CN104669727B - Composite bed lamination and its manufacture method - Google Patents

Abstract

The invention provides a composite laminated board and a manufacturing method thereof. The composite laminated board (1) of the present invention includes two surface material layers (2) and a core material layer (3), and they are laminated with the core material layer (3) sandwiched between the two surface material layers (2). The two surface material layers ( 2 ) each contain a cured product of the first thermosetting composition containing a radically polymerizable compound. The core layer (3) contains a cured product of the second thermosetting composition containing an epoxy resin and a radically polymerizable compound.

Description

Composite laminated board and its manufacturing method

technical field

The present invention relates to a composite laminate comprising a core layer made of nonwoven fabric and a surface layer made of woven fabric.

Background technique

A composite laminate generally includes a core layer made of a nonwoven fabric and a surface layer made of a woven fabric, and these are laminated such that the core layer is sandwiched between two surface layers. The composite laminate is produced, for example, by impregnating a nonwoven fabric and a woven fabric with a thermosetting composition, laminating them, and curing the thermosetting composition. An epoxy resin, a radically polymerizable compound, and the like are blended into the thermosetting composition (see Japanese Patent Laid-Open No. 2013-10344).

Contents of the invention

The problem to be solved by the invention

When an epoxy resin is blended in the thermosetting composition used for the production of the composite laminate, the properties such as heat resistance and toughness of the composite laminate are improved. However, since the thermal curing reaction rate of epoxy resin is slower than that of radically polymerizable compounds, the use of epoxy resin lowers the production efficiency of composite laminated boards.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite laminated board and a method for producing the same, which can suppress a decrease in production efficiency due to the epoxy resin even though the epoxy resin is contained in its raw material.

means to solve the problem

The composite laminated board of the first aspect has two surface material layers and a core material layer, and they are laminated in a state where the aforementioned core material layer is sandwiched between the aforementioned two surface material layers,

The aforementioned two surface material layers respectively comprise a cured product of a first thermosetting composition containing a radically polymerizable compound,

The core material layer includes a cured product of the second thermosetting composition containing an epoxy resin and a radically polymerizable compound.

In the composite laminated board of the second aspect, in the first aspect, the mass ratio of the epoxy resin and the radical polymerizable compound in the second thermosetting composition is in the range of 15:85 to 55:45 .

In the composite laminated board according to a third aspect, in the first or second aspect, the second thermosetting composition contains an imidazole-based curing agent, and the ratio of the imidazole-based curing agent to the epoxy resin is 0.1 to 1.0 mass. %In the range.

The method for producing a composite laminate according to a fourth aspect is characterized in that the method is such that a nonwoven fabric impregnated with a second thermosetting composition is sandwiched between two woven fabrics each impregnated with a first thermosetting composition. In an intermediate manner, the aforementioned woven fabric and nonwoven fabric are laminated, and the aforementioned first thermosetting composition and the aforementioned second thermosetting composition are thermally cured to produce a composite laminate,

The first thermosetting composition contains a radical polymerizable compound, and the second thermosetting composition contains an epoxy resin and a radical polymerizable compound.

The method for producing a composite laminated board according to a fifth aspect is: in the fourth aspect, the mass ratio of the epoxy resin and the radical polymerizable compound in the second thermosetting composition is 15:85 to 55 : within the range of 45.

A method for producing a composite laminated board according to a sixth aspect is: in the fourth or fifth aspect, the second thermosetting composition contains an imidazole-based curing agent, and the ratio of the imidazole-based curing agent to the epoxy resin is set to It is within the range of 0.1 to 1.0% by mass.

The effect of the invention

According to the present invention, since the second thermosetting composition as a raw material of the core layer contains an epoxy resin, the core layer has a high glass transition temperature and high toughness. This ensures high heat resistance and toughness of the composite laminated board as a whole. Furthermore, since the second thermosetting composition further contains a radically polymerizable compound having a fast thermosetting reaction rate, when the second thermosetting composition is thermally cured, the reduction in the reaction rate caused by the epoxy resin is also suppressed. . Furthermore, the heat of reaction generated when the radically polymerizable compound in the second thermosetting composition and the radically polymerizable compound in the first thermosetting composition are thermally cured accelerates the reaction heat in the second thermosetting composition. Curing of epoxy resins. This ensures a high production efficiency of the composite laminate.

Description of drawings

Fig. 1 is a schematic cross-sectional view showing a composite laminated board in one embodiment of the present invention.

Fig. 2 is a schematic view showing the manufacturing process of the composite laminated board.

detailed description

As shown in FIG. 1 , a composite laminated board 1 according to the present embodiment includes two surface material layers 2 and a core material layer 3 . These surface material layers 2 and core material layers 3 are laminated with the core material layer 3 sandwiched between the two surface material layers 2 . The two surface material layers 2 each contain a cured product of the first thermosetting composition containing a radically polymerizable compound. The core layer 3 contains a cured product of the second thermosetting composition containing an epoxy resin and a radically polymerizable compound.

Since the second thermosetting composition as a raw material of the core material layer 3 contains an epoxy resin, the core material layer 3 has a high glass transition temperature and high toughness. This ensures high heat resistance and toughness of the composite laminated board 1 as a whole. Therefore, when the composite laminated plate 1 is subjected to mechanical processing such as pressing, drilling, and cutting, the occurrence of cracks and roughening of the cut surface are suppressed. Furthermore, since the second thermosetting composition also contains a radically polymerizable compound having a high thermosetting reaction rate, when the second thermosetting composition is thermosetted, a reduction in the reaction rate due to the epoxy resin is also suppressed. Furthermore, the heat of reaction generated when the radically polymerizable compound in the second thermosetting composition and the radically polymerizable compound in the first thermosetting composition are thermally cured accelerates the reaction heat in the second thermosetting composition. Curing of epoxy resins. This ensures high production efficiency of the composite laminated board 1 of the present embodiment.

The mass ratio of the epoxy resin and the radically polymerizable compound in the second thermosetting composition is preferably in the range of 15:85 to 55:45. In this case, high heat resistance and toughness of the composite laminated board 1 and high manufacturing efficiency are particularly well secured.

Preferably, the second thermosetting composition contains an imidazole-based curing agent, and the ratio of the imidazole-based curing agent in the second thermosetting composition to the epoxy resin is within a range of 0.1 to 1.0% by mass. In this way, even if the ratio of the imidazole-based curing agent is less than usual, due to the radical polymerizable compound in the second thermosetting composition and the radical polymerizable compound in the first thermosetting composition when the composite laminate 1 is produced, The heat of reaction generated when the compound is thermally cured enables efficient thermal curing of epoxy resins. Furthermore, since the amount of the imidazole-type curing agent in the second thermosetting composition is small, gelation of the second thermosetting composition does not easily proceed at room temperature. This improves the storage stability of the second thermosetting composition.

When manufacturing the composite laminate 1 of this embodiment, the nonwoven fabric 6 impregnated with the second thermosetting composition is sandwiched between two woven fabrics 9 impregnated with the first thermosetting composition, The composite laminated board 1 can be produced by laminating the woven fabric 9 and the nonwoven fabric 6 and thermosetting the first thermosetting composition and the second thermosetting composition. As described above, the radical polymerizable compound is contained in the first thermosetting composition, and the epoxy resin and the radical polymerizable compound are contained in the second thermosetting composition.

The composite laminated board 1 of the present embodiment and its manufacturing method will be described in more detail below.

First, the core layer 3 will be described. In the present embodiment, the core layer 3 includes the nonwoven fabric 6 and a cured product of the second thermosetting composition.

Non-woven fabric 6 is made of at least one or more materials such as selected from the following materials, said material is: synthetic resin fibers such as glass fibers, aramid fibers, polyester fibers, polyamide fibers (nylon); and Paper. The thickness of the nonwoven fabric 6 is preferably within a range of 0.20 to 1.0 mm, more preferably within a range of 0.3 to 0.9 mm. The binder for bonding the fibers in the nonwoven fabric 6 preferably contains an epoxy compound such as epoxysilane excellent in thermal strength. It is preferable that the quantity of a binder exists in the range of 5-25 mass parts with respect to 100 mass parts of fibers in the nonwoven fabric 6.

The core material layer 3 may include only one piece of nonwoven fabric 6 , or may include multiple pieces of nonwoven fabric 6 . When the core layer 3 includes a plurality of nonwoven fabrics 6 , the plurality of nonwoven fabrics 6 are laminated in the core layer 3 .

As described above, the second thermosetting composition contains an epoxy resin and a radically polymerizable compound. Epoxy resins and radically polymerizable compounds are thermosetting compounds. The second thermosetting composition may contain a thermosetting compound in addition to the epoxy resin and the radical polymerizable compound, but is preferably an embodiment that does not contain a thermosetting compound other than the epoxy resin and the radical polymerizable compound.

The epoxy resin in the second thermosetting composition can contain, for example, selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, One or more resins selected from biphenyl-type epoxy resins, naphthalene-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dicyclopentadiene-type epoxy resins, and anthracene-type epoxy resins. It is particularly preferred that the epoxy resin contains a bisphenol A type epoxy resin.

It is preferable that the 2nd thermosetting composition contains the hardening|curing agent of an epoxy resin. The curing agent may contain, for example, one or more compounds selected from amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and imidazole-based curing agents. It is particularly preferable that the curing agent contains an imidazole-based curing agent. When the curing agent contains an imidazole-based curing agent, the curing rate of the second thermosetting composition increases when heated, and the stability of the second thermosetting composition at normal temperature improves. The imidazole curing agent can contain, for example, selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, trimellitic acid 1-cyanoethyl-2-undecyl imidazolium salt and epoxy group - more than one compound in the imidazole adduct.

In this embodiment, when the composite laminated board 1 is manufactured, the curing reaction of the epoxy resin in the second thermosetting composition is caused by the radical polymerizable compound in the second thermosetting composition and the first thermosetting composition. The heat of reaction of the radically polymerizable compound in the composition is accelerated, so even if the amount of the curing agent in the second thermosetting composition is small, the curing reaction of the epoxy resin is accelerated. As described above, the second thermosetting composition contains an imidazole-based curing agent, and the ratio of the imidazole-based curing agent to the epoxy resin is particularly preferably within a range of 0.1 to 1.0% by mass. By making this ratio 0.1 mass % or more, thermosetting of a 2nd thermosetting composition advances especially efficiently. Moreover, the gelation of the 2nd thermosetting composition at normal temperature is especially suppressed by making this ratio into 1.0 mass % or less, and the storage stability of a 2nd thermosetting composition becomes favorable by this. More preferably, the ratio of the imidazole-based curing agent is in the range of 0.2 to 0.8% by mass, and still more preferably in the range of 0.2 to 0.6% by mass.

The radically polymerizable compound in the second thermosetting composition may contain, for example, one or more kinds selected from unsaturated polyester resins, vinyl ester resins, epoxy vinyl ester resins, and radically polymerizable unsaturated monomers. compound. Particularly preferably, the radically polymerizable compound contains an epoxy vinyl ester resin and a radically polymerizable unsaturated monomer.

Epoxy vinyl ester resins are synthesized by reacting epoxy resins with ethylenically unsaturated monobasic acids.

The epoxy resin used as the raw material of the epoxy vinyl ester resin is not particularly limited, and may contain, for example, bisphenol-type epoxy resins, novolak-type epoxy resins, alicyclic epoxy resins, glycidyl esters, glycidyl One or more resins among amines, heterocyclic epoxy resins, and brominated epoxy resins. Examples of bisphenol epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, and bisphenol S epoxy resins. Examples of the novolak-type epoxy resin include phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolak-type epoxy resins, dicyclopentadiene novolak-type epoxy resins, and the like. Examples of alicyclic epoxy resins include 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexylmethyl ester, 3,4-epoxycyclohexyl Methyl-3,4-epoxycyclohexyl methyl ester, 1-epoxyethyl-3,4-epoxycyclohexane, and the like. Examples of glycidyl esters include diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer acid, and the like. Examples of glycidylamines include tetraglycidyl diaminodiphenylmethane, triglycidyl p-aminophenol, N,N-diglycidyl aniline, and the like. Examples of the heterocyclic epoxy resin include 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate, and the like. Examples of the brominated epoxy resin include tetrabromobisphenol A type epoxy resin, tetrabromobisphenol F type epoxy resin, brominated cresol novolak type epoxy resin, brominated phenol novolac type epoxy resin, etc. . In order to improve the flame retardancy of the composite laminated board 1, the epoxy resin which is a raw material of the epoxy vinyl ester resin preferably contains a brominated epoxy resin.

Epoxy resins that are raw materials for epoxy vinyl ester resins may be modified with carboxyl group-containing rubbery polymers. That is, it can be modified by reacting a part of the epoxy groups in the epoxy resin with the carboxyl group-containing rubbery polymer. When the epoxy resin is modified with the carboxyl group-containing rubbery polymer, the impact resistance, press workability, interlayer adhesion, and the like of the composite laminated sheet 1 are improved.

The carboxyl group-containing rubbery polymer is obtained, for example, by copolymerizing a carboxyl group-containing monomer, a conjugated diene monomer, and any monomer other than these. In addition, the carboxyl group-containing rubbery polymer can also be obtained by introducing a carboxyl group into the product after copolymerizing a conjugated diene monomer and any other monomer. The carboxyl group can be introduced into any position in the molecular terminal or side chain of the product. The number of carboxyl groups introduced into the product is preferably 1 to 5, more preferably 1.5 to 3 per molecule of the product. The conjugated diene-based monomer may contain, for example, one or more compounds selected from butadiene, isoprene, and chloroprene. The optional monomer may contain, for example, one or more compounds selected from acrylonitrile, styrene, methylstyrene, and halogenated styrene.

The ratio of acrylonitrile in all monomers used in the synthesis of the carboxyl group-containing rubbery polymer is preferably in the range of 10 to 40% by mass, more preferably in the range of 15 to 30% by mass.

The ethylenically unsaturated monobasic acid used as the raw material of the epoxy vinyl ester resin may contain, for example, a compound selected from (meth)acrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl maleate, monobutyl maleate, Esters, and one or more compounds in sorbic acid. It is particularly preferable that the ethylenically unsaturated monobasic acid contains (meth)acrylic acid.

When synthesizing an epoxy vinyl ester resin, an epoxy resin, a carboxyl group-containing rubbery polymer, and an ethylenically unsaturated monobasic acid can be simultaneously reacted. In addition, when synthesizing an epoxy vinyl ester resin, it is also possible to react an epoxy resin with a carboxyl group-containing rubbery polymer, and then react with an ethylenically unsaturated monobasic acid.

The ratio of the epoxy resin, the carboxyl-containing rubber-like polymer and the ethylenically unsaturated monobasic acid is not particularly limited, but preferably the carboxyl-containing rubber-like polymer and the ethylenically unsaturated The total carboxyl groups of the monobasic acid are in the range of 0.8 to 1.1 equivalents, more preferably in the range of 0.9 to 1.0 equivalents.

A radically polymerizable unsaturated monomer has at least one radically polymerizable unsaturated group in 1 molecule. Radical polymerizable unsaturated monomers may contain, for example, selected from diallyl phthalate, styrene, methylstyrene, halogenated styrene, (meth)acrylic acid, methyl methacrylate, ethyl methacrylate ester, butyl acrylate, divinylbenzene, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate One or more compounds of acrylate and pentaerythritol tetra(meth)acrylate. It is particularly preferable that the radically polymerizable unsaturated monomer contains styrene.

It is preferable that the quantity of a radically polymerizable unsaturated monomer exists in the range of 25-45 mass parts with respect to 100 mass parts of radically polymerizable compounds in a 2nd thermosetting composition. When the amount of the radically polymerizable unsaturated monomer is 25 parts by mass or more, the impregnation property of the second thermosetting composition in the nonwoven fabric 6 becomes high. In addition, when the amount is 45 parts by mass or less, the dimensional stability and heat resistance of the composite laminated board 1 become high. The amount of the radically polymerizable unsaturated monomer is more preferably in the range of 25 to 40 parts by mass.

The second thermosetting composition preferably contains a radical polymerization initiator. The radical polymerization initiator may contain an appropriate organic peroxide. The organic peroxide can contain, for example, ketone peroxides selected from methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide; benzoyl peroxide, iso Diacyl peroxides such as butyl peroxide; Hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide; Dioxanes such as dicumyl peroxide and di-tert-butyl peroxide Base peroxides; 1,1-di-tert-butyl peroxide-3,3,5-trimethylcyclohexanone, 2,2-di-(tert-butyl peroxide)-butane and other peroxides Ketals, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate and other alkyl peroxyesters; and bis(4-tert-butylcyclohexyl)peroxydicarbonate, peroxyiso One or more compounds of peroxycarbonate such as butyl tert-butyl carbonate.

The amount of the radical polymerization initiator is preferably in the range of 0.5 to 5.0 parts by mass, more preferably in the range of 0.9 to 2.0 parts by mass, relative to 100 parts by mass of the radical polymerizable compound in the second thermosetting composition Inside.

As described above, the mass ratio of the epoxy resin and the radically polymerizable compound in the second thermosetting composition is preferably in the range of 15:85 to 55:45. In this case, high heat resistance and toughness of the composite laminated board 1 and high manufacturing efficiency are particularly well secured. The mass ratio is more preferably in the range of 35:65 to 55:45, still more preferably in the range of 45:55 to 55:45.

The second thermosetting composition preferably contains an inorganic filler. The inorganic filler may contain, for example, one or more materials selected from the group consisting of talc, silica, carbon black, mica, aluminum hydroxide, alumina, clay, titanium oxide, and barium titanate. The amount of the inorganic filler is preferably in the range of 100 to 250 parts by mass, more preferably 150 to 200 parts by mass, relative to 100 parts by mass of the total amount of the epoxy resin and the radically polymerizable compound in the second thermosetting composition. In the range.

The second thermosetting composition may further contain additives such as a curing catalyst, a solvent, a viscosity reducer, and a coupling agent as needed.

However, the second thermosetting composition preferably does not contain a solvent. That is, the second thermosetting composition is preferably a so-called solvent-free composition. In this case, it is not necessary to remove the solvent from the second thermosetting composition during the process of impregnating the nonwoven fabric 6 with the second thermosetting composition and then curing it. Therefore, environmental deterioration due to solvent volatilization is prevented. In addition, since the process of removing the solvent is unnecessary, the production efficiency of the composite laminated board 1 is improved, and the production of the composite laminated board 1 is also facilitated in a continuous process.

Since the second thermosetting composition is a solventless composition, it is preferable that the second thermosetting composition contains a radically polymerizable unsaturated monomer that is liquid at normal temperature. At this time, by dissolving or dispersing components other than the radically polymerizable unsaturated monomer in the second thermosetting composition in the liquid radically polymerizable unsaturated monomer, it is possible to obtain a liquid or a slurry easily. The second thermosetting composition.

The second thermosetting composition is prepared by an appropriate method. For example, the second thermosetting composition can be prepared by mixing the components of the second thermosetting composition with a disper, ball mill, roller, or the like.

Next, the surface material layer 2 will be described. In this embodiment, the surface material layer 2 contains the woven fabric 9 and the hardened|cured material of the 1st thermosetting composition.

The woven cloth 9 can be selected from, for example, glass cloth and synthetic resin cloth. The synthetic resin cloth can be made of synthetic resin fibers such as aramid fibers, polyester fibers, polyamide fibers (nylon), and the like. The thickness of the woven fabric 9 is preferably within a range of 50 to 500 μm.

The first thermosetting composition contains a radically polymerizable compound. The radically polymerizable compound is a thermosetting compound. The first thermosetting composition may contain a thermosetting compound in addition to the radical polymerizable compound. However, it is preferable that the radical polymerizable compound in the first thermosetting composition relative to all thermal The mass ratio of the curable compound is higher. It is particularly preferable that the first thermosetting composition does not contain a thermosetting compound other than a radically polymerizable compound.

The radically polymerizable compound in the first thermosetting composition may contain, for example, one selected from unsaturated polyester resins, vinyl ester resins, epoxy vinyl ester resins, and radically polymerizable unsaturated monomers. above compounds. Particularly preferably, the radically polymerizable compound contains an epoxy vinyl ester resin and a radically polymerizable unsaturated monomer. The details of the epoxy vinyl ester resin and the radically polymerizable unsaturated monomer are the same as those of the second thermosetting composition.

It is preferable that the quantity of a radically polymerizable unsaturated monomer exists in the range of 25-45 mass parts with respect to 100 mass parts of radically polymerizable compounds in a 1st thermosetting composition. When the amount of the radically polymerizable unsaturated monomer is 25 parts by mass or more, the impregnation property of the first thermosetting composition in the woven fabric 9 becomes high. In addition, when the amount is 45 parts by mass or less, the dimensional stability and heat resistance of the composite laminated board 1 become high. The amount of the radically polymerizable unsaturated monomer is more preferably in the range of 25 to 40 parts by mass.

The first thermosetting composition preferably contains a radical polymerization initiator. The details of the radical polymerization initiator are the same as those of the second thermosetting composition. The amount of the radical polymerization initiator is preferably in the range of 0.5 to 5.0 parts by mass, more preferably in the range of 0.9 to 2.0 parts by mass, relative to 100 parts by mass of the radical polymerizable compound in the first thermosetting composition Inside.

The first thermosetting composition preferably contains an inorganic filler. The details of the inorganic filler are the same as those of the second thermosetting composition. The amount of the inorganic filler is preferably within a range of 100 to 250 parts by mass, more preferably within a range of 150 to 200 parts by mass, based on 100 parts by mass of the total amount of radically polymerizable compounds in the first thermosetting composition.

The first thermosetting composition may further contain additives such as a curing catalyst, a solvent, a viscosity reducer, and a coupling agent as needed.

However, the first thermosetting composition preferably does not contain a solvent. That is, the first thermosetting composition is preferably a so-called solvent-free composition. In this case, it is not necessary to remove the solvent from the first thermosetting composition during the process of impregnating the woven fabric 9 with the first thermosetting composition and then curing it. Therefore, environmental deterioration due to solvent volatilization is prevented. In addition, since the process of removing the solvent is unnecessary, the production efficiency of the composite laminated board 1 is improved, and the production of the composite laminated board 1 is also facilitated in a continuous process.

Since the first thermosetting composition is a solventless composition, it is preferable that the first thermosetting composition contains a radically polymerizable unsaturated monomer that is liquid at normal temperature. At this time, by dissolving or dispersing components other than the radically polymerizable unsaturated monomer in the first thermosetting composition in the liquid radically polymerizable unsaturated monomer, it is possible to easily obtain a liquid or a slurry The first thermosetting composition.

The first thermosetting composition is prepared by an appropriate method. For example, the first thermosetting composition can be prepared by mixing the components of the first thermosetting composition with a disper, ball mill, roller, or the like.

The composite laminate 1 can also be provided with one or two conductor layers 4 . Conductive layer 4 is formed of metal foils such as copper foil and nickel foil, for example. The conductor layer 4 is arranged to overlap on the surface of the surface material layer 2 opposite to the core material layer 3 . When the composite laminated board 1 is equipped with a conductor layer 4, two surface material layers 2 and a core material layer 3, the composite laminated board 1 has a conductor layer 4, a surface material layer 2, a core material layer 3, and a surface material laminated in sequence. Layer 2 structure. When the composite laminated board 1 has two conductor layers 4, two surface material layers 2 and one core material layer 3, the composite laminated board 1 has a conductor layer 4, a surface material layer 2, a core material layer 3, and a surface material layer stacked in sequence. Layer 2, and the structure of conductor layer 4. The thickness of the conductor layer 4 is not particularly limited, and is, for example, within a range of 0.012 to 0.07 mm.

The composite laminate 1 of the present embodiment is manufactured as described above by sandwiching two woven fabrics 9 impregnated with the first thermosetting composition between the nonwoven fabric 6 impregnated with the second thermosetting composition. In between, the woven fabric 9 and the nonwoven fabric 6 are laminated, and the first thermosetting composition and the second thermosetting composition are thermally cured to manufacture.

A specific embodiment of the manufacturing method of the composite laminated board 1 will be described with reference to FIG. 2 . In addition, in this method, the composite laminated board 1 provided with the two conductor layers 4, the two surface material layers 2, and the one core material layer 3 was manufactured.

In this method, the long nonwoven fabric 6, the long woven fabric 9 and the long metal foil 12 are continuously conveyed, the nonwoven fabric 6 is impregnated with the second thermosetting composition and the woven fabric 9 is impregnated with the first thermosetting composition. The thermosetting composition is further laminated with the nonwoven fabric 6, the woven fabric 9, and the metal foil 12, and then heated to thermoset the second thermosetting composition and the first thermosetting composition. Thus, the composite laminated board 1 was manufactured. The obtained composite laminated board 1 is cut to a predetermined size as needed. Thereby, the composite laminated board 1 is manufactured in a continuous process.

The manufacturing method will be described more specifically.

A roll 5 of a long nonwoven fabric 6 is prepared, and the nonwoven fabric 6 is pulled out from the roll 5 and conveyed. On the conveyance path of the nonwoven fabric 6, the supply device 7 is arrange|positioned, and the 2nd thermosetting composition is supplied to the nonwoven fabric 6 by this supply device 7. Thereby, the nonwoven fabric 6 is impregnated with the second thermosetting resin. The supply device 7 in FIG. 2 is a roll coater, but the supply device 7 is not particularly limited as long as it is configured to impregnate the nonwoven fabric 6 with the second thermosetting resin by supplying the second thermosetting resin to the nonwoven fabric 6. form.

It should be noted that, in this method, only one roll 5 of nonwoven fabric 6 is used in order to form the core material layer 3 comprising one nonwoven fabric 6, but when forming the core material layer 3 comprising a plurality of nonwoven fabrics 6, Correspondingly, several rolls of non-woven fabric 6 are used.

In addition, two long rolls 8 of the woven fabric 9 are prepared, and the woven fabric 9 is pulled out from each roll 8 and conveyed. A supply device 10 is arranged on the conveyance path of each woven fabric 9 , and the first thermosetting composition is applied to the woven fabric 9 by this supply device 10 . The supply device 10 in FIG. 2 is a roll coater, and the supply device 10 is not particularly limited as long as it is configured to supply the first thermosetting resin to the woven fabric 9 to impregnate the woven fabric 9 with the first thermosetting resin.

In addition, two long rolls 11 of the metal foil 12 are prepared, and the metal foil 12 is conveyed from each roll 11 .

While transporting the non-woven fabric 6 impregnated with the second thermosetting composition, the two woven fabrics 9 and the two metal foils 12 impregnated with the first thermosetting composition, the metal foil 12, the woven fabric 9, The nonwoven fabric 6 , the woven fabric 9 , and the metal foil 12 are laminated in this order to produce a laminate 16 , and the laminate 16 is introduced between two rolls 13 , 13 . Thereby, the adjustment of the thickness of the laminate 16 and the adjustment of the resin amount in the laminate 16 are performed.

This laminate 16 is heated by being continuously transported in the heating furnace 14 . Thus, the first thermosetting composition and the second thermosetting composition are thermally cured. The heating temperature and heating time can be appropriately set according to the composition of the first thermosetting composition and the second thermosetting composition. ~80 minutes range.

The composite laminated board 1 pulled out from the heating furnace 14 is cut into a predetermined size by a cutting machine 15 . Thus, a composite laminated board 1 of a predetermined size is obtained. It is also possible to perform an after cure by further heating the composite laminate 1 .

If the composite laminated board 1 is produced by this method, although the second thermosetting composition as a raw material of the core material layer 3 contains an epoxy resin, it also contains a radically polymerizable compound with a fast reaction rate, so the second thermosetting composition When the thermosetting composition is thermally cured, the reduction in the reaction rate caused by the epoxy resin is also suppressed. Furthermore, the heat of reaction generated when the radically polymerizable compound in the second thermosetting composition and the radically polymerizable compound in the first thermosetting composition are thermally cured accelerates the reaction heat in the second thermosetting composition. Curing of epoxy resins. This ensures a high production efficiency of the composite laminate 1 . A composite laminate 1 with high toughness and high glass transition temperature is thus efficiently produced. In addition, the composite laminated board 1 can be manufactured very efficiently by applying the above-mentioned continuous method. In addition, since the reduction of production efficiency is suppressed, the production equipment when only the radically polymerizable compound is used as the thermosetting component can also be used for the production of the composite laminated board 1 of this embodiment as it is.

In addition, since the second thermosetting composition does not easily gel even if it contains an epoxy resin as described above, it is difficult to change the properties and viscosity of the second thermosetting composition when manufacturing the composite laminated board 1 . Therefore, the composite laminated board 1 can be manufactured stably.

In addition, the manufacturing method of the composite laminated board 1 is not limited to the above-mentioned continuous method. For example, it is also possible to produce a laminate in such a way that a non-woven fabric impregnated with the second thermosetting composition is sandwiched between two woven fabrics impregnated with the first thermosetting composition, and the laminate is heated. Pressing, thereby producing a composite laminate.

Example

[Manufacturing of composite laminates]

A solvent-free second thermosetting composition was prepared by blending the components shown in the table below. The second thermosetting composition is impregnated into a nonwoven fabric (glass nonwoven fabric with a thickness of 0.6 mm, manufactured by Vilene Company. Ltd., the binder contains epoxy silane, and the ratio of the binder to the glass fiber 100 parts by mass is 5 to 25 parts by mass).

Moreover, the component shown in the table|surface mentioned later was mix|blended, and the 1st thermosetting composition of a solventless type was prepared. This 1st thermosetting composition was made to impregnate a woven fabric (thickness 0.18mm glass cloth, the product made by Nittobo Co., Ltd., product number 7628).

Then, the woven fabric and the nonwoven fabric are laminated in such a manner that the nonwoven fabric impregnated with the second thermosetting composition is sandwiched between the two woven fabrics impregnated with the first thermosetting composition, and further on both sides Copper foil is disposed on the outermost layer, thereby obtaining a laminate.

This laminate was heated under the following conditions.

Condition 1: The maximum heating temperature is 180° C., and the heating time is 40 minutes.

Condition 2: The maximum heating temperature is 180° C., and the heating time is 60 minutes.

Condition 3: The maximum heating temperature is 180° C., and the heating time is 80 minutes.

[Evaluation of composite laminates]

(1) Evaluation of manufacturing efficiency

The copper foils on both sides were removed by performing etching treatment on the composite laminated board obtained under each condition of Conditions 1 to 3. Then, the degree of curing of the composite laminate was confirmed based on the change in weight of the composite laminate before and after heating.

In the results, the case where the curing was completely cured under any of the conditions 1 to 3 was evaluated as "A", the case where the curing was completely cured under the conditions 2 and 3 but not completely cured under the condition 1 was evaluated as "B", and the case where the curing was not completed under the condition 1 was evaluated as "B". The case where it was completely cured under conditions 1 and 2 but not completely cured under conditions 1 and 2 was evaluated as "C". The evaluation results are shown in the table below.

It should be noted that in the following evaluation tests, when the evaluation of production efficiency is A, the composite laminated board obtained under the condition 1 is used for the test; when the evaluation is B, the composite laminated board obtained under the condition 2 is used for the test; When the evaluation was C, the composite laminate obtained under Condition 3 was used for the test.

(2) Determination of glass transition temperature

After the copper foil on both sides was removed by etching the composite laminate, the glass transition temperature of the composite laminate was measured by the TMA method. The evaluation results are shown in the table below.

(3) Bending strength test

The flexural strength of the composite laminate was measured based on IPC-TM650. The evaluation results are shown in the table below.

(4) drilling processability

Four composite laminated boards were piled up, and these composite laminated boards were drilled with a drill having a diameter of 0.4 mm. The inner surface of the hole thus formed was observed, and the case where the inner surface was smooth was evaluated as "A", the case where the inner surface was partially adhered with powder generated by cutting was evaluated as "B", and the case where the inner surface was completely adhered with powder due to cutting was evaluated as "A". The condition of the resulting powder was evaluated as "C". The evaluation results are shown in the table below.

(5) Storage stability evaluation

The second thermosetting composition was left at a temperature of 30° C., and the time required for the second thermosetting composition to gel was measured. As a result, the case where gelation did not occur after 3 days was evaluated as "A", the case where gelation occurred within 1 to 3 days was evaluated as "B", and the case where gelation occurred within 12 hours or more and less than 24 hours was evaluated as "A". The case was evaluated as "C", and the case where gelation occurred before 12 hours was evaluated as "D". The evaluation results are shown in the table below.

Table 1

Table 2

Claims (2)

1. A composite laminate comprising two surface layers and a core layer, which are laminated with the core layer sandwiched between the two surface layers, The two surface material layers each contain a cured product of a first thermosetting composition containing a radical polymerizable compound, and the first thermosetting composition does not contain a thermosetting compound other than the radical polymerizable compound. , the core material layer comprises a cured product of a second thermosetting composition containing an epoxy resin, a free radical polymerizable compound and an imidazole-based curing agent, And the mass ratio of the epoxy resin and the radical polymerizable compound in the second thermosetting composition is in the range of 15:85 to 55:45, and the imidazole-based curing agent is relative to the The ratio of the epoxy resin is in the range of 0.1 to 1.0% by mass. 2. A method for manufacturing a composite laminate, characterized in that, the method is: according to the non-woven fabric impregnated with the second thermosetting composition sandwiched between two woven fabrics impregnated with the first thermosetting composition Laminate the two woven fabrics and the non-woven fabric in a cloth-to-cloth manner, and thermally cure the first thermosetting composition and the second thermosetting composition, thereby producing a composite laminate plate, The first thermosetting composition contains a radically polymerizable compound, and the first thermosetting composition does not contain a thermosetting compound other than a radically polymerizable compound, and the second thermosetting The composition contains epoxy resin, free radical polymerizable compound and imidazole curing agent, and the mass ratio of the epoxy resin and the free radical polymerizable compound in the second thermosetting composition is 15 :85 to 55:45, the ratio of the imidazole-based curing agent to the epoxy resin is in the range of 0.1 to 1.0% by mass.