JP2001122992A - Production of prepreg, nozzle using for producing prepreg and apparatus for producing prepregs - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the production process for prepregs that can control the application of the resin varnish in high accuracy and provide the nozzle and the manufacturing equipment for the prepregs. SOLUTION: The base material (substrate) is preliminarily coated with a resin varnish diluted with the solvent or ingredients and then coated with the resin varnish from both sides under pressure to prepare the objective prepreg. The objective prepreg-manufacturing apparatus is equipped with the opening with which the base material is brought into contact, the nozzle having a device for press-feeding the varnish to the opening, the preliminary impregnation tank for preliminarily impregnating the base material with the varnish diluted with a solvent or ingredients, the opening for bringing the base material into contact with the opening, two nozzles having the means for press-feeding the resin varnish so that the two nozzles may stand opposite to each other between the base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a prepreg, a nozzle used for producing the prepreg, and an apparatus for producing the prepreg.

[0002]

2. Description of the Related Art A thermosetting resin impregnated coated cloth used for a laminate for a printed wiring board is usually manufactured as follows. That is, as shown in FIG. 1 (a), a plurality of fibrous base materials 1 are unwound, stacked, and immersed in an impregnation tank 4 storing a resin varnish 2 obtained by diluting a thermosetting resin with an organic solvent. After that, squeeze roll 3 and guide roll 5
The amount of the resin is adjusted by the above, the solvent is volatilized in the drying furnace 6, the thermosetting resin is semi-cured, cooled by the cooling device 7, and sent by the dancer roll 8 to synchronize with the cutting operation. While slicing the incoming base material, the cutting machine 9 cuts it to the required size. The resin varnish squeezed by the squeeze roll 3 accumulates in the impregnation tank 4, is pumped up by a pump, is supplied to the resin varnish reservoir 10, and is supplied onto the base material 1 supplied to the impregnation tank 4.

[0003]

The properties required for this coated cloth are the required resin adhesion amount and the resin curability.
The resin adhesion amount is adjusted by the viscosity of the resin varnish and the distance between the squeeze roll 3 and the guide roll 5, and the resin curability is adjusted by the composition of the resin, the drying temperature, and the coating speed. For adjustment, measure the thickness of the prepreg immediately after coating or the prepreg after drying with a thickness gauge, measure the amount of resin varnish adhered, and adjust the interval between the squeeze roll 3 and the guide roll 5 based on the value. By controlling the amount of resin varnish attached, the measured thickness data may vary, and the thickness after drying may be measured to control the thickness applied before drying. Because there is a time delay in control,
There is a problem that it is very difficult to control the amount of resin varnish attached with high accuracy.

An object of the present invention is to provide a method for producing a prepreg, a nozzle for use in the production of a prepreg, and an apparatus for producing a prepreg, which can control the amount of resin varnish attached with high precision.

[0005]

The present invention is characterized by the following. (1) A method for producing a prepreg in which a base material is pre-impregnated with a resin varnish diluted with a solvent or a material, and the resin varnish is applied from both sides of the base material while applying pressure. (2) A nozzle having an opening to be brought into contact with the substrate in the width direction and a means for feeding the resin varnish into the opening. (3) A pre-impregnation tank for pre-impregnating the base material with a resin varnish diluted with a solvent or a material, an opening for contacting the base material in the width direction, and a nozzle having means for pressure-feeding the resin varnish to the opening. First, a prepreg manufacturing apparatus provided so as to sandwich the base material from both sides of the base material.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A nozzle having an opening to be brought into contact with a substrate in the width direction and a means for feeding a resin varnish to the opening, for example, as shown in FIG. A coating chamber 102 having an opening 101 to be brought into contact with the material 1; a front chamber 103 for supplying the resin varnish 2 to the coating chamber 102 and increasing the pressure of the resin varnish for coating;
A resin supply port 104 for supplying the resin to the varnish, a pressure sensor 105 for detecting the pressure of the resin varnish, and a comma knife 106 for smoothing the applied resin varnish 2 can be used. In combination with a target nozzle on the surface in contact with the substrate, the substrate can be provided so as to sandwich the substrate from both sides of the substrate. Two such nozzles and the pre-impregnation tank 201 for pre-impregnating the resin varnish 2 obtained by diluting the base material 1 with a solvent or a material can be combined with a conventional coating apparatus to form a prepreg manufacturing apparatus. Such a nozzle can be formed by forming a metal with a mold, drilling and cutting, screwing several metal blocks, or combining these methods. At this time, the gap between the comma knives formed by the comma knives 106 of the two nozzles is preferably adjusted so that the pressure detected by the pressure sensor 105 is constant when the supply amount of the resin varnish is constant. .

The substrate used in the present invention includes a glass cloth substrate,
There are paper base, etc., resin varnish, phenolic resin,
Thermosetting resins such as epoxy resin, polyimide resin and bismaleimide-triazine resin, and thermoplastic resins such as fluororesin and polyphenylene ether resin can be used.

[0008] Phenol resins include phenol, meta-cresol, para-cresol, ortho-cresol, isopropylphenol, para-tert-butylphenol,
Paraisopropenyl phenol oligomer, nonyl phenol, bisphenol A and the like can be used. For the modification of the thermosetting resin, a drying oil such as tung oil, polyester, polyether, epoxidized polybutadiene, or the like can be used. Further, a phosphorus compound such as a phosphoric acid ester, a bromo compound such as a brominated phenol or a brominated epoxy compound, a nitrogen compound such as a melamine compound or a triazine compound, or an inorganic compound such as antimony trioxide alone or It can also be mixed and added to a thermosetting resin to make it flame-retardant.

The epoxy resin may be any epoxy resin having an epoxy group in the molecule, such as a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, an alicyclic epoxy resin, Group epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolak epoxy resin, diglycidyl etherified biphenol, diglycidyl etherified naphthalene diol, diglycidyl etherified phenol And diglycidyl ethers of alcohols, and alkyl-substituted, halogenated and hydrogenated products thereof. These may be used in combination,
Components other than the epoxy resin may be included as impurities.

In the present invention, a halogenated bisphenol compound such as tetrabromobisphenol A such as a halogenated bisphenol A type epoxy resin, a halogenated bisphenol F type epoxy resin or a halogenated bisphenol S type epoxy resin is reacted with epichlorohydrin. When an epoxy resin in which the ortho position is substituted with a halogen atom such as chlorine or bromine with respect to the ether group of the benzene ring to which the ether group is bonded as in the case of the epoxy resin to be used, the treatment liquid of the present invention is used. The efficiency of decomposition and / or dissolution of the cured epoxy resin is particularly good.

The curing agent for an epoxy resin used in the present invention can be used without any limitation as long as it can cure an epoxy resin. Examples thereof include polyfunctional phenols, amines, imidazole compounds, acid anhydrides, organic anhydrides, and the like. Phosphorus compounds and their halides.

Examples of the polyfunctional phenols include monocyclic bifunctional phenols such as hydroquinone, resorcinol, catechol, and polycyclic bifunctional phenols such as bisphenol A, bisphenol F, naphthalene diols, biphenols, and halides thereof. There are alkyl group substituents and the like. Further, there are novolaks and resols which are polycondensates of these phenols and aldehydes.

Examples of amines include aliphatic or aromatic primary amines, secondary amines, tertiary amines, quaternary ammonium salts and aliphatic cyclic amines, guanidines, urea derivatives and the like. is there.

Examples of these compounds include N, N-
Benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, N, N'-dimethylpiperazine, 1,
4-diazabicyclo [2,2,2] octane, 1,8-
Diazabicyclo [5,4,0] -7-undecene, 1,
5-diazabicyclo [4,4,0] -5-nonene, hexamethylenetetramine, pyridine, picoline, piperidine, pyrrolidine, dimethylcyclohexylamine, dimethylhexylamine, cyclohexylamine, diisobutylamine, di-n-butylamine, diphenylamine, N -Methylaniline, tri-n-propylamine,
Tri-n-octylamine, tri-n-butylamine,
Examples include triphenylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, triethylenetetramine, diaminodiphenylmethane, diaminodiphenylether, dicyandiamide, tolylbiguanide, guanylurea, and dimethylurea.

Examples of the imidazole compound include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole,
Benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-
Methylimidazoline, 2-phenylimidazoline, 2-
Undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-phenyl-4-methylimidazoline, benzimidazole, 1- And cyanoethylimidazole.

Examples of the acid anhydride include phthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride and benzophenonetetracarboxylic dianhydride.

As the organic phosphorus compound, any phosphorus compound having an organic group can be used without any particular limitation. Examples thereof include hexamethylphosphoric triamide, tri (dichloropropyl) phosphate, tri (chloropropyl) phosphate, Examples include triphenyl phosphite, trimethyl phosphate, phenylphosphonic acid, triphenylphosphine, tri-n-butylphosphine, and diphenylphosphine.

These curing agents can be used alone or in combination. The amount of the curing agent for the epoxy resin can be used without any particular limitation as long as the curing reaction of the epoxy group can proceed, but is preferably 0.01 to 5.0 with respect to 1 mol of the epoxy group.
It is used in the range of equivalents, particularly preferably in the range of 0.8 to 1.2 equivalents.

Further, the thermosetting epoxy resin composition of the present invention may optionally contain a curing accelerator. Representative curing accelerators include, but are not limited to, tertiary amines, imidazoles, quaternary ammonium salts, and the like.

As the polyimide resin, those obtained by curing a bismaleimide resin with amines, and those obtained by curing these prepolymers with an epoxy resin, a biscyanate monomer, aminophenol, bisphenol, dicarboxylic acid, or the like can be used.

The above resin is dissolved in a soluble solvent to form a resin varnish, and if necessary, a hardening agent, a reaction accelerator and various additives are added to prepare the resin varnish.

The resin varnish prepared as described above is applied and impregnated on a fiber base material to produce a prepreg. In order to manufacture a prepreg, a vertical coating and drying machine is usually used.
As the fiber base material, one having a tensile strength that does not tear inside the vertical coating and drying machine when the resin varnish is applied can be used. The thickness is preferably 200 to 800 μm, and the substrate width is preferably about 1000 to 2000 mm.

[0023]

EXAMPLE Instead of the squeeze roll 3, impregnation tank 4 and guide roll 5 of the conventional coating apparatus shown in FIG. 2, an opening for bringing a resin varnish 2 to be applied into contact with a substrate 1 shown in FIG. A coating chamber 102 having a coating chamber 101; a prechamber 103 for supplying the resin varnish 2 to the coating chamber 102 and increasing the pressure of the resin varnish for coating; a resin supply port 104 for supplying a resin to the front chamber 103; Pressure sensor 105 for detecting the pressure of the resin, and a comma knife unit 1 for smoothing the applied resin varnish 2
No. 06, two nozzles provided so as to sandwich the base material from both sides of the base material in combination with the target nozzle on the surface in contact with the base material, and a resin varnish 2 obtained by diluting the base material 1 with a solvent or a material. And a pre-impregnation tank 201 for pre-impregnation. As shown in FIG. 1, both of the nozzles cut out a steel block, and the mounting portion 121 for mounting the nozzle to the mount, the pressure transmission hole 141 for transmitting the pressure of the resin varnish to the pressure sensor 105, and the applied resin A support block 131 provided with a comma knife section 106 for smoothing the varnish, a front chamber block 113 forming the front chamber 103 in combination with the support block 131, and a coating chamber together with the support block 131 and the front chamber block 113. 102
And a resin supply pipe 114 attached to the resin supply port 104 for supplying a resin varnish to the dance chamber. Holes were made in respective blocks, female screws were cut out, and screws were fixed to each other. The epoxy resin varnish to be applied is a brominated bisphenol A type epoxy resin 6
0 parts by weight, 40 parts of bisphenol A type epoxy resin, 25 parts of bisphenol A novolak resin and 0.2 part of ethylmethylimidazole were mixed with a filler such as aluminum hydroxide 9
0 parts of the composition, the viscosity of the resin varnish is 0.1 Ns
/ M ² in a methyl ethyl ketone solvent and mixed to obtain an epoxy resin varnish having a resin content of about 50% by weight.
A glass woven substrate 1 having a thickness of 0.1 mm is immersed in a pre-impregnation tank 201 containing a methyl ethyl ketone solvent for 5 seconds, and the above-mentioned epoxy resin varnish is supplied to each nozzle at a rate of 1200 g / m from a quantitative supply device (mono pump). Minute by minute (required resin application amount 2400 g / min), and the nozzle coating chamber 102
In order to keep the internal pressure at 133.2 ± 6.65 MPa, the gap amount between the comma knives was automatically adjusted, and coating was performed. The coating speed at this time was about 10 m / min. The resin content of the prepreg thus obtained was 53 ± 0.9.
%, And the sheet thickness after forming by heating and pressing is 121 ±
6 μm.

Comparative Example A prepreg was prepared in the same manner as in the example except that the squeeze roll gap was adjusted to 96% of the thickness of the substrate by using the conventional prepreg manufacturing apparatus shown in FIG. Was manufactured. The resin content of the obtained prepreg was 53 ±
The sheet thickness after molding was 1.5 ± 10 μm.

According to the present invention, the fibrous base material is pre-impregnated with a solvent and a diluting resin, and the resin fed by the metering device is fed to a resin coating nozzle having a front chamber, a slit, a coating chamber, and a comma knife. By controlling the amount of the comma knife gap so as to keep the pressure in the coating chamber constant, it is possible to stabilize the amount of resin impregnation into the fiber base material with high accuracy.

[0026]

As described above, according to the present invention, it is possible to provide a prepreg manufacturing method, a nozzle used for prepreg manufacturing, and a prepreg manufacturing apparatus capable of controlling the amount of applied resin varnish with high accuracy.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a main part of an impregnation device showing one embodiment of the present invention.

FIG. 2 is a side view of an apparatus showing a conventional example.

[Explanation of symbols]

1. Substrate 2. Resin varnish 3. 3. Squeeze roll Impregnation tank 5. Guide roll 6. Drying oven 7. Cooling device 8. Dancer roll 9. Cutting machine 101. Opening 102. Coating room 103. Front room 104. Resin supply port 105. Pressure sensor 106. Comma knife section 201. Pre-impregnation tank 121. Mounting part 141. Pressure transmission hole 131. Support block 113. Anterior chamber block 112. Resin stopper plate 114. Resin supply piping

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // B29K 105: 08 B29K 105: 08 B29L 7:00 B29L 7:00 F term (Reference) 4D075 AB01 AB36 AB52 AC53 AC72 DA03 DB20 DC21 4F042 AA22 BA06 CB03 DD08 ED01 ED03 4F072 AB09 AB30 AD28 AD29 AE01 AF03 AG03 AH02 AH25 AH42 AH52 AJ04 AJ13 AJ36 AL13

Claims (3)

[Claims] 1. A method for producing a prepreg, comprising preliminarily impregnating a substrate with a solvent or a resin varnish diluted with a solvent, and applying a resin varnish from both sides of the substrate while applying pressure. 2. A nozzle having an opening to be brought into contact in the width direction of a base material and means for feeding a resin varnish into the opening. 3. A nozzle having a pre-impregnation tank for pre-impregnating a substrate with a resin varnish diluted with a solvent or a material, an opening for contacting the substrate in the width direction, and a means for feeding the resin varnish to the opening. And a prepreg manufacturing apparatus provided with two of them so as to sandwich the base material from both sides of the base material.