JPS62158715A - Thermosetting resin composition and prepreg and laminated sheet using the same - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin which is excellent in heat resistance, flexibility and adhesion to copper foil, low in specific dielectric constant and applicable to a multilayer printed circuit board, etc., by using 1,2-polybutadiene and epoxy-modified polybutadiene. CONSTITUTION:The titled composition essentially consisting of an epoxy- modified polybutadine (A) which is a block polymer of the formula (wherein A is a glycidyl ether type epoxy copolymer and B is an oligomeric polybutadiene having double bonds in side chains and having 0-10 OH groups bonded to the carbon main chain), e.g., epoxy-modified polybutadiene modified with diglycidyl ether bisphenol A, 1,2-polybutadiene (B) and a radical polymerization initiator (C) (e.g., benzoyl peroxide). This composition can be improved in moldability, flexibility and adhesion to copper foil by using both components A and B, and therefore it can be applied to multilayer printed circuit boards, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermosetting resin composition and a prepreg and a laminate using the same.

[Conventional technology]

Conventionally, phenolic resins, epoxy resins, polyimide resins, and the like are known as laminated materials for multilayer printed circuit boards. However, in recent years, with the increasing demand for faster arithmetic processing in large computers, there is an increasing need to improve signal transmission speed.

Therefore, there is a strong demand for printed circuit boards with excellent electrical characteristics. In particular, low dielectric constant printed circuit boards are needed to shorten signal transmission delay time and reduce circuit width. Tetrafluoroethylene resin (PTFE), polybutadiene resin, and the like have been developed as such low dielectric constant laminated materials. However, since PTF''E is a thermoplastic resin, it has problems with one-dimensional safety and through-hole reliability when bonding multilayers.Therefore, when applied to multilayer printed boards, it requires the same level of wiring as epoxy resin. It is only possible to obtain density, and there is not much merit as a low dielectric constant material.Also, P
Since TFE does not have a suitable solvent, it is generally bonded by hot melt pressure bonding, but it has the disadvantage of a very high rej melting temperature. As described above, compared to conventional methods, PTFE has many difficult aspects in terms of workability and moldability, and it is necessary to significantly change the manufacturing method.

[Problem that the invention seeks to solve]

Conventional polybutadiene resin is a relatively low-molecular polymer that can be used as a varnish to impregnate the base material and has good hardening properties, but it remains sticky at the prepreg stage, causing problems in winding, laminating, etc. often occurs. In addition, laminated I+,
ν had problems with the peel strength of the bonded copper foil, mechanical strength, flame retardancy, heat resistance, etc. Regarding stickiness,
As described in JP-A No. 55-9613, improvement has conventionally been achieved by using a high molecular weight polymer.

However, at the same time, problems such as brittleness and cracking occurred. Moreover, the disadvantages in laminate properties such as heat resistance, flame retardance, and copper foil adhesion, along with the advantage of low dielectric constant, were based on the nature of polybutadiene resin.

In the present invention, polybutadiene resin is modified in order to take advantage of the advantages described above and overcome the disadvantages.

The object of the present invention is 1. It has excellent mechanical strength and heat resistance, and can be applied to multilayer printed circuit boards. Low dielectric constant and formability,
An object of the present invention is to provide a thermosetting resin composition having excellent dimensional stability, and prepregs and laminates using the same.

[Means for solving problems]

The first invention is (a) a block polymer represented by the following general formula El) (where A is glycidylny A-B-A [I
] It is a copolymer of tezyl ether-based epoxy resin, and B
is a polybutadiene low polymer (molecule, t
It3oo~5000) theal) theal epoxy-modified polybutadiene, (b) 1,2-polybutadiene, (
c) a radical polymerization initiator as an essential component. To the above (b) 1,2-polybutadiene, (
a) By adding epoxy modified polybutadiene,
Improves moldability, flexibility, and adhesion to copper foil. Moreover, the 2nd invention is the said resin composition (a), (b).

By further adding an epoxy curing agent to (c),
In addition to further improving the various properties mentioned above, the dielectric constant has been reduced.

In the epoxy-modified polybutadiene, which is one of the essential components of the thermosetting resin of the present invention represented by the general formula [I], specific examples of glycidyl ether-based epoxy resins used for modification include diglycidyl Ether bisphenol A, diglycidyl ether 2,2'-dibromobisphenol A, diglycidyl ether 2.2',
4.4'-tetrabromobisphenol A, diglycidyl ether 2,2'-dimethylbisphenol A, diglycidyl ether 2.2', 4-trimethylbisphenol A, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin . One or more of these may be used as desired.

In addition, the 1,2-polybutadiene component in the resin composition of the present invention includes 1,2-polybutadiene homopolymer, cyclized 1,2-polybutadiene, 1,2-polybutadiene glycol, and 1,2-polybutadiene carboxylic acid. Various kinds of polymers, copolymers, etc., each of which has 1,2-polybutadiene as a basic component having double bonds in side chains can be used.

Blending ratio (weight) with the epoxy modified polybutadienes
is selected in the range of 80:20 to 20:,30,
If the former ratio is larger than this, the relative dielectric constant of the thermosetting resin will increase and the one-dimensional stability will also decrease. If the amount is too small, the flow of the synthetic resin is poor during molding, and lipoids and smudges are likely to occur.

After curing, the resin is brittle and prone to cracking.

Furthermore, the effect of bisphenol A type and novolac type carbon skeletons having good heat resistance becomes insignificant, and the adhesion to copper foil also decreases. A particularly preferable ratio of the same components is 70:3.
0-30:70.

Typical examples of radical polymerization agents include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxylaurate, di-butyl peroxy phthalate, dibenzyl oxide, and 2,5-dimethyl. -2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide,
di-butyl hydroperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(di-butylperoxy)hexyne (3), diisopropylbenzene hydroperoxide, p-menthane hydroperoxide oxide, pinane hydroxide, 2,5-dimethylhexane-2,5-sibide loba-oxide, cumene hydroperoxide, and the like. These are resin composition 10
Preferably, 0.1 to 10 parts by weight are added to 0 parts by weight.

Typical examples of epoxy curing agents include 4,4'-diaminodicyclohexylmethane, 1,4-diaminodicyclohexane, 2,6-diamitupyridine, 5m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane. , 2.2'-bis(4-aminophenyl)propane.

Benzine, 4.4'-diaminophenyl oxide24.
4'-diaminophenyl sulfone, bis(4-aminophenyl)methylphosphine oxide.

Bis(4-aminophenyl)phenylphosphine oxyto, bis(4-aminophenyl)methylamine, 1.5
-diaminonatutanone, m-xylylenediamine, 1
, 1'-bis(p-aminophenyl)frazi, p-xylyleninodiamine, hexamethylenediamine, 6.6
'-Diamino-2゜2'-dipyridyl,4.4' -
Diaminobenzophenone, 4,4'-diaminoazobenzene, bis(4-aminophenyl)phenylmethane, 1
．． 1-bis(4-aminophenyl)cyclohexane, 1
．． 1-bis(4-amino-3-methylphenyl)cyclohexane, 2.5-bis(m-aminophenyl)-1,
3,4-oxadiazole, 2,5-bis(p-aminophenyl)-1,3,4-oxadiazole, 2,5-
Bis(m-aminophenyl)thiazolo(4,5-d)thiazole, 5゜5-di(m-aminophenyl)-(2,
2') bis(1,3,4-oxadiazolyl), 4.
4'-diaminodiphenyl ether, 4,4'-bis(
p-aminophenyl)-2,2'-dithiazole, m-
Bis(4-p-7minophenyl-2-thiazolyl)benzene, 4.4'-diaminobenzanilide, 4.4'
-diaminophenylbenzoate.

N,N'-bis(4-aminobenzyl)-p-phenylenediamine, 4,4'-methylenebis(2-dichloroaniline), benzoguanamine, methylguanamine, tetramethylbutanediamine, phthalic anhydride, trimellitic anhydride , pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), maleic anhydride, 2-methylimidazole, 2-phenylimidazole, 2-ethyl -4-methylimidazole, 2-undecylimidazole, etc., and at least one of them is used. The blending amount is 0.1 parts by weight per 100 parts by weight of epoxy-modified polybutadiene.
It is appropriate to use it in a range of 30 parts by weight, preferably 0.3 to 10 parts by weight.

Solvents used when the resin is used in the form of varnish include xylene, toluene, methyl ethyl ketone, acetone, N,N-dimethylformamide, N-methyl-
2-pyrrolidone, dimethyl sulfoxide, trichloroethyl! Examples include non-carbon, 1,1,2-1 to dichloroethane, and any solvent that can uniformly mix the component polymers can be used without limitation. Next, the obtained impregnating varnish is impregnated and coated on a sheet-like base material, dried at room temperature to 170°C, and made into a non-tacky prepreg. obtain. The drying temperature settings at this time depend on the solvent and radical polymerization agent used.

Determined by hardening agent, etc. Layer the required number of prepregs finally obtained, preferably at 100-250°C.
A heat curing reaction is performed under a pressure of kgf/ad to obtain a laminate.

Almost all commonly used sheet-like base materials can be used. Inorganic fibers include 5iOz,
E-glass containing Aura etc.

C glass, A glass, S glass, D glass, 'YM-3
There are various types of glass fibers such as 1-A glass and Q glass using quartz. Examples of organic fibers include aramid fibers containing a polymer compound having an aromatic polyamide-imide skeleton.

〔Example〕

Example 1 Epoxy-modified polybutadiene modified with diglycidyl ether bisphenol A and l,2-polybutadiene (molecule 1i1.5 Xl06. Side chain vinyl group content 9
0%''-) in xylene at 80°C.

1 polymer blending ratio 4:6 (weight ratio) by heating and dissolving for 30 minutes,
A varnish with a solids content of 25% was obtained. moreover.

As a radical 11 initiator, 5 parts by weight of dicumyl peroxide was added to the entire resin composition. This varnish was applied to a 50 μm glass sheet (sheet-like base material),
It was dried in a constant temperature bath at 110°C for 20 minutes to obtain a tack-free prepreg. Stack 10 sheets of the prepreg and press 4
The material was heated at 0 to 50 kg weight/d at a temperature of 130° C. for 30 minutes, and then the temperature was further raised to 170° C. to 240° C., and an adhesive curing reaction was performed in a press for 2 hours to produce a laminate.

Example 2 To the resin composition of Example 1 and the radical polymerization initiator, an epoxy curing agent, l,4'-diaminodiphenylmethane, and 7 parts by weight were added to 100 parts by weight of epoxo-modified polybutadiene. A laminate was obtained in the same manner as in Example 1.

Example 3 A laminate was obtained using phenol novolac type epoxy modified polybutadiene and 1,2-polybutadiene in the same manner as in Example 1.

Example 4 Two hydroxyl groups are added to the polybutadiene main chain. Diglycidyl ether bisphenol A type epoxy modified polybutadiene and 1,2-polybutadiene were prepared in Example 1.
A laminate was obtained using the method as described above.

Example 5 Brominated diglycidyl ether bisphenol A epoxy-modified polybutadiene (3% bromine) and 1,2
- A laminate was obtained using polybutadiene in the same manner as in Example 1.

Comparative Example 1 An attempt was made to create a laminate using a varnish obtained by dissolving the 1,2-polybutadiene used in Example 1 and dicumyl peroxide in xylene in the same manner as in Example 1, but cracks occurred. A large amount of was generated and the laminate could not be formed.

Comparative Example 2 A varnish obtained by dissolving diglycidyl ether bisphenol A type epoxy resin and 4,4'-diaminodiphenylmethane in methyl ethyl ketone was used in the same manner as in Example 1 to obtain a laminate.

The main properties of the laminates obtained from the Examples and Comparative Examples and the heat resistance of the cured resin are shown in the table.

As can be seen from Comparative Example 1, when 1,2-polybutadiene is used alone, many cracks occur and a laminate cannot be formed. Furthermore, as seen from Comparative Example 2, epoxy resin has too high a dielectric constant, making it impossible to increase wiring density. However, the laminate in which epoxy-modified polybutadiene was added to 1,2-polybutadiene of the present invention had improved moldability, flexibility, and copper foil adhesion.

Further addition of an epoxy curing agent further improved the above properties and also lowered the dielectric constant. For example, when comparing Comparative Example 2 and Example 3, the signal transmission speed increases by about 20% by changing the dielectric constant from 5.0 to 3.3. Further, by adding brominated epoxy-modified polybutadiene to the polybutadiene resin as shown in Example 5, @thermal properties were also improved.

〔Effect of the invention〕

By using the thermosetting resin composition of the present invention, it is possible to obtain a laminated material that has excellent properties not only in heat resistance and adhesive properties but also in electrical properties and is applicable to multilayer printed circuit boards and the like.

Claims (1)

[Claims] 1. (a) Block A- represented by the following general formula [I]
B-A [I] Polymer {However, A is a copolymer of glycidyl ether-based epoxy, and B is a polybutadiene having a double bond in the side chain and 0 to 10 hydroxyl groups bonded to the main carbon chain. It is a low polymer. }, (b) 1,2-polybutadiene, and (c) a radical polymerization initiator as essential components. 2. The thermosetting resin composition according to claim 1, wherein the blending ratio (weight) of the block polymer and 1,2-polybutadiene is from 90:10 to 10:90. 3. (a) Block A- represented by the following general formula [I]
B-A [I] Polymer {However, A is a copolymer of glycidyl ether-based epoxy, and B is a polybutadiene having a double bond in the side chain and 0 to 10 hydroxyl groups bonded to the main carbon chain. It is a low polymer. }, in the epoxy-modified polybutadiene, each of the phenyl groups contained in A has 1 to
The thermosetting resin composition according to claim 1, wherein four halogen groups or alkyl groups are bonded. 4, (a) Block A- represented by the following general formula [I]
B-A [I] Polymer {However, A is a copolymer of glycidyl ether-based epoxy, and B is a polybutadiene having a double bond in the side chain and 0 to 10 hydroxyl groups bonded to the main carbon chain. It is a low polymer. }; (b) 1,2-polybutadiene; (c) a radical polymerization initiator; and (d) an epoxy curing agent. . 5, (a) Block A- represented by the following general formula [I]
B-A [I] Polymer {However, A is a copolymer of glycidyl ether-based epoxy, and B is a polybutadiene having a double bond in the side chain and 0 to 10 hydroxyl groups bonded to the main carbon chain. It is a low polymer. }, (b) 1,2-polybutadiene, and (c) a radical polymerization initiator. . 6, (a) Block A- represented by the following general formula [I]
B-A [I] Polymer {However, A is a copolymer of glycidyl ether-based epoxy, and B is a polybutadiene having a double bond in the side chain and 0 to 10 hydroxyl groups bonded to the main carbon chain. An epoxy-modified polybutadiene which is a low polymer (molecular weight 300 to 5000), (b) 1,2-polybutadiene, (c) a radical polymerization initiator, and (d) an epoxy curing agent as essential components. Prepreg is produced by impregnating a sheet-like base material with varnish and drying it. 7. In a laminate in which prepregs formed by impregnating and drying a resin into a base material are laminated and bonded, the resin is (a) a block polymer represented by the following general formula [I] (however, A-B-A [ I
] A is a copolymer of glycidyl ether-based epoxy resin, and B has a double bond in the side chain and 0 in the main carbon chain.
epoxy-modified polybutadiene which is a polybutadiene low polymer to which ~10 hydroxyl groups are bonded;
) 1,2-polybutadiene and (c) a radical polymerization initiator as essential components. 8. In a laminate in which prepregs formed by impregnating and drying a resin into a base material are laminated and bonded, the resin is (a) a block polymer represented by the following general formula [I] (however, A-B-A [ I
] A is a copolymer of glycidyl ether-based epoxy resin, and B has a double bond in the side chain and 0 in the main carbon chain.
epoxy-modified polybutadiene (which is a polybutadiene low polymer with ~10 hydroxyl groups bonded);
A laminate comprising:) 1,2-polybutadiene, (c) a radical polymerization initiator, and (d) an epoxy curing agent as essential components.