JP2002194313A - Flame-retardant resin adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin adhesive containing neither a halogen nor antimony, having environmental safety, sufficient flame retardance and excellent electric characteristics. SOLUTION: This flame-retardant resin adhesive is characterized by comprising 10-100 pts.wt. of an epoxy resin compound containing 0.01-10 wt.% of a phosphorus component in a resin skeleton represented by formula (1), 10-100 pts.wt. of another epoxy resin compound and 10-100 pts.wt. of a phenolic curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin adhesive suitably used for bonding a metal foil such as a copper foil to a heat-resistant support material.

[0002]

2. Description of the Related Art
For flexible wiring boards, epoxy resin adhesives with excellent electrical properties, cost, workability, etc. are mainly used,
Since epoxy resin has insufficient flame retardancy, it must be manufactured by adding a bromine-containing epoxy resin, antimony trioxide, red phosphorus, metal hydrate, etc., and bonding a heat-resistant film and copper foil. There were many.

[0003] However, halogen (bromine) flame retardants such as decabromide are suspected of producing dioxins during combustion, and antimony oxide is known to be toxic. There are environmental and safety issues regarding the disposal method of electronic component devices using agents and their adhesives, and the demand for use regulations is increasing. Under these circumstances, various non-halogen and non-antimony flame retardants have been proposed. For example, the use of metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide has been proposed, which has the advantage of high safety and low cost.
For the purpose of flame retardation, a large amount of addition is required, and there has been a problem that electrical properties at the time of an environmental acceleration test are impaired, and film formability is poor.

[0004] The present invention has been made in view of the above circumstances, shows sufficient flame retardancy, has high environmental safety,
It is an object of the present invention to provide a flame-retardant resin adhesive having good electric characteristics.

[0005]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies in order to achieve the above object, and as a result, a phosphorus component in a resin skeleton represented by the following general formula (1) has been obtained. Flame-retardant resin adhesive obtained by using an epoxy resin containing 0.01 to 10% by weight in combination with another epoxy resin and a phenolic curing agent is used to form a heat-resistant supporting material with various metal foils such as a copper foil. (For example, a heat-resistant film, an inorganic sheet, or the like) can be bonded at a relatively low temperature, and in the laminate bonded with the flame-retardant resin adhesive, the adhesive layer exhibits a sufficient adhesive strength. Therefore, for example, a flexible wiring board, TAB (Tape Auto
The present inventors have found that productivity can be remarkably improved if used for manufacturing a copper-clad substrate for a mated bonding, etc., and that it can be used safely because it shows sufficient flame retardancy, and the present invention has been accomplished.

Now, the present invention will be described in further detail. The present invention relates to 10 to 100 parts by weight of an epoxy resin compound containing 0.01 to 10% by weight of a phosphorus component in a resin skeleton represented by the following general formula (1). , Other epoxy resin compounds 10 to 100 parts by weight, phenolic curing agent 10 to 1
A flame-retardant resin adhesive characterized by containing 00 parts by weight.

[0007]

Embedded image Wherein k is a number from 1 to 10, and X is

Embedded image Wherein R ¹ is a hydrogen atom or a group having 1 to 1 carbon atoms
18 represents a monovalent hydrocarbon group), and Y represents the following formulas (i) to
And a group selected from (xiv). ]

[0008]

Embedded image

[0009]

Embedded image

[0010]

Embedded image (Wherein, R ² may be the same or different from each other;
A hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms,
m is a number from 0 to 10. )

Here, the monovalent hydrocarbon group for R ¹ and R ² is an alkyl group having 1 to 18 carbon atoms, especially 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group,
Examples include an alkyl group such as an n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group, and an aryl group such as a phenyl group.

In the above formula, k is 1 to 10, preferably 1 to 5, more preferably 1 to 3, and m is 0 to 10, preferably 1 to 5,
More preferably, it is 1-3.

Furthermore, the compound of the above formula (1) contains 0.01 to 10% by weight of a phosphorus component (phosphorus atom) in the resin skeleton, and the amount is preferably 0.1 to 7.5.
%, More preferably 1 to 5% by weight. If the content of the phosphorus component is less than 0.01% by weight, the effect of imparting sufficient flame retardancy cannot be obtained, and if the content exceeds 10% by weight, aromatics such as phenol skeleton, phenylene skeleton, and naphthalene skeleton are inevitably. Since the number of aromatic ring units increases and the viscosity of the resin increases, it becomes difficult to use the resin as an adhesive composition.

The flame-retardant resin adhesive of the present invention uses, in addition to the above-mentioned phosphorus-containing epoxy resin, a conventionally known epoxy resin as another phosphorus-free epoxy resin. For example, bisphenol A, bisphenol F, resorcinol,
Glycidyl ethers of phenols such as phenol novolak and cresol novolac, glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol, glycidyl esters of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid, aniline and isocyanurate Glycidyl type (including methyl glycidyl type) epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as an acid is substituted with a glycidyl group, vinylcyclohexene diepoxide obtained by epoxidizing an olefin bond in a molecule, 3,4 -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m Alicyclic epoxy resins such as dioxane, glycidyl ether of para-xylylene-modified phenol resin, glycidyl ether of meta-xylylene / para-xylylene-modified phenol resin, glycidyl ether of terpene-modified phenol resin, glycidyl ether of dicyclopentadiene-modified phenol resin, and cyclopentadiene-modified phenol resin Glycidyl ether, glycidyl ether of a polycyclic aromatic modified phenol resin, glycidyl ether of a naphthalene ring-containing phenol resin, and a biphenyl type epoxy resin. These can be used alone or in combination of two or more. However,
In the present invention, no halogenated epoxy resin is blended.

In this case, the epoxy resin other than the phosphorus-containing epoxy resin has a melting point of 100 ° C. or less, especially 0 to 80 ° C.
Particularly preferable are those which are in a liquid state at a temperature of 30 ° C. or lower. This is because, in particular, when the melting point of the epoxy resin is higher than 100 ° C., the adhesive performance is extremely poor when bonding the heat-resistant film and the copper foil.
This is because the workability may decrease, and it may be difficult to perform a sufficient temporary fixing before starting the main curing.

Here, the epoxy resin [A] of the above formula (1) and the other phosphorus-free epoxy resin are 10 to 100 parts (parts by weight, hereinafter the same) of the former [A] and the latter [B] Is mixed at a ratio of 10 to 100 parts, and the total amount of the epoxy resin [A] is 90 to 91% by weight, preferably 20 to 90% by weight, more preferably 30 to 100% by weight.
It is desirably contained in an amount of from 80 to 80% by weight, more preferably from 40 to 75% by weight. If the amount of the epoxy resin [A] is too small, a sufficient flame-retardant effect cannot be obtained. If the amount is too large, the adhesive strength is lowered or the humidity resistance is poor.

Examples of the phenolic curing agent include phenols such as phenol, cresol, xylenol, hydroquinone, resorcin, catechol, bisphenol A, bisphenol F, and α-naphthol;
Resins obtained by condensing or co-condensing naphthols such as β-naphthol and dihydroxynaphthalene with aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde; from phenols and dimethoxyparaxylene A phenol resin having a xylylene skeleton to be synthesized; a phenol resin having a dicyclopentadiene skeleton; a phenol resin having a cyclopentadiene skeleton;
Melamine-modified phenolic resin; terpene-modified phenolic resin; polycyclic aromatic-modified phenolic resin; naphthol resin having a xylylene skeleton, and the like can be used alone or in combination of two or more. Among them, those represented by the following general formula (2) are particularly preferable.

[0018]

Embedded image In and, R ³ may be the same or different from each other,
It is a hydrogen atom, a C1-C4 alkyl group, or a phenyl group, and n is a number of 0-10, preferably 0-5, more preferably 0-2. )

The mixing amount of the phenolic curing agent is 10 to 100 parts in 10 to 100 parts of the epoxy resin [A] and 10 to 100 parts of the epoxy resin [B]. 50-200 for
Parts, preferably 70-150 parts, more preferably 80-
It is desirable to mix them in a proportion of 120 parts. In this case, the total epoxy resin and the phenolic curing agent have a chemical equivalent ratio of the epoxy group to the phenolic hydroxyl group of 0.7.
To 1.3, particularly preferably 0.8 to 1.2,
By setting the content in such a range, each unreacted component is suppressed to be small, and it is effective to reduce the deterioration with time of the adhesive force, the water absorption, the electric characteristics and the like.

In the present invention, in addition to the phenolic curing agent, a curing agent for another epoxy resin such as an acid anhydride may be blended within a range not to impair the effects of the present invention.

The flame retardant resin adhesive of the present invention preferably further contains a curing accelerator. The curing accelerator is not particularly limited as long as it accelerates the curing reaction between the epoxy resin and the curing agent. For example, one or more selected from imidazole compounds, tertiary amine compounds, and organic phosphorus compounds are used. Can be blended.

Here, as the imidazole compound, 2
-Methylimidazole, 2-ethylimidazole, 4-
Methylimidazole, 4-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4
-Methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.

Examples of the tertiary amine compound include amine compounds having an alkyl group or an aralkyl group as a substituent bonded to a nitrogen atom, such as triethylamine, benzyldimethylamine, benzyltrimethylamine and α-methylbenzyldimethylamine. -Diazabicyclo [5.4.0] undecene-7 and phenol salts thereof,
Examples thereof include salts with cycloamidine compounds such as octylates and oleates and salts thereof with organic acids, and salts or complex salts of cycloamidine compounds such as compounds of the following formulas with quaternary boron compounds.

[0024]

Embedded image

The organic phosphorus compounds include triphenylphosphine, tributylphosphine, tri (p-
Methylphenyl) phosphine, tri (nonylphenyl)
Examples include triorganophosphine compounds such as phosphine and triphenylphosphine / triphenylborane, and quaternary phosphonium salts such as tetraphenylphosphonium / tetraphenylborate.

The amount of these curing accelerators is usually 10 parts with respect to 100 parts in total of the epoxy resin and the curing agent.
Or less (0 to 10 parts), desirably 0.01 to 10 parts,
More desirably, about 0.5 to 5 parts is preferable. If the amount is more than 10 parts, the curability is excellent, but the storage stability tends to decrease.

The flame-retardant resin adhesive of the present invention may be formed of a metal hydrate such as aluminum hydroxide, magnesium hydroxide, or calcium hydroxide for the purpose of supporting flame retardancy in addition to the phosphorus-containing epoxy resin. You may mix | blend in the range which does not have a problem.
However, a halogenated epoxy resin and an antimony compound are not blended.

The flame-retardant resin adhesive of the present invention contains, in addition to the above components, silicone rubber, silicone oil, liquid or solid butadiene nitrile rubber, etc., in order to impart flexibility, as long as there is no problem in film formability. May be.

The flame-retardant resin adhesive of the present invention comprises, as a main component, a resin component having a specific composition ratio of the above-mentioned phosphorus-containing epoxy resin, another epoxy resin, and a phenolic epoxy resin curing agent. Particularly preferably 90% by weight or more,
More preferably, it is a flame-retardant resin adhesive containing about 95 to 100% by weight. The flame-retardant resin adhesive is preferably used in an amount of 3 to 50% by weight, more preferably 5 to 40% by weight, in a tacky dry film or sheet-like flame-retardant resin adhesive or a suitable organic polar solvent. It may be a solution composition of a flame-retardant resin adhesive that is uniformly dissolved in concentration.

The solution composition of the flame-retardant resin adhesive has a solution viscosity (30 ° C.) of 0.1 to 10,000 poise, particularly 0.2 to 5,000 poise, and furthermore 1 to 1,000.
It is preferably about 0 poise.

The flame-retardant resin adhesive of the present invention has a softening point (temperature at which softening starts on a hot plate) of an uncured resin component alone of 150 ° C. or lower, particularly 120 ° C. or lower. More preferably, the temperature is 100 ° C. or lower. The flame-retardant resin adhesive of the present invention is preferably one that can be thermally cured by heating to a curing temperature of 130 to 250 ° C, more preferably 140 to 180 ° C. When the softening point of the flame-retardant resin adhesive is higher than 150 ° C., the adhesive property is extremely poor when bonding the heat-resistant film and the copper foil. This is because it may be difficult to perform temporary fixing. If the heat curing temperature is lower than 130 ° C., the curing may take a long time due to the low temperature curing, or the storage stability may be extremely poor. If the reaction temperature exceeds 250 ° C., the copper foil may be oxidized, and the bonded flexible copper substrate may not be used.

The flame-retardant resin adhesive of the present invention is prepared by mixing a solution composition of the flame-retardant resin adhesive in which all of the above-mentioned resin components are uniformly dissolved in an organic polar solvent with a suitable metal foil, aromatic resin, A heat-resistant film surface such as a polyimide film, or a film of a thermoplastic resin such as polyester or polyethylene is applied on the film surface, and the coating layer is applied at 60 to 140 ° C, particularly 80 ° C.
20 to 100 minutes at a temperature of ~ 130 ° C, especially 30 ~ 6
By drying for 0 minutes, the solvent was substantially removed (preferably the solvent remaining ratio was 1% by weight or less, particularly 0.1% by weight.
It is possible to form a thin film (dry film or sheet having a thickness of about 1 to 200 μm) of an uncured flame-retardant resin adhesive (not more than 5% by weight).

The uncured flame-retardant resin adhesive thin film produced as described above has suitable flexibility and can be wound around a thin tube or the like. It is also possible to perform a punching process such as a punching method, and further, for example, a laminated sheet in which a thin layer of an uncured transparent and flame-retardant resin adhesive is formed on the heat-resistant or thermoplastic film. And a metal foil or a heat-resistant film or the like for the transfer destination are overlapped and passed between a pair of rolls (lamination rolls) heated to a temperature of about 20 to 140 ° C., particularly 30 to 130 ° C. It is also possible to transfer onto a metal foil or a heat-resistant film for use.

In order to form a laminate such as a copper-clad substrate by bonding a heat-resistant film and a metal foil using the flame-retardant resin adhesive of the present invention, for example, the above-described method is used. A heat-resistant film and a metal foil are laminated (laminated) at a temperature of 80 to 180 ° C., particularly 100 to 170 ° C., via a thin-film flame-retardant resin adhesive. 30 minutes at 80-250 ° C
By heating and curing the flame-retardant adhesive layer by heating for 40 hours, especially for 1 to 30 hours, the above-mentioned laminate can be easily and continuously manufactured without any trouble.

The flame-retardant resin adhesive of the present invention comprises a heat-resistant film such as an aromatic polyimide film, a polyamide film, a polyetheretherketone, a PEEK film, a polyethersulfone film, and a suitable metal foil such as a copper foil. Besides being suitably used for bonding, it can be effectively used as a resin adhesive for a built-up substrate.

[0036]

According to the flame-retardant resin adhesive of the present invention, it is non-halogen, non-antimony, has environmental safety, shows sufficient flame retardancy, and has good electric characteristics.

[0037]

EXAMPLES The following shows synthesis examples, examples and comparative examples,
The present invention will be specifically described, but the present invention is not limited to the following examples. In addition, in the following examples, a part shows a weight part.

[Synthesis Example 1] 162 parts of ethyldichlorophosphite (manufactured by Aldrich) was added to an ice-cooled mixed solution of 456 parts of bisphenol A (manufactured by Nippon Rika Co., Ltd.) and 600 parts of toluene (manufactured by Kanto Chemical Co., Ltd.). Is 20-30 ° C
Drop slowly so that it is maintained at Stir for 3 hours after dropping. Here, 200 parts of a 48% by weight aqueous NaOH solution is added, and the toluene phase is separated by a separating funnel to remove generated hydrochloric acid. This operation is repeated three times to completely remove the hydrochloric acid. The toluene phase obtained here is heated under reduced pressure to remove toluene and take out a pale yellow solid.
580 parts of the pale yellow solid obtained here was stirred and dissolved in 460 parts of epichlorohydrin (manufactured by Aldrich), and the pressure in the reaction system was adjusted to 150 mmHg.
The temperature was raised to 8 ° C. The mixture was reacted for 3.5 hours while continuously adding 75 parts of a 48% by weight aqueous sodium hydroxide solution dropwise thereto. During this time, water generated by the reaction and water of an aqueous sodium hydroxide solution were separated by refluxing a water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After completion of the reaction, the reaction system was returned to normal pressure, and the temperature was raised to 110 ° C. to completely remove water from the reaction system. Excess epichlorohydrin was removed by evaporation under normal pressure, and evaporation was further performed at 140 ° C. under a reduced pressure of 15 mmHg. To a mixture of the resulting resin and sodium chloride, 175 parts of 2-butanone and 24 parts of a 10% by weight aqueous sodium hydroxide solution were added, and 80 to 85%
The reaction was performed at a temperature of 150C for 1.5 hours. After the reaction, 2-
350 parts of butanone and 200 parts of water were added, and the lower layer aqueous sodium chloride solution was separated and removed. The 2-butanone solution layer was washed by adding 100 parts of water and neutralized with phosphoric acid, and after separating the aqueous layer, further washing with 100 parts of water and separating the aqueous layer. After removing most of the 2-butanone by evaporating the 2-butanone resin solution under normal pressure, the 2-butanone resin solution was removed under reduced pressure of 5 mmHg.
By evaporating and drying at a temperature of 0 ° C., the following phosphorus-containing epoxy resin having a phosphorus content of 4.2% and an epoxy equivalent of 352 g / eq was obtained.

[0039]

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[Synthesis Example 2] A mixture of 680 parts of bisphenol A (manufactured by Nippon Rika) and 600 parts of toluene (manufactured by Kanto Chemical Co.) was ice-cooled and mixed with 178 parts of ethyldichlorophosphate (manufactured by Aldrich) at a temperature of 178 parts. 20-30 ° C
Drop slowly so that it is maintained at Stir for 3 hours after dropping. Here, 200 parts of a 48% by weight aqueous NaOH solution is added, and the toluene phase is separated by a separating funnel to remove generated hydrochloric acid. This operation is repeated three times to completely remove the hydrochloric acid. The toluene phase obtained here is heated under reduced pressure to remove toluene and take out a pale yellow solid.
580 parts of the pale yellow solid obtained here was stirred and dissolved in 460 parts of epichlorohydrin (manufactured by Aldrich), and the pressure in the reaction system was adjusted to 150 mmHg.
The temperature was raised to 8 ° C. The mixture was reacted for 3.5 hours while continuously adding 75 parts of a 48% by weight aqueous sodium hydroxide solution dropwise thereto. During this time, water generated by the reaction and water of an aqueous sodium hydroxide solution were separated by refluxing a water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After completion of the reaction, the reaction system was returned to normal pressure, and the temperature was raised to 110 ° C. to completely remove water from the reaction system. Excess epichlorohydrin was removed by evaporation under normal pressure, and evaporation was further performed at 140 ° C. under a reduced pressure of 15 mmHg. To a mixture of the resulting resin and sodium chloride, 175 parts of 2-butanone and 24 parts of a 10% by weight aqueous sodium hydroxide solution were added, and 80 to 85%
The reaction was performed at a temperature of 150C for 1.5 hours. After the reaction, 2-
350 parts of butanone and 200 parts of water were added, and the lower layer aqueous sodium chloride solution was separated and removed. The 2-butanone solution layer was washed by adding 100 parts of water and neutralized with phosphoric acid, and after separating the aqueous layer, further washing with 100 parts of water and separating the aqueous layer. After removing most of the 2-butanone by evaporating the 2-butanone resin solution under normal pressure, the 2-butanone resin solution was removed under reduced pressure of 5 mmHg.
By evaporating and drying at a temperature of 0 ° C., the following phosphorus-containing epoxy resin having a phosphorus content of 4.1% and an epoxy equivalent of 365 g / eq was obtained.

[0041]

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[Synthesis Example 3] Phenol novolak resin T
162 parts of ethyldichlorophosphite (manufactured by Aldrich) was added to an ice-cooled mixed solution of 220 parts of D-2131 (manufactured by Dainippon Ink and phenolic hydroxyl equivalent 110 g / eq) and 600 parts of toluene (manufactured by Kanto Kagaku). Temperature 2
Add dropwise slowly to keep the temperature between 0 and 30 ° C. Stir for 3 hours after dropping. Here, 200 parts of a 48% by weight aqueous NaOH solution is added, and the toluene phase is separated by a separating funnel to remove generated hydrochloric acid. This operation is repeated three times to completely remove the hydrochloric acid. The toluene phase obtained here is heated under reduced pressure to remove toluene and take out a pale yellow solid. 580 parts of the obtained pale yellow solid was dissolved under stirring in 460 parts of epichlorohydrin (manufactured by Aldrich), the pressure in the reaction system was adjusted to 150 mmHg, and the temperature was raised to 68 ° C. 2. While continuously dropping 75 parts of a 48% by weight aqueous sodium hydroxide solution,
The reaction was performed for 5 hours. During this time, water generated by the reaction and water of an aqueous sodium hydroxide solution were separated by refluxing a water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After the completion of the reaction, the reaction system was returned to normal pressure, and the temperature was raised to 110 ° C. to completely remove water from the reaction system. The excess epichlorohydrin is removed by evaporation under normal pressure, and a further 15 m
Evaporation was carried out at 140 ° C. under a reduced pressure of mHg. 175 parts of 2-butanone and 24 parts of a 10% by weight aqueous sodium hydroxide solution were added to the resulting mixture of the resin and sodium chloride, and the mixture was reacted at a temperature of 80 to 85 ° C. for 1.5 hours. After completion of the reaction, 350 parts of 2-butanone and 200 parts of water were added, and the lower layer aqueous sodium chloride solution was separated and removed. 2-
The butanone solution layer was washed by adding 100 parts of water, neutralized with phosphoric acid, separated from the aqueous layer, and further washed with 100 parts of water to separate the aqueous layer. After removing most of the 2-butanone under normal pressure by evaporating the 2-butanone resin solution, 5 mmH
The evaporative drying was carried out at 140 ° C. under a reduced pressure of g to obtain the following phosphorus-containing epoxy resin having a phosphorus content of 3.2% and an epoxy equivalent of 280 g / eq.

[0043]

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[Synthesis Example 4] Phenol novolak resin T
178 parts of ethyldichlorophosphate (manufactured by Aldrich) was added to an ice-cooled mixed solution of 220 parts of D-2131 (manufactured by Dainippon Ink, phenolic hydroxyl equivalent 110 g / eq) and 600 parts of toluene (manufactured by Kanto Kagaku). Is 2
Add dropwise slowly to keep the temperature between 0 and 30 ° C. Stir for 3 hours after dropping. Here, 200 parts of a 48% by weight aqueous NaOH solution is added, and the toluene phase is separated by a separating funnel to remove generated hydrochloric acid. This operation is repeated three times to completely remove the hydrochloric acid. The toluene phase obtained here is heated under reduced pressure to remove toluene and take out a pale yellow solid. 580 parts of the pale yellow solid obtained here was stirred and dissolved in 460 parts of epichlorohydrin (manufactured by Aldrich), the pressure in the reaction system was adjusted to 150 mmHg, and the temperature was raised to 68 ° C. 2. While continuously dropping 75 parts of a 48% by weight aqueous sodium hydroxide solution,
The reaction was performed for 5 hours. During this time, water generated by the reaction and water of an aqueous sodium hydroxide solution were separated by refluxing a water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After completion of the reaction, the reaction system was returned to normal pressure, and the temperature was raised to 110 ° C. to completely remove water from the reaction system. The excess epichlorohydrin is removed by evaporation under normal pressure, and a further 15 m
Evaporation was carried out at 140 ° C. under a reduced pressure of mHg. 175 parts of 2-butanone and 24 parts of a 10% by weight aqueous sodium hydroxide solution were added to the resulting mixture of the resin and sodium chloride, and the mixture was reacted at a temperature of 80 to 85 ° C. for 1.5 hours. After completion of the reaction, 350 parts of 2-butanone and 200 parts of water were added, and the lower layer aqueous sodium chloride solution was separated and removed. 2-
The butanone solution layer was washed by adding 100 parts of water, neutralized with phosphoric acid, separated from the aqueous layer, and further washed with 100 parts of water to separate the aqueous layer. After removing most of the 2-butanone by evaporation under normal pressure, the 2-butanone resin solution is 5 mmH
By evaporating and drying at 140 ° C. under a reduced pressure of g, a phosphorus-containing epoxy resin having a phosphorus content of 3.0% and an epoxy equivalent of 290 g / eq was obtained.

[0045]

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[Examples 1 to 8, Comparative Examples 1 to 5] As shown in Tables 1 and 2, the phosphorus-containing epoxy resin and bisphenol A type epoxy resin (Japanese Chemical product name: RE310), phenolic epoxy resin curing agent (biphenyl aralkylphenol resin, Meiwa Kasei Co., Ltd., product name: MEH-780)
0SS), a reactive liquid synthetic rubber (manufactured by Ube Industries, Ltd., trade name: CTBN1300x8), toluene and 2-butanone as a low-stressing agent, and a flask inner temperature of 80 ° C.
After stirring for about 2 hours to produce a uniform solution, triphenylphosphine (trade name: TPP, manufactured by Hokuko Chemical Co., Ltd.) was added to prepare a solution composition of a flame-retardant resin adhesive. This solution composition maintained a uniform solution state even when left at room temperature for one week.

[0047]

[Table 1]

[0048]

[Table 2]

Comparative Examples 6 and 7 A bromine-containing epoxy resin (trade name: AER-8049, manufactured by Nippon Kayaku Co., Ltd.) and a bisphenol A type epoxy resin (Nippon Kagaku Product name: RE31, manufactured by Yakusha
0), phenolic epoxy resin curing agent (biphenylaralkylphenol resin, manufactured by Meiwa Kasei Co., Ltd., trade name: ME
H-7800SS) antimony trioxide (manufactured by Mitsubishi Chemical Corporation, trade name: antimony trioxide RX), a reactive liquid synthetic rubber as a low-stressing agent (trade name: C, manufactured by Ube Industries, Ltd.)
TBN 1300x8), toluene and 2-butanone were added, 2 kg of alumina balls were added, and about 8 rpm at 45 rpm.
After stirring for an hour to prepare a uniform solution, triphenylphosphine (trade name: TPP, manufactured by Hokuko Chemical Co., Ltd.) was added to prepare a solution composition of the flame-retardant resin adhesive. This solution composition maintained a uniform solution state even when left at room temperature for one week.

[0050]

[Table 3]

The solution composition of the flame-retardant resin adhesive prepared as described above was peeled off and the flame-retardant (JIS C 647).
1), solder heat resistance, and insulation resistance between wires.
In the following experiments, a polyimide film “Kapton 100” manufactured by Du Pont-Toray Co., Ltd. was used as a heat-resistant film substrate.
V "25 μm thick, and a rolled copper foil“ BHY22BT ”manufactured by Japan Energy Co., Ltd. having a thickness of 35 μm was used as the copper foil. The adhesive strength is a result of measurement at a peeling speed of 50 mm / min using a tensile tester manufactured by Shimadzu Corporation.

[Production of Laminate for Adhesion Test Using Flame-Retardant Resin Adhesive] The solution composition of the above-described flame-retardant resin adhesive was applied on a polyimide film with a doctor blade to a thickness of 30 μm. Apply the coating layer at 60 ° C for 5 minutes, 80
5 minutes at 100 ° C, and further dried by heating at 100 ° C for 5 minutes.
A flame-retardant resin adhesive layer having a thickness of about 15 μm was formed on the polyimide film.

The polyimide film having the flame-retardant resin adhesive layer and the copper foil were overlaid and pressed twice by applying pressure between laminate rolls heated to 115 ° C. while applying pressure. The laminate was heated at 80 ° C. for 3 hours, 120 ° C. for 2 hours, 150 ° C. for 2 hours, 180 °
C. for 3 hours in a nitrogen stream to heat-treat the flame-retardant resin adhesive layer to produce a laminate. The copper foil of the obtained laminate was etched to prepare a test piece in accordance with JIS C6471, and the adhesive strength was measured. For peeling in the 90-degree direction, a rotating drum-type support was used.

[Production of Flame-Retardant Test Specimen] In the same manner as in the production of the laminate for adhesion test described above, a solution composition of a flame-retardant resin adhesive was applied on a 12.7 × 125 mm polyimide film to form a film.
μm in thickness and then the coated layer is
And then dried at 80 ° C. for 5 minutes and further at 100 ° C. for 5 minutes to form a flame-retardant resin adhesive layer having a thickness of about 13 μm on the polyimide film.

The polyimide film having the flame-retardant resin adhesive layer was cured at 80 ° C. for 3 hours, at 120 ° C. for 2 hours,
Heat treatment was performed in a nitrogen stream at 0 ° C. for 2 hours and at 180 ° C. for 3 hours to cure the flame-retardant resin adhesive layer, thereby producing a polyimide film having an adhesive layer. The obtained test piece is J
According to IS C6471, the total burning time of 5 samples during a 3-second indirect flame was measured.

[Production of Solder Heat Specimen] In the same manner as in the production of the laminate for adhesion test described above, a solution composition of a flame-retardant resin adhesive was applied on a 20.0 × 20.0 mm polyimide film to a thickness of 30 μm. And then apply the applied layer at 60 ° C.
For 5 minutes, at 80 ° C. for 5 minutes, and then at 100 ° C. for 5 minutes for drying.
Was formed.

Tables 4 and 5 show Examples 1 to 8 and Comparative Examples 1 to 7.
4 shows test results of peel strength, flame retardancy (according to JIS C6471), solder heat resistance, and line insulation resistance. As shown here, the flame-retardant resin adhesive obtained in the present invention has flame retardancy,
It was found to be excellent in adhesive strength, solder heat resistance, line insulation resistance and environmental safety.

[0058]

[Table 4]

[0059]

[Table 5]

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J036 AA01 AA02 AA05 AD22 AF13 AJ20 DB05 FB07 JA06 JA08 4J040 EB021 EB022 EB081 EB082 EB091 EB092 EC021 EC022 EC091 EC092 EC161 EC162 EC181 EC182 EC251 EC08 GA02 MA03 MA09

Claims (3)

[Claims] 1 to 10 parts by weight of an epoxy resin compound containing 0.01 to 10% by weight of a phosphorus component in a resin skeleton represented by the following general formula (1), 10 to 100 parts by weight of another epoxy resin compound, Phenolic curing agent 10-1
A flame-retardant resin adhesive characterized by containing 00 parts by weight. Embedded image Wherein k is a number from 1 to 10, and X is Group selected from (wherein, R ¹ is 1 a hydrogen atom or a carbon atoms
18 represents a monovalent hydrocarbon group), and Y represents the following formulas (i) to
And a group selected from (xiv). ] Embedded image Embedded image (Wherein, R ² may be the same or different from each other;
A hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms,
m is a number from 0 to 10. ) 2. The phenolic curing agent is represented by the following general formula (2): R ³ may be the same or different from each other;
It represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and n is a number of 0 to 10. The flame-retardant resin adhesive according to claim 1, which is represented by the following formula: 3. A phenolic curing agent is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of an epoxy resin containing 9 to 91% by weight of an epoxy resin compound represented by the general formula (1). Item 3. The flame-retardant resin adhesive according to Item 1 or 2.