

[0002]

2. Description of the Related Art Laminates made of epoxy resin are widely used as structural materials because they are excellent in mechanical strength, dimensional stability and chemical resistance. In the field of electronics, in addition to the above-mentioned properties, it is often used as a printed circuit board because it has good physical properties such as electric insulation, water resistance, and dielectric properties. However, miniaturization of electrical products,
It is strongly demanded that the heat resistance and tracking resistance of laminated plates be improved, arc resistance be improved, and metal corrosion be reduced due to the reduction of impurities such as chlorine due to the miniaturization of printed circuits and the influence of heat treatment temperature in the manufacturing process. . For these reasons, it has been desired to develop an epoxy resin laminate having excellent heat resistance, tracking resistance and arc resistance, and having a low impurity content such as chlorine. On the other hand, in the field of electrical products, the demand for flame retardancy has become very strict recently, and therefore it is necessary to impart flame retardancy to epoxy laminated boards as well.

In the epoxy laminate, an epoxy resin produced from tetobrombisphenol A or tetrachlorobisphenol A and epichlorohydrin is used in combination with a usual epibis type epoxy resin or novolac epoxy resin or used alone. This gives flame retardancy.

[0004]

However, when it is used in combination with an epoxy resin laminated plate made of tetrabromobisphenol A or tetrachlorobisphenol A as a raw material, or an ordinary epibis type epoxy resin or novolac epoxy resin. When the flame retardancy is increased, the heat resistance and electric characteristics are deteriorated, and conversely, when the heat resistance and electric characteristics are maintained, sufficient flame retardancy cannot be obtained.

As a result of investigations by the present inventors, the epoxy resin recited in claims 1 to 11 is used in combination with the epoxy resin containing tetrabromobisphenol A or tetrachlorobisphenol A as a raw material. As a result, it was found that an epoxy laminate having excellent heat resistance and electrical properties and flame retardancy was obtained, and the present invention was completed.

Further, it has been clarified that the characteristics of the flame-retardant laminate can be changed and various characteristics can be given by combining various kinds of (a), (b) and (c) to be used.

[0007]

Means for Solving the Problems That is, the present invention provides: (A) (a) a compound having at least one vinyl group and one epoxy group in one molecule, (b) a polybasic acid anhydride By reacting at least one selected from polybasic acids, acid-terminated polymers, and polymers containing carboxylic acid groups and (c) at least one selected from compounds having one or more active hydrogens. Epoxy resin obtained by further epoxidizing the obtained resin having a vinyl group 20 to 80
Parts by weight (B) halogenated epoxy resin represented by the general formula 1 8
It is a flame-retardant laminated board characterized by comprising 0 to 20 parts by weight and (C) a curing agent for epoxy resin.

Next, the present invention will be described in more detail.

The compound having one epoxy group and one or more vinyl groups in one molecule used in the present invention is (IV) << i is an integer of 1 to 5, R ¹ and R ⁴ are hydrogen atoms or an alkyl group having 1 to 50 carbon atoms or a substituted phenyl group,
R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 50 carbon atoms, and R ² and R ³ may be wrapped around a ring.

Examples of the compound represented by (IV) are the compounds shown below.

4-vinylcyclohexene-1-oxide, 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide, limonene monoxide, trivinylcyclohexane monoxide, divinylbenzene monoxide, butadiene monooxide. Oxide and 1,2-epoxy-
Examples include compounds represented by (I) such as 9-decene, compounds represented by (II) such as allyl glycidyl ether, and compounds such as glycidyl styryl ether.

Further, the following compounds can also be used.

[0013]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5] These may be used alone or in combination of two or more.

If desired, ethylene oxide,
Propylene oxide, cyclohexene oxide, styrene oxide, monoepoxides such as α-olefin epoxide, vinyl cyclohexene dioxide, 3,4-
A diepoxide such as epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate may be used at the same time as the compound having one epoxy group and one or more vinyl groups in one molecule.

The polybasic acid anhydrides or polybasic acids (b) used in the present invention include aromatic polybasic acids and acid anhydrides thereof, and aliphatic polybasic acids and acid anhydrides thereof. Examples of aromatic polybasic acids and acid anhydrides thereof include:
Examples include phthalic anhydride, isophthalic acid, terephthalic acid and trimellitic anhydride. Examples of the aliphatic polybasic acid and its acid anhydride include tetrahydrophthalic acid, 4-methylhexahydrophthalic acid, hexahydrophthalic acid, adipic acid, maleic acid, and their acid anhydrides, fumaric acid and sebacic acid. , Dodecane diacid, and their acid anhydrides.

The acid-terminated polymer used in the present invention is an acid-terminated polymer obtained by reacting a polybasic acid with polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol, polyvinyl cyclohexene glycol or the like. Examples include ethers, acid-terminated polyesters, acid-terminated polybutadienes and acid-terminated polycaprolactones.

Further, an acrylic copolymer having a carboxylic acid group can be used instead of the acid terminal polymer, and it contains a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and a carboxylic acid group. These polymers may be used alone or in combination of two or more.

Next, as the compound (c) having active hydrogen used in the present invention, alcohols, phenols, carboxylic acids, amines, thiols, hydroxyl-terminated polymers, and hydroxyl groups can be used. The polymer etc. which are contained are mentioned.

The alcohols are monovalent, divalent, trivalent or higher, and include, for example, methanol, ethanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol. Examples thereof include butanediol, hexanediol, glycerin, butanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol, triglycerol and the like. In addition, neopentyl glycol, neopentyl glycol ester of hydroxyhyvalic acid, dipentaerythritol,
1,4-cyclohexanedimethanol, trimethylpentanediol, 1,3,5-tris (2-hydroxyethyl) cyanuric acid, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, etc. Can also be used.

Examples of the phenols include phenol, cresol, catechol, pyrogallol, hydroquinone,
Hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, ethylene oxide adduct of bisphenol A, propione oxide adduct of bisphenol A, phenol Resin and cresol-novolak resin.

Examples of the hydroxyl group-terminated polymer used in the present invention include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, polycyclohexene glycol and polyvinyl cyclohexene glycol, hydroxyl group-terminated polyester, hydroxyl group-terminated polybutadiene, Examples include hydroxyl-terminated polycaprolactone and polycarbonate diol.

Further, an acrylic copolymer having a hydroxyl group may be used instead of the hydroxyl group-terminated polymer.

As carboxylic acids, formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane diacid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid. Acid, terephthalic acid, etc.

Further, compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid and oxycaproic acid, can also be mentioned.

The amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine,
Octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine and the like.

As the thiols, methyl mercaptan,
Mercapto such as ethyl mercaptan, propyl mercaptan, phenyl mercaptan, mercaptopropionic acid or polyhydric alcohol ester of mercaptopropionic acid, for example, ethylene glycol dimercaptopropionic acid ester, trimethylolpropane trimercaptopropionic acid, pentaerythritol pentamercaptopropionic acid, etc. Can be given.

Further, as the compound having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, Styrene-maleic acid copolymer resin, alkyd resin, polyester polyol resin,
Examples include polyester carboxylic acid resins, polycaprolactone polyol resins, polypropylene polyols, polytetramethylene glycol, and the like.

The compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples thereof include allyl alcohol, acrylic acid, methacrylic acid,
There are 2-hydroxyethyl methacrylate, 3-cyclohexenemethanol, tetrahydrophthalic acid and the like.

Any compound having these active hydrogens can be used, and two or more kinds thereof may be mixed.

The epoxy resin used in the flame-retardant laminate of the present invention includes the compound (a) having at least one vinyl group and one epoxy group in the above molecule, a polybasic acid anhydride, and a polybasic compound. Obtained by reacting at least one selected from an acid, an acid terminal polymer, and a polymer (b) containing a carboxylic acid group with at least one selected from a compound (c) having active hydrogen. It is obtained by further epoxidizing a resin having a vinyl group with an epoxidizing agent.

The charging ratio of the starting materials (a), (b), and (c) is 1 to 99 parts by weight of (a), preferably 30 to 80 parts, and 99 to 1 parts by weight of (b). Parts, preferably 20 to 70 parts, and 0 to 99 parts by weight of (c), preferably 0 to 30 parts. The component (c) may not be used depending on the case. When the component (c) is not used,
It is necessary to control the molecular weight while detecting the dehydration amount by controlling the reaction time, the degree of reduced pressure, the reaction temperature, and the like.

When the amount of component (a) used is relatively small, the content of epoxy groups in the target epoxy resin is small. The molar ratio of component (a) / component (b) is 0.
It is 4 to 5.0, preferably 0.5 to 3.0.

When the ratio of the component (a) is increased, the ratio of hydroxyl groups at the terminals increases, and when the hydroxyl group terminals and the carboxyl group terminals are present, all the terminals become hydroxyl groups as the dehydration reaction proceeds.

On the contrary, when the ratio of the component (b) is increased, the ratio of the terminal to be the carboxyl group is increased, and in the case where the hydroxyl group end and the carboxyl group end are present, all the terminals become the carboxyl group as the dehydration reaction proceeds. Become. However,
If the ratio of the component (a) is unnecessarily large, part of the component (a) will remain unreacted. Further, when the ratio of the component (b) becomes unnecessarily large, the component (b) remains without reacting.

In the reaction for synthesizing the resin having a vinyl group, a catalyst for promoting the ring-opening reaction of the epoxy group with a carboxyl group and, if necessary, a catalyst for promoting the (dehydration) esterification reaction may be used in combination. Good.

As the catalyst for promoting the ring-opening reaction of an epoxy group with a carboxyl group which can be used in the present invention, a tertiary amine such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine and tri-n-octylamine, tetramethylammonium chloride. , Quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide, alkylureas such as tetramethylurea, and alkylguanidines such as tetramethylguanidine.

The catalyst for promoting the ring-opening reaction that can be used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0.1 to 5.0 relative to the epoxy compound.
%, Preferably 0.5 to 3.0% by weight. The ring-opening reaction is 50 to 200 degrees, preferably 1
Perform at 00 to 180 degrees.

Examples of the catalyst for promoting the (dehydration) esterification reaction that can be used in the present invention include Sn compounds such as tin octylate and dibutyltin laurate, and Ti compounds such as tetrabutyl titanate.

The catalyst for promoting the (dehydration) esterification reaction used in the present invention may be used alone or in combination of two or more kinds. This catalyst is 0-100 with respect to the reaction system.
It is recommended to use 0 ppm, preferably 50 to 500 ppm. This (dehydration) esterification reaction is 180 to 240 ° C.
Done in.

The epoxy group ring-opening reaction with a carboxyl group and the (dehydration) esterification reaction may be carried out sequentially, but after the raw materials and the catalyst have been charged all at once, the reaction temperature is raised stepwise according to the progress of the reaction. Method is preferred. If necessary, after the component (c) and the catalyst are charged at once,
The components (a) and (b) may be dropped.

The resin having a cyclic olefin or vinyl group thus synthesized is reacted with an epoxidizing agent to synthesize the resin having an epoxy group used in the flame-retardant laminate of the present invention. However, examples of the epoxidizing agent that can be used include peracids and hydroperoxides.

Examples of peracids include formic acid, peracetic acid, perbenzoic acid and trifluoroperacetic acid. Of these, peracetic acid is industrially produced in large quantities and is available at low cost.
It is also a preferred epoxidizing agent because of its high stability.

Hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumene peroxide and the like.

In the epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst.

In the case of hydroperoxides,
A mixture of tungstic acid and caustic soda with hydrogen peroxide,
Alternatively, a catalytic effect can be obtained by using an organic acid in combination with hydrogen peroxide or molybdenum hexacarbonyl in combination with tertiary butyl hydroperoxide.

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

The reaction temperature range that can be used depends on the reactivity of the epoxidizing agent used.

With respect to peracetic acid, which is a preferred epoxidizing agent, 0 to 70 ° C. is preferable.

The reaction is slow at 0 ° C or lower, and the decomposition of peracetic acid occurs at 70 ° C.

In the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system, which is an example of hydroperoxide, 2 is used for the same reason.
0 degreeC-150 degreeC is preferable.

The solvent can be used for the purpose of reducing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent.
In the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used.

The charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed according to the purpose such as the amount of the unsaturated bond to be left.

When a compound having a large number of epoxy groups is intended,
The epoxidizing agent is preferably added in an equimolar amount or more with respect to the unsaturated group. However, it is usually disadvantageous to exceed the 2-fold molar amount in view of economical efficiency and side reactions, and in the case of peracetic acid, the 1- to 1.5-fold molar amount is preferable.

The composition of interest can be removed from the reaction crude liquid by chemical engineering means such as concentration.

The epoxy resin used in the flame-retardant laminate of the present invention can be used as a mixture with other epoxy resins as long as the characteristics of the composition are not impaired. Here, the other epoxy resin may be any one that is generally used, for example, epibis type epoxy, bisphenol F epoxy, novolac epoxy, alicyclic epoxy and styrene oxide, butylglycidyl ether. Epoxy diluents such as.

Another essential component for obtaining the flame-retardant laminate of the present invention is a halogenated epoxy resin containing tetrabromobisphenol A and tetrachlorobisphenol A as raw materials. It is represented by [Chemical Formula 1]. The proportion of these halogenated epoxy resins in the composition is 80 to 20 parts by weight per 100 parts by weight of the composition. When the proportion in the composition is 80 parts by weight or more or less than 20 parts by weight, heat resistance and electric characteristics cannot be maintained while maintaining heat resistance and electric characteristics.

The halogen in the halogenated epoxy resin represented by [Chemical Formula 1] is bromine or chlorine. The number n of repeating units is an integer of 0 or more.

Further, as the curing agent used in the flame-retardant laminate of the present invention, known curing agents used in epoxy resins can be used as long as they do not impair the performance of the laminate, and amines, polyamide resins, Cationic catalysts such as acid anhydrides, polymercaptan resins, novolac resins, dicyandiamide, amine complexes of boron trifluoride, and cationic catalysts composed of organosilicon compounds and organoaluminum compounds are included. The amount used is preferably 0.3 to 2 equivalents relative to the epoxy resin. Particularly, dicyandiamide and acid anhydride are preferable. The acid anhydride includes the following. Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, Acid anhydrides such as succinic anhydride and mixtures of said acid anhydrides.

The flame-retardant laminate of the present invention is prepared by dissolving the above-mentioned epoxy resin, curing agent and curing accelerator in an organic solvent to form a varnish, impregnating the base sheet with the prepreg, and heating the prepreg. It can be manufactured by integrally molding under pressure.

Triethylamine DB as a curing accelerator
U, amine compounds such as benzyldimethylamine, 2
- can be used Le acids, the BF ₃ complexes, such as BF ₃ · piperidine complex - undecylimidazolium - le, 2-ethyl-4-methyl-imidazo - imidazo such as Le. Determined by the balance between the curability and the physical properties of the laminate, for example 0
Benzyldimethylamine, 2-undecylimidazo-
And 2-ethyl-4-methylimidazole are preferably used in an amount of 0.1 to 5 parts by weight. As the organic solvent, acetone, methyl ethyl ketone, methano-
, Dimethylformamide, methyl cellosolve and the like can be used. The varnish preferably has a nonvolatile content of 20 to 95%.

As the substrate, paper, glass cloth, glass paper, mica, polyester fiber or the like can be used.

The base material is dipped in the above varnish to obtain 100 to 20
A prepreg can be manufactured by heating and drying at 0 ° C for 1 minute to 1 hour.

Further, the prepreg can be obtained under the pressure of 10 to 100 kg under conditions of 130 to 180 ° C. and 30 to 240 minutes.

At the time of production, changes such as addition of components such as filler and omission of use of organic solvent may be carried out, if necessary. The curing agent, curing accelerator, organic solvent, base sheet, filler, etc. may be used individually or in combination of two or more.

The laminate of the present invention has excellent heat resistance, tracking resistance and arc resistance and is particularly suitable as a printed circuit board.

The present invention will be described in more detail with reference to the following examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08L 63/00 NJW 8830-4J

Claims (11)

[Claims] 1. (A) (a) a compound having at least one vinyl group and one epoxy group in one molecule, (b) a polybasic acid anhydride, a polybasic acid, an acid terminal polymer, and A resin having a vinyl group obtained by reacting at least one selected from polymers containing a carboxylic acid group and (c) at least one selected from compounds having one or more active hydrogens, Epoxy resin obtained by epoxidation 20 to 80 parts by weight (B) General formula [Wherein n is an integer of 0 or more and X is a bromine atom or a chlorine atom] 80
A flame-retardant laminate comprising: ~ 20 parts by weight and (C) a curing agent for epoxy resin. 2. The flame-retardant laminate according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is 4-vinylcyclohexene-1-oxide. 3. The compound having one or more vinyl groups and one epoxy group in one molecule is 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide. Flame-retardant laminated plate of 1. 4. The flame-retardant laminate according to claim 1, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is limonene monoxide. 5. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following formula (I): The flame-retardant laminate according to claim 1, which is a compound represented by: << n is an integer from 0 to 30 >> 6. A compound having one or more vinyl groups and one epoxy group in one molecule is represented by the following (II) The flame-retardant laminate according to claim 1, which is a compound represented by << n1 and n2 are integers from 0 to 30 >>. 7. A compound having one or more vinyl groups and one epoxy group in one molecule is represented by the following (III) The flame-retardant laminate according to claim 1, which is a compound represented by << P is a substituted phenyl group and n is an integer of 0 to 30 >>. 8. The flame-retardant laminate according to claim 1, wherein the compound having at least one active hydrogen is an alcohol, a hydroxyl group-terminated polymer, and a hydroxyl group-containing polymer. 9. The flame-retardant laminate according to claim 1, wherein the acid-terminated polymer is an acid-terminated polyester. 10. The flame-retardant laminate according to claim 8, wherein the hydroxyl-terminated polymer is a hydroxyl-terminated polyester. 11. The flame-retardant laminate according to claim 8, wherein the hydroxyl-terminated polymer is a hydroxyl-terminated polyether.