JPH0550546A - Manufacture of laminate and epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain the laminate excellent in the peeling strength between layers and chemical resistance by using an epoxy resin composition which contains the compound of the structure having the carboxyl group to which the compound having at least two oxazoline groups and polyacid anhydride are added. CONSTITUTION:In the manufacture of a compound, the compound containing at least two oxazoline groups is reacted with polyacid anhydride in the presence of a catalyst according to necessity. The reaction conditions therein is not limited, but the excessive rate of polyacid anhydride is preferably reacted with oxazoline group in the temperature range of 50-280 deg.C normally. In the manufacture of the laminate, epoxy resin compound is preferably the liquid-compound which contains the compound, epoxy resin, polyacid anhydride, the compound having ethylen ically unsaturated double bond and radical polymerization initiator as necessary components. The laminate thus obtained is excellent in the peeling strength between layers and chemical resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a laminate having excellent fibrous base material delamination strength and chemical resistance, and an epoxy resin composition suitable for use in the process.

[0002]

2. Description of the Related Art A glass epoxy resin-based laminate used as a printed circuit board is manufactured by heating and pressurizing after passing through a B-staged prepreg.
It is known that a polybasic acid anhydride having excellent heat resistance and electrical characteristics is used as an epoxy resin curing agent.

Since the above heat and pressure molding requires a long time and there is a problem in productivity, a compound having an ethylenically unsaturated double bond and a polymerization initiator are added to the epoxy resin and the curing agent for the epoxy resin. In addition, a method for producing a prepreg with improved moldability has been proposed (Japanese Patent Laid-Open No. 62-285929).

[0004]

However, although the prepreg obtained in the above method has a high curability,
Regarding the physical properties of the laminate of the final cured product, there is a problem that the delamination strength and chemical resistance are not sufficient.

[0005]

Means for Solving the Problems As a result of intensive studies in view of such a situation, the present inventors have found that a compound having at least two oxazoline groups and a structure having a carboxyl group to which a polybasic acid anhydride is added are added. It was found that a laminate having excellent delamination strength and chemical resistance can be obtained by using an epoxy resin composition containing a compound, and completed the present invention.

That is, the present invention provides an epoxy resin composition (I) containing as an essential component a compound having a structure having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added. Substrate (I
Method for producing a laminated plate, which comprises impregnating with I) and heat curing, and a compound having a structure having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added, as an essential component An epoxy resin composition (I) is provided.

Epoxy resin composition (I) used in the present invention
Is a compound having a structure having a carboxyl group obtained by adding a compound having at least two oxazoline groups and a polybasic acid anhydride [hereinafter, simply referred to as compound (A). ] As long as it is an epoxy resin composition containing as an essential component,
This usually contains the compound (A) and an epoxy resin as essential components.

That is, the compound (A) is used as a curing agent for the epoxy resin used at the same time. When the epoxy resin composition containing the compound (A) is used, for example, in a method for producing a laminated plate as described below, the laminated plate thus obtained has excellent delamination strength and chemical resistance.

Examples of the epoxy resin composition of the present invention include those obtained by adding a polybasic acid anhydride and a compound having an ethylenically unsaturated double bond to the above composition.
This composition, for example, when a laminated plate is obtained by a production method as described below, it not only gives a laminated plate excellent in delamination strength and chemical resistance, but also its precursor prepreg has fast curability. Becomes

The epoxy resin composition (I) of the present invention comprises
A polybasic acid anhydride, a compound having an ethylenically unsaturated double bond, a radical polymerization initiator, etc. are further added to the compound (A) and an epoxy resin as essential components, and other curing agent, if necessary, It can be obtained by adding other resins, polymerizable vinyl monomers, other solvents, fillers, curing accelerators, additives and the like.

In the production of a laminate, the epoxy resin composition (I) comprises a compound (A), an epoxy resin, a polybasic acid anhydride, a compound having an ethylenically unsaturated double bond, and a radical polymerization initiator. A liquid composition containing as an essential component is preferable.

The epoxy resin used in the present invention includes, for example, an epoxy resin obtained from epichlorohydrin or β-methylepichlorohydrin and bisphenol A, tetrabromobisphenol A, bisphenol F or bisphenol S; a phenol or an alkylphenol novolak resin. Polyglycidyl ethers; polyglycidyl of polyhydric alcohol such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane or ethylene oxide or propylene oxide adduct of bisphenol A Ethers; adipic acid,
Polyglycidyl esters of polycarboxylic acids such as phthalic acid, hexahydrophthalic acid or dimer acid; Cyclohexene epoxy compounds (3,4-epoxy-) obtained by epoxidizing cyclohexene or its derivative with peracetic acid 6-methyl-cyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate, 1
-Epoxyethyl-3,4-epoxycyclohexane etc.), cyclopentadiene or dicyclopentadiene or a cyclopentadiene-based epoxy compound (cyclopentadiene oxide, dicyclopentadiene) obtained by epoxidizing a derivative thereof with peracetic acid or the like. Oxide, 2,3-epoxycyclopentyl ether, etc.), limonene dioxide or diglycidyl ether of tetrabromobisphenol A, or glycidyl ether ester of hydroxybenzoic acid, and the like. Among them, the average epoxy equivalent is 100 to 100% by itself. Which is in the range of 400, or which is appropriately combined in the form of a mixture of two or more kinds so as to have an epoxy equivalent of this range, and is a solvent-free liquid at room temperature. Those are preferred.

The compound (A) of the present invention is a compound having a structure having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added. As the compound (A), any known and commonly used compound (A) can be used and is not particularly limited. The compound (A) may be produced by reacting a compound having at least two oxazoline groups with a polybasic acid anhydride in the presence of a catalyst, if necessary. The reaction conditions at this time are not limited, but it is usually preferable to react the acid anhydride group in excess of the oxazoline group in the temperature range of about 50 to 280 ° C. The compound before the completion of the reaction contains, in addition to the compound (A), a compound having at least two unreacted oxazoline groups, a polybasic acid anhydride, etc., but such compounds should also be used. You can

The compound having at least two oxazoline groups used to obtain the compound (A) is, for example,
2-m-phenylene bis (2-oxazoline), 2-p
-Phenylenebis (2-oxazoline), 2.2'-
(1.2 ethylene) -bis (2-oxazoline), 2.
2 '-(1.4 Butylene) -bis (2-oxazoline)
Etc.

The polybasic acid anhydride used to obtain the compound (A) and the polybasic acid anhydride which is further added as required include, for example, phthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride. , Methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl Succinic anhydride, chlorendic anhydride, benzophenone tetracarboxylic acid anhydride, cyclopentatetracarboxylic acid anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid , Ethylene glycol bis trimellitate anhydride or glycerin Trimellitate such as anhydrides, but these alone, or used in the form of a mixing of two or more. Of these, liquid divalent carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methyl nadic nadic acid anhydride are preferable.

Epoxy resin composition (I) in the present invention
In preparing, the epoxy resin and the compound (A) may be appropriately mixed. The mixing ratio of the epoxy resin and the compound (A) is not particularly limited, but it is generally preferable that the mixing ratio is such that the epoxy groups of the epoxy resin and the carboxyl groups of the compound (A) are equivalent.

Epoxy resin composition (I) used in the present invention
In addition, it is preferable to further contain a compound having an ethylenically unsaturated double bond from the viewpoint that the heat and pressure molding in the laminated plate manufacturing process can be performed in a short time and the productivity can be improved.

The compound having an ethylenically unsaturated double bond which can be used here is not particularly limited, but a typical example thereof is an epoxy obtained by an esterification reaction between an epoxy resin and an unsaturated monobasic acid. Vinyl ester resins, unsaturated polyester resins obtained by the reaction of dibasic acids containing unsaturated dibasic acids and polyhydric alcohols, allyl resins such as prepolymers of diallyl phthalate,
In preparing these resins, it is preferable to use a known and commonly used polymerization inhibitor for the purpose of preventing gelation during resin preparation and adjusting storage stability or curability of the produced resin. These resins thus obtained can be used as a stable resin solution by dissolving them in known and commonly used solvents and polymerizable vinyl monomers other than the above compounds, such as styrene, if necessary.

When the compound having an ethylenically unsaturated double bond is used in combination, the amount thereof is 2 to 230 parts by weight per 100 parts by weight of the epoxy resin component composed of the total of the epoxy resin and the compound (A). However, the range of 5 to 100 parts by weight is preferable from the viewpoint of obtaining a laminate having excellent delamination strength and heat resistance.

Examples of the radical polymerization initiator include cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylonexanone peroxide, 1,1-bis (t-butylperoxy) 3,3. , 5-trimethylcyclohexane, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide,
Di-myristyl peroxydicarbonate, t-butyl peroxy (2-ethylhexanoate), t-butyl peroxy-3,5,5-trimethylhexanoate,
Examples thereof include organic peroxides such as t-butyl peroxybenzoate and cumyl peroxy octoate.

Epoxy resin composition (I) used in the present invention
It is preferable to use another curing agent such as polybasic acid anhydride together with the compound (A) as the curing agent component. As the polybasic acid anhydride used here, any of the polybasic acid anhydrides used for obtaining the compound (A) can be used, among which methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylnadic acid anhydride can be used. Liquid such as 2
Divalent carboxylic acid anhydrides are preferred. Also, 5- (2,5-
A solution obtained by dissolving a solid acid anhydride such as dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid with a liquid acid anhydride is also preferably used.

Epoxy resin composition (I) used in the present invention
In addition, it is preferable to further add a curing accelerator for the epoxy resin, and among them, a latent curing accelerator which exhibits an acceleration function at a temperature of 50 ° C. or higher is particularly preferable.

If desired, a filler may be added to the epoxy resin composition (I), which may be appropriately selected depending on the required performance and working conditions.
Examples include aluminum hydroxide, aluminum silicate, colloidal silica, calcium carbonate, calcium sulfate, mica, talc, titanium dioxide, quartz powder, zirconium silicate, glass powder, asbestos powder, diatomaceous earth, and antimony trioxide. is there.

The mixing method and mixing order of the respective components for obtaining the epoxy resin composition (I) are not particularly limited, but after mixing the liquid components, the solid components are added in powder form. The method of dispersing or dissolving is preferable.

On the other hand, typical examples of the fibrous base material (I) used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, etc., among which glass fibers are preferable. Among these, as glass fiber,
Although E-glass, C-glass, A-glass, S-glass and the like exist from the viewpoint of their raw materials, any kind of materials can be applied to the present invention.

These fibrous base materials (II) include rovings, chopped strand mats, continuous mats, cloths, non-woven fabrics, roving cloths, surfacing mats and chopped strands, depending on their shapes. Is appropriately selected depending on the intended use and performance of the molded product, and may be a mixed use of two or more kinds or shapes if necessary. Of these, cloth and non-woven fabric are preferable.

When the epoxy resin composition (I) of the present invention contains an epoxy resin and the compound (A) as a reaction component, the epoxy resin composition (I) is applied to a fibrous base material. A laminate can be manufactured by a method of impregnating, superimposing a predetermined number of sheets, further covering both upper and lower surfaces thereof with a metal foil and / or a cover film, preheating by heating if necessary, and then heat curing.

On the other hand, as a method of obtaining a laminated board using the epoxy resin composition (I) in which a compound having an ethylenically unsaturated double bond is used in combination, for example, the epoxy resin composition (I) is applied to a fibrous base material. Impregnated with
Laminate a specified number of sheets, and further top and bottom metal foil and /
Alternatively, a method of covering with a cover film, preheating by heating or irradiation with active energy rays, etc., if necessary, and then heat curing, impregnating a fibrous base material with the epoxy resin composition (I),
Examples thereof include a method in which the polymerizable vinyl monomer is removed in a drying furnace to be B-staged, and then a predetermined number of the B-staged products are superposed and heat-cured.

The above-mentioned heat curing may be carried out in a continuous heating furnace without pressure, or may be continuously heated and pressed by a continuous double belt press. Alternatively, the pre-heated laminated body or the B-staged B-staged product may be cut and heat-press molded by batchwise. Pre-heating and B-staging of
Usually, it is carried out in the temperature range of 70 to 150 ° C, and both of the heat curing are carried out at 130 to 190 ° C. The heat and pressure molding is usually performed at a pressure of 5 to 40 kg / cm ² .

The epoxy resin composition is not limited to the use as a laminated plate, but can be used for applications such as paints, adhesives, sealants, insulating varnishes, castings and fiber reinforced plastics.

[0031]

EXAMPLES Next, the present invention will be described more specifically with reference to production examples, examples and comparative examples. All parts and% in the examples are by weight unless otherwise specified.

Production Example 1 [Production of Compound (A)] 20 g of 2-m-phenylbis (2-oxazole) and 120 g of methylhexahydrophthalic anhydride were reacted at 100 ° C. for 1 hour.

This is mainly composed of a compound (1) having a structure having a carboxyl group formed by the addition of 2-m-phenylbis (2-oxazol) and methylhexahydrophthalic anhydride. Bis (2-oxazole),
It contained methylhexahydrophthalic anhydride. Hereinafter, this is referred to as a mixture (1).

Production Example 2 [Same as above] 60 g of 2-m-phenylbis (2-oxazol) and 120 g of methylhexahydrophthalic anhydride were reacted at 100 ° C. for 3 hours.

This is mainly composed of a compound (1) having a structure having a carboxyl group formed by the addition of 2-m-phenylbis (2-oxazol) and methylhexahydrophthalic anhydride. Bis (2-oxazole),
It contained methylhexahydrophthalic anhydride. This is unreacted 2-m as compared with that of Production Example 1.
-Phenylbis (2-oxazole) and methylhexahydrophthalic anhydride were abundant. Hereinafter, this is referred to as a mixture (2).

Production Example 3 [Same as above] 20 g of 2-p-phenylbis (2-oxazol) and 120 g of methylhexahydrophthalic anhydride were reacted at 150 ° C. for 4 hours.

This is mainly composed of the compound (2) having a structure having a carboxyl group formed by addition of 2-p-phenylbis (2-oxazol) and methylhexahydrophthalic anhydride. Bis (2-oxazole),
It contained methylhexahydrophthalic anhydride. Hereinafter, this is referred to as a mixture (3).

Example 1 Epoxy resin 16.3 having an epoxy equivalent of 190 obtained by reacting bisphenol A with epichlorohydrin 16.3
Parts, 24.3 parts of an epoxy resin having an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin, and the mixture (1) 21.
6 parts, methyl tetrahydrophthalic anhydride 6.5 parts, epoxy vinyl obtained by the reaction of tetrabromobisphenol A and epichlorohydrin, which is an epoxy resin having an epoxy equivalent of 370. Epoxy vinyl composed of methacrylic acid (60%) and styrene (40%). A liquid epoxy resin composition was prepared by mixing 24.7 parts of an ester resin, 0.56 part of benzoyl peroxide, 4.3 parts of a styrene monomer, and 0.54 part of 2-ethyl-4-methylimidazole.

Immediately thereafter, a long glass cloth having a thickness of 0.18 mm and a width of 1050 mm was impregnated with the epoxy resin composition so that the content of the epoxy resin composition was 43%, and eight pieces of this were stacked. Then, the copper foil having a thickness of 35 μm is laminated on the upper and lower sides of the foil, conveyed while heating in a heating furnace at 110 ° C. for 4 minutes, and then heated at a pressure of 20 kg / cm 2 for 10 minutes by a double belt press machine heated to 170 ° C. After pressure molding, cut into 1000mm x 1000mm, then 1
It was post-cured at 70 ° C. for 50 minutes to obtain a laminated plate having a thickness of 1.6 mm.

Using each of the obtained laminated plates, the interlaminar peel strength and the chemical resistance were measured as follows. The results are shown in Table 1. Delamination strength: peeling the fibrous base material of the outermost layer from the fibrous base material adjacent to the outermost layer with the copper foil attached, keeping the angle of the peeling direction to the outermost layer base material removal surface at 90 ° C. The peel strength was measured with Tensilon at a speed of 5 cm / min.

Chemical resistance: The copper foils on both sides of the obtained laminate were removed by etching, and the laminate was exposed to methylene chloride at 40 ° C. for 30 minutes.
After immersion for a minute, the state of the surface of the laminate was visually determined.

Comparative Example 1 Epoxy resin 16.3 having an epoxy equivalent of 190 obtained by the reaction of bisphenol A and epichlorohydrin 16.3
Parts, 24.3 parts of an epoxy resin having an epoxy equivalent of 370 obtained by the reaction of tetrabromobisphenol A and epichlorohydrin, 2 parts of methyltetrahydrophthalic anhydride
8.2 parts, epoxy vinyl ester resin composed of styrene (40%) and methacrylic acid (60%) of an epoxy resin having an epoxy equivalent of 370 obtained by reaction of tetrabromobisphenol A and epichlorohydrin.
Example 1 except that 7 parts, benzoyl peroxide 0.56 parts, styrene monomer 4.3 parts and 2-ethyl-4-methylimidazole 0.54 parts were mixed to use a liquid epoxy resin composition. Similarly, a laminated plate having a thickness of 1.6 mm was obtained. Using this laminated plate, a physical property test was conducted in the same manner as in Example 1. The results are shown in Table 1.

[0043]

[Table 1] Example 2 Except that 21.6 parts of mixture (1) and 6.5 parts of methyltetrahydrophthalic anhydride were replaced with 10.8 parts of mixture (2) and 26.5 parts of methylhexahydrophthalic anhydride. A laminate having a thickness of 1.6 mm was obtained in the same manner as in 1. Using this laminated plate, a physical property test was conducted in the same manner as in Example 1. The results are shown in Table 2.

Example 3 A thickener was prepared in the same manner as in Example 2 except that 10.8 parts of the mixture (2) and 26.5 parts of methylhexahydrophthalic anhydride were replaced with 21.6 parts and 19.3 parts, respectively. A 1.6 mm thick laminated plate was obtained. Using this laminated plate, a physical property test was conducted in the same manner as in Example 1. The results are shown in Table 2.

Example 4 21.6 parts of mixture (1) and 6.5 parts of methyltetrahydrophthalic anhydride were replaced by 21.6 parts of mixture (3) and 6.5 parts of methylhexahydrophthalic anhydride. A laminated board having a thickness of 1.6 mm was obtained in the same manner as in Example 1. Using this laminated plate, a physical property test was conducted in the same manner as in Example 1. The results are shown in Table 2.

[0046]

[Table 2]

[0047]

The epoxy resin composition of the present invention uses, as a curing agent, a compound having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added. A particularly remarkable effect is obtained in that a laminated plate having remarkably excellent peeling strength and chemical resistance can be obtained.

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Claims (6)

[Claims] 1. A fibrous substrate (II) comprising an epoxy resin composition (I) containing as an essential component a compound having a structure having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added. ), And heat-curing the laminated plate. 2. An epoxy resin composition (I) having a structure having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added,
The method according to claim 1, which is an epoxy resin composition containing an epoxy resin as an essential component. 3. An epoxy resin composition (I) having a structure having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added,
The method according to claim 1, which is an epoxy resin composition containing an epoxy resin and a compound having an ethylenically unsaturated double bond as essential components. 4. An epoxy resin composition (I) comprising as an essential component a compound having a structure having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added. 5. An epoxy resin composition comprising, as essential components, a compound having a structure having a carboxyl group to which a compound having at least two oxazoline groups and a polybasic acid anhydride are added, and an epoxy resin. . 6. A compound having a structure having a carboxyl group in which a compound having at least two oxazoline groups and a polybasic acid anhydride are added, an epoxy resin, and a compound having an ethylenically unsaturated double bond. An epoxy resin composition characterized by: