JP2002265918A - Insulating adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insulating adhesive which exhibits excellent electrical properties, processability, storability, and reliability in uses of electronic materials, especially, multilayer wiring boards. SOLUTION: This adhesive is prepared by formulating a cyanate compound with a thermoplastic resin and a silica filler containing 10-1,000 ppm 1-10C alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating adhesive, and more particularly to an insulating adhesive used for electronic and electric parts, for example, for semiconductor devices and the like, particularly for a semiconductor mounting substrate and a multilayer wiring substrate. is there.

[0002]

2. Description of the Related Art In recent years, with the demand for higher functionality and lighter, thinner and smaller electronic devices, high-density integration and high-density mounting of electronic components have been progressing. Semiconductor packages have been increasingly miniaturized and have more pins than ever before.

[0003] A conventional circuit board is called a printed wiring board, which is formed by laminating a glass fiber woven fabric with an epoxy resin. In general, a wiring board in which a through-hole is formed by drilling, a through-hole is drilled, a via is formed by plating the wall surface of the hole with a copper, and an electrical connection between the layers is made. However, the mounting components have been reduced in size and density, and the wiring density of the above-mentioned wiring boards has become insufficient, and problems have arisen in mounting components.

[0004] Against this background, recently, build-up multilayer wiring boards have been adopted. The build-up multilayer wiring board is formed while stacking an insulating layer made of only a resin and a conductor. As the via forming method, a variety of methods such as a laser method, a plasma method, and a photo method are used instead of the conventional drilling, and a high-density is achieved by freely arranging small-diameter via holes. Examples of the interlayer connection portion include a blind via (Blind Via) and a buried via (Buried Via: a structure in which a via is filled with a conductor). A buried via hole, in which a stacked via in which a via is formed on a via, is possible, is particularly noted. Have been. The buried via hole is classified into a method of filling the via hole by plating and a method of filling the via hole with a conductive paste or the like. On the other hand, as a method of forming a wiring pattern, there are a method of etching a copper foil (subtractive method), a method of electrolytic copper plating (additive method), and the like. Is starting to be.

As the density and speed of multilayer wiring boards increase, not only the density of wiring circuits and the diameter of vias become smaller, but also the characteristics required for insulating resins are becoming increasingly severe. In particular, the demands on the electrical characteristics are severe,
In the epoxy resin formulation with high handling properties,
The limits are beginning to appear. Therefore, in the high-end multilayer wiring board, a polyimide resin having excellent electrical properties, reliability, and heat resistance is actively used.However, the high heat-resistant polyimide resin requires a high-temperature process at the time of ring closure from polyamic acid to polyimide, and However, since the resin is very excellent in heat resistance, there is a problem that the processability is very poor and the cost is high.

Further, in a semiconductor package substrate on which a semiconductor is directly mounted, there is a problem of thermal stress caused by a difference in thermal expansion coefficient between the semiconductor and the semiconductor package substrate. Therefore, it is important for the resin used for the semiconductor package substrate to have a small thermal expansion coefficient of the insulating resin as well as the electrical characteristics. When the thickness of the insulating resin layer is 100 microns or more, low expansion has been achieved by impregnating the insulating resin into glass cloth. However, in a higher-density semiconductor package substrate, the thickness of the insulating resin layer is 50 microns or less. And thin, glass cloth can not be used. Therefore,
In order to reduce the expansion, a method of using a high heat-resistant polyimide resin having a low expansion coefficient or filling an insulating resin with an inorganic filler has been adopted. In the case of using a high heat-resistant polyimide resin, the above-mentioned problems are present, and the method of filling the insulating resin with an inorganic filler can achieve a low expansion to some extent, but as the insulating resin layer becomes thinner, insulation reliability, The filling rate of the inorganic filler is limited in terms of processability, and low expansion cannot be achieved.

On the other hand, from the viewpoint of controlling the impedance of the semiconductor package substrate, controlling the thickness of the insulating resin layer is also important. In the method of applying an insulating resin directly to the package substrate, it is difficult to control the film thickness.
A dry film type in which an insulating resin layer is previously formed on T is suitable for controlling the film thickness. The characteristics required for the insulating resin of the dry film include sufficient film properties, and further, low-temperature processability and film preservability are important from the viewpoint of productivity. However, there is no insulating resin which is a dry film type insulating resin and satisfies all the above-mentioned characteristics such as the electrical characteristics, the low expansion coefficient, and the high workability.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made in consideration of the electric characteristics,
An object of the present invention is to provide an insulating adhesive excellent in processability, storage stability and reliability.

[0009]

That is, the present invention provides an insulating adhesive comprising a cyanate compound, a thermoplastic resin, and a silica filler containing 10 to 1000 ppm of an alcohol having 1 to 10 carbon atoms. Agent.

In the present invention, preferably, the thermoplastic resin is 5 to 400 parts by weight, and the alcohol having 1 to 10 carbon atoms is 10 to 1000 ppm based on 100 parts by weight of the cyanate compound.
5 to 400 parts by weight of a silica filler containing the metal acetylacetonate 0.0001 to
Preferably, it comprises 0.1 parts by weight. More preferably, the metal acetylacetonate is a coordination selected from copper, manganese, nickel, cobalt, lead, zinc and tin in the divalent state, aluminum, iron, cobalt and manganese in the trivalent state, and titanium in the tetravalent state Comprising metal.

More preferably, the cyanate compound used in the present invention is a cyanate compound represented by the general formula (1), a cyanate compound represented by the general formula (2), and a compound having a cyanate group of 40 or less. % Or less, and at least one or more selected from the group consisting of cyanate compounds having at least two or more cyanate groups.

[0012]

Embedded image (In the formula (1), R _{1 to} R ₆ are each independently a hydrogen atom,
Represents any of a methyl group, a fluoroalkyl group, and a halogen atom. )

[0013]

Embedded image (In the formula (2), R _{1 to} R ₃ are each independently a hydrogen atom,
A methyl group, a fluoroalkyl group, a halogen atom,
n represents the integer of 0-6. )

More preferably, the thermoplastic resin used in the present invention is 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride or 3,3', 4,4'-benzophenonetetracarboxylic dianhydride. At least one aromatic tetracarboxylic acid component selected from the group consisting of a compound, 4,4′-oxydiphthalic dianhydride and 4,4′-diphenylsulfonetetracarboxylic dianhydride;
10 to 80 mol% of a diaminopolysiloxane represented by
And a soluble polyimide siloxane, phenoxy resin, or polyether sulfone synthesized by reacting a diamine component comprising 20 to 90 mol% of an aromatic diamine.

[0015]

Embedded image (In the formula (3), R ₇ represents a divalent hydrocarbon group, R ₈ to R
₁₁ represents a lower alkyl group or a phenyl group;
Indicates an integer of 0. )

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The cyanate compound used in the present invention is preferably a compound represented by the general formula (1), a compound represented by the general formula (2), or a compound having a cyanate group of these compounds. At least one selected from the group consisting of compounds having at least two or more cyanate groups, trimerized from 1% to 40%, and specifically, bisphenol-A dicyanateethylidenebis-
4,1-phenylenedi cyanate, tetraorthomethylbisphenol-F dicyanate, phenol novolak polycyanate, cresol novolac polycyanate, dicyclopentadienyl bisphenol dicyanate, hexafluorobisphenol A dicyanate, etc. And the compound trimerized by the above. Of these, phenol novolak polycyanate and cresol novolak polycyanate are particularly preferred. By using the cyanate compound, the workability at low temperature and the elastic modulus at the time of heating are high and 200 ° C.
It is possible to obtain an insulating adhesive having excellent heat resistance at high temperatures exceeding the above, having a low expansion coefficient, a low dielectric constant, and a low dielectric loss tangent.

The thermoplastic resin used in the present invention is preferably 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride or 3,3', 4,4'-benzophenonetetracarboxylic dianhydride. And at least one aromatic tetracarboxylic acid component selected from the group consisting of 4,4′-oxydiphthalic dianhydride and 4,4′-diphenylsulfonetetracarboxylic dianhydride; A soluble polyimide siloxane, a phenoxy resin, and a polyether obtained by polymerizing and imidizing 10 to 80 mol% of a diaminopolysiloxane represented by the formula and a diamine component of 20 to 90 mol% of an aromatic diamine. Sulfone, and any of them can be used. By using a thermoplastic resin, an insulating adhesive having excellent sheet properties in an uncured state and excellent film strength and flexibility of a cured product can be obtained.

Examples of the diaminopolysiloxane represented by the general formula (3) include 1,3-bis (3-aminopropyl) tetramethylsiloxane and α, ω-bis (3-aminopropyl) polydimethylsiloxane. And contributes to the solubility and thermoplasticity of the obtained polyamic acid and polyimide resin in organic solvents. In addition, by using this structure, the glass transition temperature can be lowered, which is particularly suitable for applications requiring low-temperature processing. The amount ratio of the diaminopolysiloxane to the total diamine component can be used within the range of 10 to 80 mol% of the total diamine component from the viewpoint of solubility and thermoplasticity. More preferably, it is within the range of 50 mol%. In particular, when 1,3-bis (3-aminopropyl) tetramethylsiloxane is used, solubility and thermoplasticity are improved without reducing heat resistance, which is preferable.

The aromatic diamines include p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4
-Diaminotoluene, 2,5-diaminotoluene, 2.5
-Diamino-p-xylene, 2,5-diamino-m-xylene, 2,5-diaminopyridine, 2,6-diaminopyridine, 3,3′-diaminodiphenylmethane, 4,4′-
Diaminodiphenylmethane, 3,3′-diaminodiphenylpropane, 4,4′-diaminodiphenylpropane,
3,3′-diaminodiphenylhexafluoropropane,
4,4′-diaminodiphenylhexafluoropropane,
3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, benzidine, 3,3′-diaminobiphenyl,
3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulphone, 4,4'-diaminodiphenyl sulphone, 4,4'-diaminobenzanilide, 4,4'- Methylenedi-o-toluidine, 4,4'-methylenedi-2,6-
Xylidine, 4,4′-methylenedi-2,6-diethylaniline, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxybenzidine, 1,3-bis (3
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4
-(4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy)
Phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether and the like. It is preferable to use one or more aromatic diamines selected from these.

The equivalent ratio of the aromatic tetracarboxylic acid component to the total diamine component in the polymerization reaction of the polyimidesiloxane is an important factor for determining the molecular weight of the obtained polyimidesiloxane. It is well known that there is a correlation between the molecular weight and physical properties of a polymer, especially the number average molecular weight and mechanical properties. The higher the number average molecular weight, the better the mechanical properties. Therefore, in order to obtain practically superior strength,
It is necessary to have a certain high molecular weight. In the present invention, the equivalent ratio r between the acid component and the amine component is 0.95 ≦ r ≦
Preferably, the molar ratio is 1.05. Further, from the viewpoint of both mechanical strength and heat resistance, 0.97 ≦ r ≦ 1.03
Is more preferable. There is no problem even if an endcap agent is used to control the molecular weight. Examples of the end cap agent include phthalic anhydride and trimellitic anhydride.

The reaction between the aromatic tetracarboxylic acid component and the diamine component is carried out by a known method in an aprotic polar solvent, and a higher degree of final imide ring closure is better.
If the imidation rate is low, imidation occurs due to heat during use,
Since the generation of water is not preferable, it is desirable that an imidization ratio of 95% or more, more preferably 98% or more is achieved.

Examples of the phenoxy resin include bisphenol-A, bisphenol-F, and bisphenol-
The type of S is not particularly limited as long as it is a phenoxy resin composed of one type or a plurality of types. For heat resistance, the amount of residual monomer is
It is preferably at most 500 ppm.

The greatest feature of the present invention is that a silica filler containing 10 to 1000 ppm of an alcohol having 1 to 10 carbon atoms is used. Silica filler has 1 to 1 carbon atoms
By containing 10 to 1000 ppm of the alcohol of No. 10, the compatibility between the silica filler and the resin is remarkably improved. As a result, the viscosity of the insulating adhesive decreases,
Formability is improved. In addition, when the insulating adhesive of the present invention is applied on a support film to form a dry film, the surface roughness of the film is reduced due to good compatibility between the resin and the silica filler, and a smooth dry film can be obtained.
Preferably, an alcohol having 1 to 8 carbon atoms, 10 to 500 p
It is a silica filler containing pm.

As the silica filler, a high-purity spherical synthetic quartz filler is preferable.
It is preferred to have a maximum particle size smaller than μm. As the alcohol having 1 to 10 carbon atoms, specifically, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, One or more of 1-hexanol, 2-hexanol, 3-hexanol, 2-methylhexanol, 2-ethylhexanol, 2-propylhexanol, and 2-butylhexanol.

As a method for incorporating 10 to 1000 ppm of an alcohol having 1 to 10 carbon atoms into the silica filler, the silica filler is dispersed in an excessive amount of alcohol by a method such as ultrasonic waves, left standing for 24 hours, and then heated. There is a method of quickly drying with a spray drier. Care must be taken during heating and drying to ensure that all alcohol does not evaporate. 1000 ppm of residual alcohol
If the amount is larger, the obtained silica filler powder is undesirably degraded. If the amount of the residual alcohol is less than 10 ppm, the affinity between the resin and the silica filler is poor, which is not preferable.

The metal acetylacetonate used in the present invention is a metal chelate in which two or more acetylacetonate ligands are bonded to a central metal atom. Examples of preferred coordinating metals are copper, manganese, nickel, cobalt, lead, zinc and tin in the divalent state, aluminum, iron, cobalt and manganese in the trivalent state, and titanium in the tetravalent state. . Metal acetylacetonate acts as a curing catalyst for the cyanate compound, and it is possible to freely control the reactivity of the insulating adhesive by its compounding amount,
Excellent storage stability.

In the insulating adhesive of the present invention, the preferable amount of each component is 5 to 400 parts by weight of a thermoplastic resin and 100 to 1 part by weight of a cyanate compound.
5 to 400 parts by weight of a silica filler containing 10 to 1000 ppm of alcohol, more preferably,
15 to 200 parts by weight of a thermoplastic resin and 20 to 400 parts by weight of a silica filler containing 10 to 1000 ppm of an alcohol having 1 to 10 carbon atoms. Further, the preferable compounding amount of the metal acetylacetonate is as follows.
0.0001 to 0.1 parts by weight with respect to 0 parts by weight,
More preferably, it is 0.005 to 0.05 parts by weight.

Additives such as a leveling agent and an antifoaming agent can be used in the insulating adhesive of the present invention according to the purpose.

The insulating adhesive of the present invention can be obtained by mixing the above-mentioned components. When using the same, it is preferable to dissolve it in a solvent and use it as a varnish. Specific examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone,
1,4-dioxane, γ-butyl lactone, diglyme, cyclohexanone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve and the like. The solvent may be used alone or as a mixture of two or more.

The insulating adhesive of the present invention preferably has a softening point of 200 ° C. or lower in a composition comprising an uncured resin component. Preferably, it is 150 ° C. or lower, more preferably 100 ° C. or lower. The heat-curing temperature of the heat-resistant adhesive is preferably from 120 ° C to 300 ° C, more preferably from 130 ° C to 250 ° C.

As the method of using the insulating adhesive of the present invention, the insulating adhesive varnish is prepared by using a metal foil, an aromatic polyimide,
A thickness of, for example, 1 to 100 μm is applied on a base film of polyethylene, polyester, or the like, and the applied layer is
By drying at a temperature of 0 ° C. to 200 ° C. for 20 seconds to 30 minutes, the solvent in the varnish is removed until it becomes about 0.5% by weight or less, and a thin film of an uncured or semi-cured insulating adhesive is removed. Can be formed. The uncured or semi-cured insulating adhesive thin film thus produced has flexibility and can be wound around a paper tube or the like or cut with a cutter. Furthermore, it has excellent storage properties,
It can withstand use after one month storage at room temperature.

In order to laminate the thin film of the uncured or semi-cured insulating adhesive produced as described above on the surface of the printed wiring board on which the circuit is formed, a vacuum laminator, a vacuum press, or the like is used. Can be. Lamination can be carried out at a temperature between 60C and 200C, especially between 70C and 150C.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

(Synthesis of polyimidesiloxane (PI) -1) 791 g of dehydrated and purified N-methyl-2-pyrrolidone (NMP) was placed in a four-necked flask equipped with a dry nitrogen gas inlet tube, a condenser, a thermometer, and a stirrer. And stir vigorously for 10 minutes while flowing nitrogen gas. Next, 73.8926 g (0.180 mol) of 2,2-bis (4- (4-aminophenoxy) phenyl) propane (BAPP),
1,3-di (3-aminophenoxy) benzene (AP
B) 17.5402 g (0.060 mol) of α, ω-bis (3-aminopropyl) polydimethylsiloxane (A
(PPS) 50.2200 g (average molecular weight 837, 0.0
(60 mol), heat the system to 60 ° C. and stir until uniform. After dissolving uniformly, the system was cooled to 5 ° C. in an ice water bath, and 44.1330 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) (0.150 g) was added.
Mol), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA) 48.4110 g
(0.150 mol) was added over 15 minutes while keeping the powdery state, and then stirring was continued for 3 hours. During this time, the flask was kept at 5 ° C. Thereafter, the nitrogen gas inlet tube and the condenser were removed, a Dean-Stark tube filled with xylene was attached to the flask, and 198 g of xylene was added to the system. Instead of the oil bath, the system was heated to 175 ° C., and generated water was removed from the system. After heating for 4 hours, no water was generated from the system. After cooling, the reaction solution was poured into a large amount of methanol to precipitate polyimide siloxane.
After the solid content was filtered, the residue was dried under reduced pressure at 80 ° C. for 12 hours to remove the solvent and obtain 227.79 g (yield: 92.1%) of a solid resin. When the infrared absorption spectrum was measured by the KBr tablet method, an absorption of 5.6 μm derived from the cyclic imide bond was observed, but an absorption of 6.06 μm derived from the amide bond was not observed. It was confirmed that the imidization was 100%.

(Synthesis of Polyimidesiloxane (PI) -2) As a diamine component, 4,4-methylenedi-2,6
-Xylidine (MDX) 0.15 mol, 2,2-bis (4- (4-aminophenoxy) phenyl) propane (BAPP) 0.09 mol, 1,3-bis (3-aminopropyl) tetramethylsiloxane ( APDS) 0.0
6 moles of aromatic tetracarboxylic acid component, 3,
0.135 mol of 3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 3,3', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA)
Except that 0.015 mol was used, polyimide resin PI
A soluble polyimide siloxane was synthesized in the same manner as in the synthesis of -1.

(Example 1) Phenol novolac polycyanate resin (Primas, manufactured by Lonza Co., Ltd.)
etPT-15), 100 g of spherical synthetic silica filler (SE2100 manufactured by Admatex Co., Ltd.
5 μm, isopropyl alcohol content 120 ppm)
After mixing 250 g, 50 g of the above-obtained polyimidesiloxane-2 and cobalt (III) acetylacetonate (Co (AA)) (Wako Pure Chemical Industries, Ltd.)
0.02 g) and 160 g of NMP, stirring,
It melt | dissolved and the insulating adhesive varnish was prepared. This insulating adhesive varnish is coated with a 25 μm thick polyester film (PET).
(Mitsubishi Chemical Polyester Film Co., Ltd., trade name:
T-100G), using a comma coater,
The coating was dried at 80 ° C. for 10 minutes and at 130 ° C. for 10 minutes to form a 25 μm thick insulating adhesive layer. The insulating adhesive layer coated on the PET was stored at a temperature of 25 ° C. for one month, and the calorific value of the film before and after storage was measured by DSC measurement to evaluate the storability. Table 2 shows the results. A sample having no change in the heat of reaction was rated as ○, and a sample having a decreased heat of reaction was rated as x. Line width / line spacing / thickness = 40 μm / 40 μm / 12 μ
m and the insulating adhesive layer are vacuum-compressed by passing the wiring between the laminating rolls heated to 100 ° C. while applying pressure in a vacuum, and further dried at 100 ° C. For 10 minutes to bury the wiring pattern. Circuit embedding here,
Workability was defined as workability, and the results are shown in Table 2. Good workability was evaluated as ○, and poor workability was evaluated as ×. Subsequently, the PET film was peeled off, and a wiring pattern with an insulating adhesive and a 18 μm-thick copper foil (trade name: 3EC-VLP, manufactured by Mitsui Kinzoku Co., Ltd.) were pressed between laminating rolls heated to 120 ° C. And vacuum-press-bonded. This crimped laminate is heated at 180 ° C. for 1 hour,
The insulating adhesive layer was cured by performing a heat treatment at 220 ° C. for 1 hour and at 250 ° C. for 1 hour. This laminate is heated at a temperature of 3
After treatment in a thermo-hygrostat at 0 ° C. and 70% humidity for 168 hours, the mixture was put twice into an IR reflow apparatus set at a peak top of 240 ° C., and it was checked for blisters. Indicated. A sample without swelling was evaluated as ○, and a sample with swelling was evaluated as ×. In addition, a 70 μm thick copper foil (manufactured by Mitsui Kinzoku Co., Ltd.,
(Trade name: 3EC-VLP) and the insulating adhesive layer coated on PET are vacuum-pressed by being passed under pressure between laminating rolls heated to 100 ° C. while applying pressure, and then the PET film is pressed. It was peeled and cured at 180 ° C. for 1 hour, 220 ° C. for 1 hour, and 250 ° C. for 1 hour.
Further, by removing the copper foil having a thickness of 70 μm by etching, a single insulating adhesive film was obtained, and a dielectric constant (1 MH) was obtained.
Table 2 shows the results of z), dielectric loss tangent (1 MHz), and coefficient of linear expansion.
It was shown to.

(Examples 2 to 4, Comparative Examples 1 to 3) A laminate was produced in the same manner as in Example 1 except that the composition of each component was as shown in Table 1. Table 2 summarizes the results of the evaluation.

[0038]

[Table 1]

[0039]

[Table 2]

In Table 1, AroCyB3 of Example 2
0 is bisphenol-A dicyanate (Cyanate group trimerization rate 30%) manufactured by Asahi Ciba Co., Ltd., and Cu (A
A) is copper (II) acetylacetonate manufactured by Wako Pure Chemical Industries, Ltd., and YP-70 of Example 3 is (bisphenol-A / bisphenol-
F) SO-2 of Comparative Example 1 which is a copolymerized phenoxy resin
5H is a spherical synthetic silica filler (average particle size: 0.6 μm, isopropyl alcohol content: 0 ppm) manufactured by Admatex Corporation.

[0041]

According to the present invention, a thin film having excellent preservability and workability in an uncured state can be obtained by coating and drying an insulating adhesive on a support film, and a circuit is formed. Can be bonded at a low temperature on a substrate that has been peeled off, and by peeling off the support film, the insulating adhesive layer can be transferred.Furthermore, copper foil, circuit products, etc. can be laminated on the insulating adhesive layer, The obtained laminate can provide an insulating adhesive exhibiting excellent electrical characteristics and reliability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 183/10 C09J 183/10 // H05K 3/46 H05K 3/46 TF term (Reference) 4J040 EE001 EE061 EH031 EJ031 EK071 EK111 GA03 GA22 GA25 HA306 HB08 HC16 HD43 KA16 KA23 LA07 LA09 MA02 NA19 NA20 4J043 PA05 PA06 QB15 QB26 RA35 SB03 TA22 TB01 TB02 UA121 UA131 VA132 UA261 UA1 UB1 UB1 UB1 UB1 UB1 VA102 XA03 XA19 ZA21 ZA46 ZB01 ZB50 5E346 AA16 CC10 CC32 CC43 DD02 DD12 HH01

Claims (6)

[Claims] 1. A cyanate compound, a thermoplastic resin,
An insulating adhesive comprising: a silica filler containing 10 to 1000 ppm of an alcohol having 1 to 10 carbon atoms. 2. A composition comprising 5-400 parts by weight of a thermoplastic resin and 5-400 parts by weight of a silica filler containing 10-1000 ppm of an alcohol having 1-10 carbon atoms, based on 100 parts by weight of a cyanate compound. The insulating adhesive according to claim 1, wherein 3. The method according to claim 1, wherein the metal acetylacetonate is 0.1%.
3. The insulating adhesive according to claim 2, comprising 0001 to 0.1 parts by weight. 4. The metal acetylacetonate is selected from copper, manganese, nickel, cobalt, lead, zinc and tin in the divalent state, aluminum, iron, cobalt and manganese in the trivalent state, and titanium in the tetravalent state. The insulating adhesive according to claim 3, comprising a coordination metal. 5. A cyanate compound represented by the general formula (1), a cyanate compound represented by the general formula (2), and a cyanate compound in which the cyanate group of these compounds is trimerized at 40% or less. The insulating adhesive according to any one of claims 1 to 4, wherein the adhesive is at least one selected from the group consisting of a cyanate compound having at least two or more cyanate groups. Embedded image (In the formula (1), R _{1 to} R ₆ are each independently a hydrogen atom,
Represents any of a methyl group, a fluoroalkyl group, and a halogen atom. ) (In the formula (2), R _{1 to} R ₃ are each independently a hydrogen atom,
A methyl group, a fluoroalkyl group, a halogen atom,
n represents the integer of 0-6. ) 6. The method according to claim 6, wherein the thermoplastic resin is 3,3 ′, 4,4′-
Biphenyltetracarboxylic dianhydride, 3,3 ', 4
4′-benzophenonetetracarboxylic dianhydride, 4,
At least one or more aromatic tetracarboxylic acid components selected from the group consisting of 4'-oxydiphthalic dianhydride and 4,4'-diphenylsulfonetetracarboxylic dianhydride, and represented by the general formula (3) A soluble polyimide siloxane, phenoxy resin or polyether sulfone synthesized by reacting a diamine component comprising 10 to 80 mol% of diaminopolysiloxane and 20 to 90 mol% of aromatic diamine. 1
6. The insulating adhesive according to claim 5. Embedded image (In the formula (3), R ₇ represents a divalent hydrocarbon group, R ₈ to R
₁₁ represents a lower alkyl group or a phenyl group;
Indicates an integer of 0. )