JPH05140403A - Fluorine-containing photocurable resin composition and method for producing varnish, prepreg and laminate using the same - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a resin composition which provides an insulating resin having excellent heat resistance and flame retardancy after curing and a low dielectric constant. [Structure] General formula [1] (where R ¹ and R ² are H, F and CH
₃ , CF ₃ and R ³ and R ⁴ are selected from CH ₂ and CF ₂ . x and y show 0-4. ), Which contains a polymer having a fluorine or fluorine-containing group and a photopolymerization initiator, is solid at room temperature, melts at 100 to 200 ° C., and has a melt viscosity of 10 ⁶
A fluorine-containing photocurable resin composition, which is photocurable below poise. [Chemical 3]

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing photocurable resin composition and a method for producing a varnish, a prepreg and a laminate thereof using the composition.

[0002]

2. Description of the Related Art Conventionally, as an insulating material having a relative dielectric constant of 3 or less, a fluororesin typified by polytetrafluoroethylene or a tetrafluoroethylene-hexafluoropropylene copolymer, or a hydrocarbon such as polyethylene, polystyrene or polypropylene. System resins are known and these are widely and commonly used.

Fluorine-based resins have superior flame retardancy compared to hydrocarbon-based resins. However, both of them are thermoplastic resins and are inferior in mechanical properties or dimensional stability at high temperature. As a means for solving this, there is a method of adding a fluorine resin such as polytetrafluoroethylene to a thermosetting resin forming a crosslinked structure. For example, a fluorine-based resin such as polytetrafluoroethylene is added to a resin composition composed of epoxy-modified polybutadiene, epoxy resin, carboxylic acid anhydride, and radical polymerization initiator to reduce the dielectric constant of the insulating layer forming resin. Method (JP-A-2-72700)
Issue).

Further, in a method for manufacturing a laminate by laminating and bonding resin plates impregnated with a resin on a reinforcing material,
A method of forming a three-dimensional cross-linking fluorocarbon resin layer on the surface of a substrate by plasma polymerization or sputtering to reduce the dielectric constant of an insulating resin having improved mechanical properties and dimensional stability at high temperature (Japanese Patent Application Laid-Open No. HEI-2) -106344)
Etc. are known.

[0005]

However, even if an attempt is made to reduce the dielectric constant by adding a saturated fluorine resin such as polytetrafluoroethylene to an epoxy resin or a polybutadiene resin which is a general insulating resin, The insulating resin has a low affinity for the fluororesin. In addition, saturated fluororesins such as polytetrafluoroethylene have a high melting point,
Moreover, since it is insoluble in a solvent, it is difficult to prepare a varnish. Therefore, a non-uniform portion is formed in the resin layer after curing, and the resin is further cured by heating, which causes problems in dimensional accuracy and dimensional stability. Therefore, the use as an insulating material is limited, and it cannot be applied as an insulating material for a multilayer wiring board that requires high density and high accuracy because it is likely to cause misalignment.

Further, in the method of plasma polymerization or sputtering, the resin is synthesized from the gas phase, so that the efficiency of forming the resin layer is low and it takes a long time to obtain a predetermined thickness. Further, since it is difficult to control the cross-linking structure, random cross-linking occurs and the free volume in the resin becomes large, so that the coefficient of thermal expansion is large. Furthermore, a high vacuum device is required to perform the plasma polymerization, resulting in poor productivity.

An object of the present invention is to provide a resin composition which gives an insulating resin having excellent heat resistance and flame retardancy after curing and a low dielectric constant.

Another object of the present invention is to provide a varnish and a prepreg made of the resin composition.

Still another object of the present invention is to provide a method for producing a laminate using the above prepreg.

[0010]

Means for Solving the Problems The gist of the present invention for solving the above problems is as follows.

(1) General formula [1]

[0012]

[Chemical 2]

(However, R ¹ and R ² are H, F, CH ₃ and CF ₃
R ³ and R ⁴ are selected from CH ₂ and CF ₂ .
x and y show 0-4. ) Represented by a polymer containing fluorine or a fluorine-containing group, and a solid at room temperature containing a photopolymerization initiator,
A fluorine-containing photocurable resin composition which is melted at 100 to 200 ° C. and has a melt viscosity of 10 ⁶ poise or less and is photocurable.

(2) Fluorine-containing photocurable resin composition containing 100 parts by weight of the polymer having the fluorine or fluorine-containing group represented by the general formula [1] and 0.5 to 100 parts by weight of a photopolymerization initiator. ..

(3) A resin composition in which the fluorine-containing photocurable resin composition of the above (2) contains 0.5 to 100 parts by weight of an organic compound polymerizable by light or a polymerization initiator.

(4) The fluorine-containing photocurable resin composition of (2) above contains 0.5 to 1 of an acrylate compound monomer.
A resin composition containing 100 parts by weight.

(5) A fluorine-containing photocurable resin composition in which the photopolymerization initiator is a benzophenone-based, benzoin-based, acetophenone-based, or thioxanthone-based photoradical initiator.

(6) A fluorine-containing photocurable resin composition containing 100 parts by weight of the resin composition and 10 to 100 parts by weight of perfluorocarbon resin powder.

(7) A varnish composition containing the fluorine-containing photocurable resin composition and an organic solvent.

(8) A fibrous base material, and a prepreg containing 10 to 50% by volume of the fluorine-containing photocurable resin composition.

(9) A method for producing a laminate in which the prepregs are laminated and cured by irradiation with light.

(10) A prepreg containing a thermosetting resin in a fibrous base material, coated with the varnish composition containing the fluorine-containing photocurable resin composition and an organic solvent, dried, and then irradiated with light. A method for producing a laminated body, which comprises laminating and press-molding at the curing temperature of the above thermal prepreg.

(11) A method for producing a laminate, in which a conductive metal layer is formed on at least the surface of the laminate at the time of molding the laminate.

(12) A conductive metal layer pattern is formed on at least one surface of a laminate, a plurality of the laminates are laminated, and the fluorine-containing photocurable resin composition or the prepreg is provided between the laminates. A method of manufacturing a multi-layer circuit board that is laminated and adhered via.

(13) A method for producing a multilayer circuit board, characterized in that an aqueous solution of an amine compound is brought into contact with the laminated adhesive surface of the laminate and irradiated with light.

The fluorocarbon polymer represented by the above general formula [1] includes hexafluoro-1,3-butadiene, 1,1,2-trifluoro-1,3-butadiene, 2-trifluoromethyl-1, 3-butadiene, 2
-Homopolymers such as trifluoromethyl-1,3-pentafluorobutadiene and hexafluoro-2-butyne, polymers that undergo an isomerization reaction, or copolymers using at least two of these monomers Can be mentioned.
The number average molecular weight of the polymer is 5,000 to 160,000.

The compound which can be polymerized by light or a photoinitiator used in the present invention is an acrylic group,
A compound having a polymerizable functional group such as a methacryl group or an epoxy group, or a cinnamoyl group, a cinnamylidene group,
Examples thereof include compounds having a photofunctional group such as a chalcone residue, an isocoumarin residue, a dimethoxystilbene residue, a styrylpyridinium residue and an α-phenylmaleimide group.

The acrylate compounds are monofunctional compounds such as methyl acrylate and ethyl acrylate, polyfunctional acrylate compounds such as ethylene glycol diacrylate, diethylene glycol diacrylate, glycerin triacrylate and pentaerythritol triacrylate, poly (vinyl acrylate) and poly ( 4-acryloyloxystyrene) and other polymers having an acrylic group in the side chain. In particular, a polyacrylate compound that functions as a cross-linking agent and a polymer having an acrylic group in its side chain are preferable.

As the photofunctional initiator, a benzophenone-based, benzoin-based, acetophenone-based, thioxanthone-based photoradical generator or the like is used. The polymerization initiator is preferably used in an amount of 0.5 to 100 parts by weight based on 100 parts by weight of the resin component represented by the general formula [1]. Outside this range, the photocuring reaction may be insufficient, the reaction rate may be difficult to control, and the cured resin may be cracked.

The resin composition can form a resin film or film. In particular, the varnish can be obtained by dissolving the resin composition using a solvent. Examples of the solvent include toluene, xylene, benzene, hexafluorobenzene, acetone, methyl ethyl ketone, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, trichloroethylene, trichloroethane, dichloromethane, dioxane, ethyl acetate, and other resin compositions. A solvent capable of dissolving the substance can be selected.

As the prepreg base material, epoxy base materials, imide base materials, phenol base materials and the like which are generally used for laminating materials can be used. Further, the varnish is directly film-bonded to a substrate such as glass cloth, organic fiber cloth, or non-woven fabric,
It is preferable to apply it by a method such as casting or spin coating and dry it. These can be three-dimensionally crosslinked by exposing. Although ultraviolet rays and visible light are used as the light source, ultraviolet rays, particularly i-line (436 nm) and g-line (365 nm) of a high pressure mercury lamp are preferable from the viewpoint of workability.

The polymer represented by the above general formula [1] and containing a fluorine- or fluorine-containing group is excited by irradiation with ultraviolet light of 290 nm or more from a high pressure mercury lamp, and exhibits functionality such as reduction of water to hydrogen. .. In the reaction system, amine compounds such as triethylamine, trimethylamine and triphenylamine as electron donors, various noble metal chlorides as cocatalysts, and alcohol solvents such as methanol and ethanol as solvents are preferable. The reduction system allows not only reduction of water but also reduction of olefinic compounds.

[0033]

In the case of a general resin, a three-dimensional crosslinked resin layer can be obtained by forming a resin layer in a prepolymer state and then performing a crosslinking reaction. However, a fluororesin having a low dielectric constant and excellent heat resistance and flame retardancy is generally a thermoplastic resin, and a resin layer cannot be formed by the above method.

Since the fluorine-containing photocurable resin composition of the present invention has an unsaturated bond, it is a solvent-soluble type, can easily form the resin layer, and is easily cured by irradiation with light. be able to. In addition, since the molecule contains a fluorine atom, the cured product has a low dielectric constant and excellent heat resistance and flame retardancy.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 Synthesis of Hexafluoro-1,3-Butadiene Polymer All synthesis was carried out in a nitrogen atmosphere, and the nitrogen introduced into the experimental system used was sufficiently dehydrated and purified. Benzoyl peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was purified by a reprecipitation method in which it was dissolved in chloroform, poured into a large amount of cold methanol, filtered, and dried. Toluene (manufactured by Wako Pure Chemical Industries, special grade reagent) was refluxed for 2 hours in the presence of calcium hydride,
What was distilled under reduced pressure was used.

A 100 ml ampoule tube is connected to a vacuum line and is thoroughly purged with nitrogen. Hexafluoro-1,3-liquefied hexafluorobutadiene gas (made by PCR) purified by molecular sieves and calcium sulfate was introduced into the line and cooled by dry ice methanol.
Butadiene is collected in an ampoule tube and weighed (3 m
1, 39.26 mmol). Benzoyl peroxide dissolved in purified toluene as an initiator 0.19 g (0.7
9 mmol) and 20 ml of purified toluene as a solvent is added by a syringe. After dissolving well, the solution was frozen with liquid nitrogen, the pressure in the ampoule tube was reduced again, and the ampoule tube was sealed with a burner. After sealing the tube, the mixture was reacted in an oil bath at 60 ° C for 7 days. After a predetermined time, the solution was frozen with liquid nitrogen, the ampoule tube was opened, and methanol was added to
The reaction was stopped by adding 3 ml. The solution was poured into about 200 ml of methanol-hydrochloric acid, and the generated precipitate was filtered off with a glass filter (1G3), washed with distilled water and methanol, and dried under reduced pressure by heating at 80 ° C until a constant weight was obtained to obtain a polymer. .. The yield was about 60%. A predetermined amount of hexafluorobutadiene polymer was synthesized by the above method.

The IR spectrum (Hitachi I-5040) of the above polymer is shown in FIG. -CF to 1730cm ~ ¹
= CF-, absorption by -CF = CF ₂ appears at 1768 cm ~ ¹ , and it is considered that hexafluoro-1,3-butadiene 1,2- and 1,4-polymers were obtained.

Preparation of varnish Poly (hexafluoro-1,3-butadiene) 1 above
A resin composition comprising 00 parts by weight, 10 parts by weight of benzophenone (manufactured by Wako Pure Chemical Industries) as a photopolymerization initiator, and 10 parts by weight of triphenylamine (manufactured by Aldrich) is dissolved in a solvent hexafluorobenzene (manufactured by Wako Pure Chemical Industries). Then, a varnish of a 50% solution was prepared.

Preparation of prepreg and laminated plate Glass-polyimide prepreg (Hitachi Kasei Kogyo I-
67) as a base material, the varnish was uniformly applied to the surface of the base material, and dried in constant temperature air at 80 ° C. for 10 minutes. This was exposed to i-line (436 nm) of a high pressure mercury lamp to form a three-dimensional crosslinked fluorocarbon resin layer on the surface. The exposure amount was 3 mJ / cm ² . 10 sheets of the prepreg are stacked, and the pressure is 30 kgf / cm ² and the temperature is 130 ° C. in the press.
At 30 ° C. for 30 minutes, followed by an adhesive curing reaction at 200 ° C. for 1 hour to obtain a laminated plate.

As a sample for measuring the copper foil peel strength, 10 prepregs and copper foil (made by Furukawa Electric Co., Ltd., thickness 70
μm) were laminated and laminated and adhered under the same conditions as above.

The characteristics of the sample were evaluated. The relative permittivity was measured using JIS-C-648 using LF impedance analyzer 4192A (manufactured by Hewlett-Packard Co.).
According to 1, the capacitance of the sample was measured to determine the relative permittivity.

The peel strength of the copper foil is the rheometer NRM-3.
101D (manufactured by Fudo Kogyo), JIS-C-6481
Then, the peel strength in the vertical direction was measured under the condition of the peeling speed of 50 mm / min.

The thermal decomposition start temperature is the high-speed differential thermal balance TGD.
It was measured using -7000RH (manufactured by Vacuum Riko). For 10 mg of powder sample obtained by crushing the resin component, He
A heating loss curve was measured at a temperature rising rate of 5 ° C./min in an atmosphere having a flow rate of 100 cm ³ / min, and the temperature showing 5% by weight loss was defined as the thermal decomposition start temperature.

The coefficient of thermal expansion was measured by using a thermomechanical property measuring device TM-3000 manufactured by Vacuum Riko Co., Ltd. and measuring 7 mm × 7 m from the laminated plate.
Thermal expansion coefficient (50 to 22) in the thickness direction of the sample cut out to m.
0 ° C.) was measured. The measurement was performed in a compression mode with a temperature rising rate of 2 ° C./min and a load of 10 g.

The flame retardancy was measured by UL-94. The results of these measurements are summarized in Table 1.

Example 2 Synthesis of hexafluoro-1,3-butadiene isomerized polymer
It is known that formed hexafluoro-1,3-butadiene is isomerized to hexafluoro-2-butyne by a cesium compound. By using a cesium compound such as cesium fluoride as an initiator, poly (hexafluoro-
It produces an isomerized polymer having the same structure as 2-butyne). The isomerized polymer has excellent crystallinity as compared with a polymer using hexafluoro-2-butyne as a monomer, and has high solubility in a solvent.

All experiments are carried out under a nitrogen atmosphere, and the nitrogen introduced into the experimental system is one that has been sufficiently dehydrated and purified. Cesium fluoride (manufactured by Wako Pure Chemical Industries) is used while reducing the pressure to 120
Heat to ~ 160 ° C and dry for 2 hours. Toluene (manufactured by Wako Pure Chemical Industries, special grade reagent) is used in the presence of calcium hydride.
After refluxing for an hour, vacuum distillation is performed. In a glove box purged with nitrogen, 0.12 g (0.79 mmol) of cesium fluoride is put into a 100 ml ampoule tube and connected to a vacuum line. Hexafluorobutadiene gas purified by molecular sieves and calcium sulfate (PCR
Liquefied hexafluoro-1,3-butadiene was collected in an ampoule tube and weighed (3 ml, 39.26).
mmol). Purified toluene is used as a solvent by a syringe.
Add 0 ml. After dissolving well, the solution was frozen with liquid nitrogen, the pressure in the ampoule tube was reduced again, and the ampoule tube was sealed with a burner. After sealing, 7 in an oil bath at 60 ° C
Reacted for a day. After a predetermined time, the solution was frozen with liquid nitrogen, the ampoule tube was opened, and methanol hydrochloric acid was added to 2-3 m.
1 was added to stop the reaction.

The above solution was poured into about 200 ml of methanol / hydrochloric acid, and the resulting precipitate was filtered with a glass filter (1G3).
Was filtered off, washed with methanolic hydrochloric acid, distilled water and methanol, and dried under reduced pressure by heating at 80 ° C. until a constant weight was obtained to obtain a powdery polymer. The yield was about 60%. A predetermined amount of hexafluoro-1,3-butadiene isomerized polymer was synthesized by the above method.

The IR spectrum (Hitachi I-5040) of the above polymer is shown in FIG. 1715cm ~ ^1- (C
F ₃ ) CF = C (CF ₃ )-appears to be absorbed, and hexafluoro-1,3-butadiene hexafluoro-2
An isomerized polymer to butyne was obtained.

Synthesized poly (hexafluoro-1,3-
Butadiene) 100 parts by weight, a photopolymerization initiator 10 parts by weight of benzophenone (manufactured by Wako Pure Chemical Industries), and 10 parts by weight of triphenylamine (manufactured by Aldrich) as a solvent hexafluorobenzene (manufactured by Wako Pure Chemical Industries). )
To prepare a 50% solution. Using the solution as a varnish, a laminate was prepared and evaluated in the same manner as in Example 1.

Example 3 Poly (hexafluoro-1,
3-butadiene) 100 parts by weight, diethylene glycol diacrylate 10 parts by weight, a resin composition comprising 10 parts by weight of benzophenone as a photopolymerization initiator and 10 parts by weight of triphenylamine in a solvent hexafluorobenzene (manufactured by Wako Pure Chemical Industries) It was dissolved at 50% to obtain a varnish. This was applied to a base material in the same manner as in Example 1 to prepare a prepreg, and using this, a laminated board was prepared and evaluated.

Example 4 100 parts by weight of isomerized poly (hexafluoro-1,3-butadiene), Resin M manufactured by Maruzen Co., Ltd.
A resin composition comprising 10 parts by weight of poly (4-acryloyloxystyrene) obtained by reacting acryloyl chloride with the hydroxyl groups of the side chains of 10 parts by weight, 10 parts by weight of benzophenone as a photopolymerization initiator, and 10 parts by weight of triphenylamine, A varnish was obtained by dissolving the solvent in hexafluorobenzene at a concentration of 50%. This was applied to a base material in the same manner as in Example 1 to prepare a prepreg, and using this, a laminated board was prepared and evaluated.

Example 5 Poly (hexafluoro-2-
Butyne) 100 parts by weight, diethylene glycol diacrylate 10 parts by weight, benzophenone as a photopolymerization initiator 10 parts by weight, triphenylamine 10 parts by weight in a solvent acetone (manufactured by Wako Pure Chemical Industries) concentration 50.
% To dissolve and obtain a varnish. This was applied to a base material in the same manner as in Example 1 to prepare a prepreg, and using this, a laminated board was prepared and evaluated.

Example 6 100 parts by weight of poly (1,1,2-trifluoro-1,3-butadiene), 10 parts by weight of benzophenone (manufactured by Wako Pure Chemical Industries, Ltd.) as a photopolymerization initiator,
A resin composition consisting of 10 parts by weight of triphenylamine (manufactured by Aldrich) was dissolved in a solvent acetone at a concentration of 50% to obtain a varnish. This was applied to a base material in the same manner as in Example 1 to prepare a prepreg, and using this, a laminated board was prepared and evaluated.

Example 7 Hexafluoro-1,3-butadiene / hexafluoro-2-butyne 1: 1 copolymer 100 parts by weight, diethylene glycol diacrylate 1
A resin composition comprising 0 parts by weight, 10 parts by weight of benzophenone as a photopolymerization initiator, and 10 parts by weight of triphenylamine was dissolved in a solvent dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) at a concentration of 50% to obtain a varnish. This was applied to a base material in the same manner as in Example 1 to prepare a prepreg, and using this, a laminated board was prepared and evaluated.

Example 8 A varnish produced in the same manner as in Example 1 was molded into a film by a casting method, and the film and prepreg I-67 were alternately laminated to prepare a 10-layer laminate.

Example 9 Polyhexafluoro-1,3
A resin composition comprising 100 parts by weight of butadiene, 10 parts by weight of an epoxy resin (Epicoat 828 manufactured by Yuka Shell Co., Ltd.), and 10 parts by weight of an aryl diazonium salt CH ₃ ON ₂ PF ₆ as a photopolymerization initiator in a solvent hexafluorobenzene. It was dissolved at 50% to obtain a varnish. This was applied to a base material in the same manner as in Example 1 to prepare a prepreg, and using this, a laminated board was prepared and evaluated.

Example 10 Poly (hexafluoro-2)
-Butyne) 100 parts by weight, bismaleimide 10 parts by weight,
A resin composition containing 10 parts by weight of benzophenone and 10 parts by weight of triphenylamine as a photopolymerization initiator was dissolved in a solvent acetone (manufactured by Wako Pure Chemical Industries, Ltd.) at a concentration of 50% to obtain a varnish. This was applied to a base material in the same manner as in Example 1 to prepare a prepreg, and using this, a laminated board was prepared and evaluated.

[Example 11] A prepreg was prepared in the same manner as in Example 2 except that benzoyl methyl ether (Nisso Cure-MBO manufactured by Nippon Soda Co., Ltd.) was used as the photopolymerization initiator. It was produced and evaluated.

Example 12 A prepreg was prepared in the same manner as in Example 2 except that 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure-1173 manufactured by Merck & Co., Inc.) was used as the photopolymerization initiator. Was prepared, and a laminated board was prepared using this and evaluated.

[Example 13] A prepreg was prepared in the same manner as in Example 2 except that 2-methylthioxanthone (Nisso Cure-MTX manufactured by Nippon Soda Co., Ltd.) was used as the photopolymerization initiator. Was produced and evaluated.

Comparative Example 1 As a comparative example, a polytetrafluoroethylene-based copper-clad laminate R47 manufactured by Matsushita Electric Works, Ltd.
37 was evaluated in the same manner as in Example 1.

Comparative Example 2 Polymers: Vol. 47, No. 7, pages 549 to 552
A plasma polymerized film was formed on the surface using prepreg I-67 as a substrate. Hexafluoroethane (manufactured by Asahi Glass Co., Ltd.) was used as the monomer gas. A plasma polymerization apparatus was used in which a high frequency power supply had a frequency of 13.56 MHz, an output of 1000 W, an electrode made of an inductively coupled copper tube having an outer diameter of 6 mm, and a reaction tube having a quartz tube having an inner diameter of 10 cm and a length of 20 cm installed horizontally. Output 450W, pressure 400P
Polymerization reaction was carried out at a gas flow rate of 100 cm ³ / min for 12 hours to obtain a film having a thickness of 40 μm. The obtained prepreg was laminated and adhered in the same manner as in Example 1 and its characteristics were evaluated.

[Comparative Example 3] MCL-I-67 manufactured by Hitachi Chemical Co., Ltd., which is a glass-polyimide type copper-clad laminate, was evaluated in the same manner as in Example 1.

The results of the above Examples and Comparative Examples are summarized in Table 1. In addition, although the glass-polyimide prepreg (I-67 manufactured by Hitachi Chemical Co., Ltd.) was used as the base material of the prepreg in the above Examples, the photocurable resin composition varnish of the present invention was applied to an ordinary glass fiber base material. It goes without saying that it can be formed by direct impregnation.

[0067]

[Table 1]

The photocurable resin composition of this example is made of heat-resistant material,
It is possible to provide a cured product having excellent flame retardancy, a low dielectric constant, and a low thermal expansion property. In particular, when used as an adhesive for a polyimide-based laminated material having a low thermal expansion property, the relative dielectric constant can be lowered while maintaining the low thermal expansion property. The coefficient of thermal expansion is about 1/3 of that of a laminated plate made of low-dielectric-constant thermoplastic polytetrafluoroethylene, and a laminated plate having excellent dimensional stability can be provided.

[Embodiment 14] Next, an example of a high-density wiring board using the prepreg obtained in the above embodiment will be shown.

Using the prepreg obtained in Example 2, the surface of the prepreg was coated with the varnish obtained in the same manner as in Example 2 to form a photocurable resin layer. The resin layer was exposed using a circuit pattern mask, and the unexposed portion was dissolved with hexafluorobenzene, which is the solvent used for preparing the varnish, to form a resin pattern on the prepreg surface. A conductor pattern was formed on this pattern portion by a chemical copper plating method.

The laminated plates having the above-mentioned circuit patterns were laminated and adhered via the prepreg, and through holes were formed at predetermined places by drilling, and conductors were formed in the through holes by the chemical copper plating method.

As described above, the pin grid array substrate for mounting the LSI was manufactured. The substrate has a six-layer structure and has a surface layer, a power supply layer and a signal layer.

FIG. 3 shows a schematic sectional view of the produced pin grid array substrate.

Example 15 Using the prepreg obtained in Example 2, copper foil (70 μm) was applied on both sides under a pressure of 30.
kgf / cm ^2, for 30 minutes heat-pressing at a temperature 220 ° C., to obtain a copper-clad laminate was further cured for one hour at 250 ° C.. A circuit pattern was formed on both surfaces of this copper-clad laminate with an etching photoresist (SR-3200 manufactured by Hitachi Chemical Co., Ltd.), and a conductor circuit was formed by an etching method. The laminate having the circuit pattern formed thereon was laminated and adhered via a prepreg to produce a multilayer laminate. Further, a through hole was formed in the multilayer laminated plate by a drill, and a conductor was formed in the through hole by the chemical copper plating method. In this way, a pin grid array substrate for mounting an LSI was manufactured.
This substrate has a six-layer structure and has a surface layer, a power supply layer, and a signal layer.

[Example 16] Using the prepreg obtained in Example 2, a microchip carrier substrate on which an LSI was mounted was prepared in the same manner as in Example 14. This board is 6
It has a layered structure and has a surface layer, a power supply layer, and a signal layer.

Example 17 Using the prepreg obtained in Example 2, Example 16 was carried out in the same manner as in Example 14.
A module substrate on which the microchip carrier substrate of 1 was mounted was manufactured. This substrate has upper and lower surface layers and a power supply layer 10
It has a 36-layer structure composed of 16 layers, 16 signal layers, and 8 expansion layers. Further, 81 (9 × 9) microchip carrier substrates can be mounted on this substrate.

[Embodiment 18] Using the prepreg obtained in Embodiment 2 and carrying out Embodiment 17 in the same manner as in Embodiment 14.
A large-area substrate on which the module substrate of 1 was mounted was manufactured. This substrate includes upper and lower surface layers, a power supply layer 20, a signal layer 24.
It has a 54-layer structure consisting of 8 layers and 8 layers. Also, this board can mount 64 (8 × 8) of the above module boards.

Example 19 Example 17 is carried out in the same manner as in Example 14 using the prepreg obtained in Example 3.
A large-area substrate on which the module substrate of 1 was mounted was manufactured. This substrate includes upper and lower surface layers, a power supply layer 16 layers, and a signal layer 20.
It has a 46-layer structure consisting of 8 layers of expanded layers. In addition, 36 (6 × 6) of the above module substrates can be mounted on this substrate.

Each of the substrates of the above examples has a low dielectric constant and enables high-density mounting.

[0080]

The photocurable resin composition of the present invention can be easily dissolved in a solvent and can be used as various varnishes. Further, it has excellent moldability and is easy to cure because it is photocurable. In particular, when an acrylate compound is used in combination, the dielectric constant is low at 2.3 to 2.8, the glass transition temperature is relatively high at about 150 ° C, and insulation requiring mechanical strength at high temperatures is required. It is also suitable as a material.

[Brief description of drawings]

FIG. 1 Poly (hexafluoro-1,3-butadiene)
It is an IR spectrum of.

FIG. 2 is an IR spectrum of isomerized poly (hexafluoro-1,3-butadiene).

FIG. 3 is a schematic cross-sectional view of a pin grid array substrate.

[Explanation of symbols]

1 ... Base material (prepreg), 2 ... Conductor (copper) pattern, 3
… Cured photo-curable resin, 4… through holes.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 127/12 PFG 9166-4J H05K 3/46 G 6921-4E // C08L 27:12 9166-4J (72) Inventor Akio Takahashi 4026 Kuji Town, Hitachi City, Ibaraki Prefecture, Hitachi Research Laboratory, Hitachi Ltd. (72) Inventor Akio Mukai 4026 Kuji Town, Hitachi City, Hitachi City, Hitachi Ltd. Hitachi Research Laboratory, Hitachi Ltd.

Claims (14)

[Claims] 1. A general formula [1]: (However, R ¹ and R ² are selected from H, F, CH ₃ and CF ₃ ,
R ³ and R ⁴ are selected from CH ₂ and CF ₂ . x and y are 0-4
Indicates. ), A polymer containing a fluorine or fluorine-containing group and a photopolymerization initiator, and solid at room temperature, 100 to 200
A fluorine-containing photocurable resin composition which is melted at 0 ° C. and has a melt viscosity of 10 ⁶ poise or less and is photocurable. 2. The general formula [1] (wherein R ¹ and R ² are H,
Selected from F, CH ₃ and CF ₃ , and R ³ and R ⁴ are CH ₂ and CF ₂
Chosen from. x and y show 0-4, m shows 30-1000. ) A fluorine-containing photocurable resin composition comprising 100 parts by weight of a polymer having a fluorine or fluorine-containing group represented by the formula (1) and 0.5 to 100 parts by weight of a photopolymerization initiator. 3. 100 parts by weight of a polymer having a fluorine or fluorine-containing group represented by the general formula [1], 0.5 to 100 parts by weight of an organic compound polymerizable by light or a polymerization initiator, and A fluorine-containing photocurable resin composition comprising 0.5 to 100 parts by weight of a polymerization initiator. 4. 100 parts by weight of a polymer containing the fluorine or fluorine-containing group represented by the general formula [1], 0.5 to 100 parts by weight of an acrylate compound monomer, and 0.5 to 100 of a photopolymerization initiator. A fluorine-containing photocurable resin composition, characterized in that it contains a part by weight. 5. The fluorine-containing photocurable composition according to any one of claims 1 to 4, wherein the photopolymerization initiator is a benzophenone-based, benzoin-based, acetophenone-based, or thioxanthone-based photoradical initiator. Resin composition. 6. The fluorine-containing photocurable resin composition according to claim 1, which comprises 100 parts by weight of the resin composition and 10 to 100 parts by weight of perfluorocarbon resin powder. 7. The general formula [1] (wherein R ¹ and R ² are H,
Selected from F, CH ₃ and CF ₃ , and R ³ and R ⁴ are CH ₂ and CF ₂
Chosen from. x and y show 0-4. ), Which contains a polymer having a fluorine or fluorine-containing group and a photopolymerization initiator, is solid at room temperature, melts at 100 to 200 ° C., and has a melt viscosity of 10 ⁶ poise or less and is photocurable. A varnish composition comprising a curable resin composition and an organic solvent. 8. A fibrous base material, and the general formula [1] on the base material.
(However, R ¹ and R ² are selected from H, F, CH ₃ and CF ₃ ,
R ³ and R ⁴ are selected from CH ₂ and CF ₂ . x and y are 0-4
Indicates. ), A polymer having a fluorine or fluorine-containing group and a photopolymerization initiator, and solid at room temperature, 100 to 200
A prepreg, which comprises 10 to 50% by volume of a fluorine-containing photocurable resin composition which is melted at 0 ° C. and has a melt viscosity of 10 ⁶ poise or less and which is photocurable. 9. A fibrous base material, and the general formula [1] on the base material.
(However, R ¹ and R ² are selected from H, F, CH ₃ and CF ₃ ,
R ³ and R ⁴ are selected from CH ₂ and CF ₂ . x and y are 0-4
Indicates. ), A polymer having a fluorine or fluorine-containing group and a photopolymerization initiator, and solid at room temperature, 100 to 200
A laminate comprising: a prepreg containing 10 to 50% by volume of a fluorine-containing photocurable resin composition that is melted at 0 ° C. and has a melt viscosity of 10 ⁶ poise or less and is photocurable, and is cured by irradiation with light. Manufacturing method. 10. A prepreg in which a fibrous base material contains a thermosetting resin is added to the above-mentioned general formula [1] (wherein R ¹ and R ² are selected from H, F, CH ₃ and CF ₃ , and R ³ , R ⁴ is CH ₂ ,
It is selected from CF ₂ . x and y show 0-4. ), Which contains a polymer having a fluorine or fluorine-containing group and a photopolymerization initiator, is solid at room temperature, melts at 100 to 200 ° C., and has a melt viscosity of 10 ⁶ poise or less and is photocurable. A process for producing a laminate, which comprises coating a varnish composition containing a curable resin composition and an organic solvent, drying and irradiating the varnish composition, and laminating the varnish composition, and press-molding at a curing temperature of the thermosetting resin. 11. The method for producing a laminated body according to claim 9, wherein a conductive metal layer is formed on at least the surface of the laminated body when the laminated body is formed. 12. A conductive metal layer pattern is formed on at least one surface of a laminated body, a plurality of laminated bodies are laminated, and the space between the laminated bodies is represented by the general formula [1] (provided that R ¹ and R ^{2 are provided.} Is H,
Selected from F, CH ₃ and CF ₃ , and R ³ and R ⁴ are CH ₂ and CF ₂
Chosen from. x and y show 0-4. ), Which contains a polymer having a fluorine or fluorine-containing group and a photopolymerization initiator, is solid at room temperature, melts at 100 to 200 ° C., and has a melt viscosity of 10 ⁶ poise or less and is photocurable. A method for producing a multilayer circuit board, which comprises laminating and adhering via a curable resin composition. 13. A conductive metal layer pattern is formed on at least one surface of a laminated body, a plurality of laminated bodies are laminated, and the space between the laminated bodies is represented by the general formula [1] (provided that R ¹ and R ^{2 are provided.} Is H,
Selected from F, CH ₃ and CF ₃ , and R ³ and R ⁴ are CH ₂ and CF ₂
Chosen from. x and y show 0-4. ), Which contains a polymer having a fluorine or fluorine-containing group and a photopolymerization initiator, is solid at room temperature, melts at 100 to 200 ° C., and has a melt viscosity of 10 ⁶ poise or less and is photocurable. A method for producing a multilayer circuit board, which comprises laminating and bonding via a prepreg composed of a curable resin composition and a fibrous base material. 14. The method for producing a multilayer circuit board according to claim 12, wherein an aqueous solution of an amine compound is brought into contact with the surface of the laminate to be laminated and adhered, and light irradiation is performed.