JPH04185622A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. excellent in workability and curability and useful for a low-dielectric-constant laminate board excellent in resistance to heat and humidity by reacting a compd. or resin having specific chromene rings with a thermosetting resin. CONSTITUTION:A compd. and/or resin of formula I (wherein A is a group of formula II, III or IV and B is a group of formula V, VI, or VII provided that either A or B or both of them have chromene rings; X is Br or Cl; Y is a group of formula VIII, IX, X, or XI, or a direct bond; R is CH3 or C2H5; and 0<=m<=2, 0<=r<=2, and 0<=n<=30) is made to react with a thermosetting resin (e.g. an epoxy resin or a cyanate resin) to give the title compsn. excellent in workability and curability and useful for a low-dielectric-constant laminate board excellent in resistance to heat and humidity.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a method for producing a heat-resistant resin which is produced by reacting a chromene ring-containing compound or resin with a thermosetting resin, has good workability and curability, and has good heat resistance. The present invention relates to a thermosetting resin composition particularly useful for low dielectric constant laminates having excellent moisture resistance.

(Prior Art) In recent years, resins for laminates that are heat resistant, flame retardant, have a low dielectric constant, and a low dielectric loss tangent have been desired for printed wiring boards used in the high frequency range.

In response, thermoplastic resins such as fluororesins and polyphenylene oxides with low dielectric constants have been proposed, but they have problems such as low heat resistance and lack of reliability.

Additionally, rubber-modified polymaleimide (Japanese Unexamined Patent Application Publication No. E2-X27.+TO) and triazine resin (Japanese Patent Publication No. 11.712/1982) have also been proposed as resins with low dielectric constant and good heat resistance. . However, in the former case, the compatibility between rubber and polymaleimide is poor, and the cured resin is prone to bending, lacks flexibility, and is prone to cracking during through-hole processing. The latter has high hygroscopicity and is unstable, lacking moisture resistance and reliability.

Additionally, chromene resin (Japanese Unexamined Patent Publication No. 2-85275) has been proposed, but it has large curing shrinkage, tends to warp or twist when made into a laminate, and the cured resin is brittle and lacks flexibility. There is a drawback that cracks occur during through-hole processing.

(Problems to be Solved by the Invention) An object of the present invention is to provide a thermosetting resin composition for low dielectric constant laminates that has good workability and curability, and has excellent heat resistance, moisture resistance, and toughness. It is on offer.

(Means for Solving the Problems) The present invention provides a compound and/or resin containing a chromene ring represented by the following formula (1), and A -Y -+-B -Y +-A .
・(T) Of all A and B in the compound and/or resin,
At least one has a chromene ring.

X Knee Br or -C1,0≦m≦2 R knee CH3 or -C2H5,0≦r≦2, 0≦n<3
0) A composition characterized by being formed by reacting with a thermosetting resin.

The chromene ring-containing compound or resin used in the present invention is obtained by reacting polyphenols with propargyl chloride or propargyl bromide to form a globargyl ether, which is further chromenized, and is represented by the formula (I). It is something that can be done.

n is when the polyphenol is a single compound)
Indicates the number of repeats of the structural unit shown in the figure, and when composed of two or more types of compounds with different molecular weights, indicates the average number of repeats, and 0≦n<30. Preferably, 0≦
It is preferable that n≦10. If the molecular cap is too large, the solubility will be poor and the varnish viscosity will be high, making it difficult to work with.

Chromenization rate: is expressed as the ratio of chromene rings to the phenolic OH groups of the original polyphenol, and is preferably 0.3 or more and 1.0 or less. If it is too small, curing shrinkage will be large and warping and twisting will easily occur. It is difficult to make it larger than 1.0 from the viewpoint of synthesis. Although the propargyl group or the phenolic OH group is not particularly limited, the lower the ratio of the phenolic OH group, the better the water resistance, and preferably 0.5 or less.

Examples of the thermosetting resin used in the present invention include epoxy resin, cyanate resin, maleimide resin, or a combination of two or more of these resins.

Epoxy resins have at least two or more epoxy groups in their molecules, such as bisphenol A
epoxy resins, bisphenol F-based epoxy resins, brominated epoxy resins, phenol-novolac-based epoxy resins, cresol novolac-based epoxy resins, and other polyfunctional epoxy resins can be used.

The cyanate resin has at least two or more cyanate groups (-0CEN) in its molecule, such as dicyanate benzene, bis(4-cyanatophenyl)methane, and bis(3,5-dimethyl).

4-cyanatophenyl)methane, 2,2-bis(4-
cyanatophenyl)propane, 2,2-bis(4-cyanatophenyl)-1,,1,1,3,3,3-hexafluoropropane, tricyanatebenzene, phenol novolak polycyanate, etc. can be used. .

By reacting the epoxy resin, cyanate resin, or both in advance, there is no need for post-curing, and workability is improved.
Curing properties and adhesion properties are further improved. However, if the amount is too large, heat resistance, dielectric constant, and dielectric loss tangent will deteriorate.

Maleimide resin is a compound having at least two or more maleimide groups in the molecule, such as N,N'-11 phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-m-tolu Ilene bismaleimide, N,N'-4,4'-biphenylene bismaleimide,
N, N'-4,4'-(3,3'-dimethyl-biphenylene bismaleimide, N, N'-4,4'-(3,3'
-dimethyldiphenylmethane] bismaleimide, N, N
'-4,4'-(3,3'-diethyldiphenylmethane)bismaleimide, N.

N'-4,4'-diphenylmethane bismaleimide, N
, N'-4,4'-diphenylpropane bismaleimide, N, N'-4,4'-diphenyl ether bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide, N, h'-4, 4'-diphenylsulfone bismaleimide, polymaleimide represented by formula (II) or (IIT), etc. (R2nieH, alkyl group or 7z-1-l group 0
<i<10) (Q<j<10) Alternatively, examples include modified maleimide resins obtained by reacting these compounds with aromatic amines, aromatic cyanates, or allyl etherified phenols. . There is no problem even if two or more of these are included.

By reacting the maleimide resin in advance, curability and workability are further improved. However, if the amount is too large, the water absorption rate will increase and the low dielectric properties will deteriorate.

In addition, unsaturated polyester resins, diallyl phthalate resins, and the like can also be used as the thermosetting resin.

The amount of these thermosetting resins is 20 to 500 parts by weight per 100 parts by weight of the chromene ring-containing compound and/or resin.
Good weight section.

The composition containing the thermosetting resin of the present invention may optionally include:
Other flame retardants such as antimony trioxide, curing accelerators such as tertiary amines, imidazoles, phosphines, and organic peroxides can also be used in combination.

Varnish solvents are not particularly limited, but include:
For example, high-boiling polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone can be used, but ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone have good workability and can remove the solvent in a short time at low temperatures. , tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2
, 5-dimethyltetrahydrofuran, 2-ethyltetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and other cyclic ethers; and benzene, toluene, xylene, and other aromatic hydrocarbons. Two or more of these solvents may be used in combination.

(Example) Synthesis Examples 1 to 3 Potassium hydroxide and water/acetone (1,/1) were added to a reaction vessel equipped with a stirrer, reflux condenser, thermometer, and dropping funnel according to the recipe in Table 1. A mixed solvent was added and dissolved, and Boffenol was cross-linked to this and dissolved. This solution was heated, propargyl chloride was added dropwise, and the mixture was reacted under reflux for 3 hours. Thereafter, unreacted propargyl chloride with acetone was distilled off, and 1" of toluene was added.

The mixture was transferred to a separating funnel, washed with water three times, and the solvent was removed using an evaporator. The reaction rate (reaction rate of phenolic hydroxyl group) of the obtained propargyl ether compound is shown in Table 1.

Examples 1 to 3 The propargyl ether compounds obtained in Synthesis Examples 1 to 3 and stannic chloride were charged into a reaction vessel equipped with a stirrer and a thermometer according to the recipe in Table 2, and chromenated. The chromenization rate is shown in Table 2.

Examples 4 to 6 The chromenide of Examples 1 to 3 and an epoxy resin, cyanate resin, or maleimide resin were placed in six reaction vessels equipped with a stirring device, a vacuum distillation device, and a thermometer according to the recipe in Table 3. . In addition, in Example 4, 2 was further added as a reaction accelerator.
-Ethyl-4-methylimidazole was added. This was heated to 170°C and reacted under reduced pressure (approximately 2 h+mHg). The melting points of the resulting resins are shown in Table 3.

Examples 7 to 9 The chromene ring-containing resins of Examples 4 to 6 were
It was dissolved in 1,4-dioxane to a temperature of ±3 voids (25°C). A surface-treated glass cloth (E-glass) was impregnated with this varnish, and dried at 130°C in a dryer.
The solvent was removed by heating at °C for 3 minutes to prepare a prepreg. Eight sheets of this prepreg were stacked, one-sided roughened copper foil (35 μm) was stacked on both sides, and heated and pressed to obtain a copper-clad laminate. Example 9 was further post-cured at 200°C for 4 hours. The properties of these laminates are shown in Table 4.

Comparative Example 1 A maleimide resin was blended with the propargyl etherified product of Synthesis Example 1 according to the formulation in Table 4, and the same procedure as in Example 9 was carried out. Although the dielectric constant was relatively good, the curing reaction was somewhat uneven, the water absorption was rather large, and some small cracks occurred during drilling.

Comparative Example 2 Using the chromened product of Example 1 as it was, the same procedure as in Example 7 was carried out according to the formulation shown in Table 4. Curing shrinkage was large, causing warping and twisting in the laminate.

Cracks also occurred during drilling.

Comparative Example 3 Using cyanate resin, Example 8 according to the formulation in Table 4
I did the same thing. The water absorption rate was high and a small rack was generated during drilling.

Comparative Example 4 Using maleimide resin, Example 9 according to the formulation in Table 4
I did the same thing. Although the glass transition temperature is high and good, the dielectric constant and water absorption rate are high, the copper foil peeling strength is weak, and cracks occur during drilling.

(Effects of the Invention) The thermosetting resin composition of the present invention has good workability and curability, and a laminate using the same has a high Tg, low water absorption, excellent moisture resistance, and is suitable for drilling. No cracks occur, and the values of dielectric constant and dielectric loss tangent are small.

It is an extremely reliable and excellent thermosetting resin for low Wl ratio laminates and low dielectric constant multilayer printed boards.

Table 1 (Note) *1: Manufactured by Resident Durez ■ PR-5147012
: PR-51470 was subjected to an average of one bromination per phenol nucleus by a conventional method.

Table 2 Table 3 (Note) *l:l: Yuka shell epoxy Epicoat 82
8*2: High-tech polymer Alocy B-30
*3: N,N'-4,4'-diphenylmethane bismaleimide No. 4-J2

Claims (5)

[Claims] (1) A compound and/or resin containing a chromene ring represented by the following formula [I] and ▲There are mathematical formulas, chemical formulas, tables, etc.▼…[I] (A: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ B: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas , tables, etc. ▼ At least one of all A and B in the compound and/or resin has a chromene ring. X: -Br or -Cl, 0≦m≦2 Y: -CH_2- , ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or direct bond R: -CH_3 or -
C_2H_5, 0≦r≦2, 0≦n<30) A composition characterized by reacting with a thermosetting resin. (2) The composition according to claim 1, wherein the chromenization rate: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is in the range of 0.3 to 1.0. (3) The composition according to claims 1 and 2, wherein the thermosetting resin is an epoxy resin. (4) The composition according to claims 1 and 2, wherein the thermosetting resin is a cyanate resin. (5) The composition according to claims 1 and 2, wherein the thermosetting resin is a maleimide resin.