JPH01286850A - Continuous manufacture of laminate - Google Patents

Abstract

PURPOSE:To contrive contact between base materials by reducing further a matter on the surface of the base material out of an impregnating resin solution as much as possible, by a method wherein after continuous impregnation of a paper base material with a resin composition consisting mainly of side chain double bond type resin, a plurality of which is led into the same impregnating resin solution again under a state where the base materials are superposed upon each other and pass them through squeeze rollers in the solution. CONSTITUTION:An impregnating resin solution consisting mainly of side chain double bond type resin and crosslinking vinyl monomer is used. Paper base materials 1 pass respectively through a device 2 of dehumidification treatment or pretreatment with melamine resin and the resin solution is fed sufficiently within the base material, in a resin impregnating device 3. Resin-solution-imdpregnated paper base materials 6 are integrated on a rollers 7, removal of the impregnating resin solution of a desired quantity is performed. The piled up resin- solution-impregnated base materials are led immediately to rollers 8 provided by immersing into an impregnating solution bath 8a, pressurized within the impregnating solution and a laminated body A obtained by pulling out the same is sent into a heating oven 9 by passing through over the rollers 7. The laminated body A is pressurized with a pressurizing rolls 11 within the oven 9d, cured through heating while removing a desired quantity of the impregnating solution and a laminate 13 is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for continuously manufacturing a laminate, and more particularly to a method for continuously manufacturing a laminate while impregnating it with a resin liquid.

[Prior art] Conventionally, phenolic resin has been used in some cases, but in order to prevent partial lifting of the laminate due to reaction by-products, 50k resin was used.
A molding pressure of more than g/cd is required, and it is extremely difficult to continuously secure the above pressure in a continuous manufacturing method.

By using a thermosetting resin that does not substantially generate reaction byproducts such as condensed water and gas during curing, the pressurizing pressure can be reduced. Such resins include unsaturated polyester resins, and in the case of a styrene solution thereof, it is sufficient to lightly press the laminate from the top and bottom surfaces with an endless belt. Conversely, under high pressure, due to its low viscosity, not only the resin liquid existing between the base materials but also the resin liquid contained within the base materials is discharged, impairing the performance of the laminate.

However, if the pressure is low, a cured layer consisting only of resin liquid is formed between the base materials, which is undesirable in terms of both the strength and rigidity of the laminate. From this point of view, it is desirable to bring the base materials into contact with each other by applying pressure.

In order to make this contact between the base materials, the impregnated resin liquid on the surface of the base material should be used as much as possible under pressure, since if the resin liquid contained in the base material is discharged, the result will be the same as in the case of unsaturated polyester. It is desirable to be able to remove more liquid than is present in the material.

Also, a resin suitable for this has not yet been found.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to find a method for reducing the amount of the impregnating resin liquid on the surface of the substrate as much as possible to achieve contact between the substrates.

[Means for Solving the Problem] In order to solve this problem, the inventor of the present invention has found that even if the impregnating resin is present within the base material, it will hardly be present between the base materials if the inventors concentrate on their research. The present invention has been completed. That is,
The gist of the present invention is to continuously impregnate a paper base material with a resin composition containing a side chain double bond type resin as a main component, and then to superimpose a plurality of the resin compositions and then introduce the same impregnating resin solution again into the same impregnated resin solution. This is a continuous method for manufacturing a laminate, in which the material is passed through a squeezing roller inside, drawn out, and heated and cured while draining excess impregnated resin liquid under pressure.

The present invention will be explained in detail below.

The side chain double bond type resin referred to in the present invention is a polymer consisting of a main chain and a side chain, where the main chain is a backbone polymer containing a vinyl monomer unit having a functional group, and the side chain is a backbone polymer containing a vinyl monomer unit having a functional group. A radically reactive carbon formed through the functional group of the chain.
Refers to a side chain double bond type resin which is a branch having a carbon double bond, and the vinyl monomer unit that constitutes the main chain of the side chain double bond type resin is an essential unit when it has a functional group. It contains vinyl monomer units that do not have functional groups as necessary, and these polymerize to form the main chain.

Monomers constituting the above essential units include acrylic acid,
Vinyl monomers having a carboxyl group as a functional group such as methacrylic acid, maleic anhydride, and maleic acid monoester, vinyl monomers having a glycidyl group as a functional group such as glycidyl methacrylate, glycidyl acrylate, etc. Allyl alcohol, 2-hydroxy Typical examples include vinyl monomers having a hydroxyl group as a functional group, such as ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, and N-methylol acrylamide. and methacrylic acid are most preferably used.

In the present invention, a functional group-containing monomer unit may be present as an active functional group when the main chain is formed by polymerization, or may be polymerized by reacting the side chain described below with the functional group of the monomer in advance. It refers to a type of vinyl monomer unit that has a functional group that serves to form a side chain into the main chain, regardless of whether the main chain is formed by forming a side chain.

Non-functional monomers include styrene,
α-methylstyrene, chlorostyrene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl bromide, acrylonitrile, ethylene, propylene, butadiene, acrylic ester, methacrylic ester, vinyl acetate, vinyl propionate, diester maleate, ethyl vinyl Examples include benzene.

The weight average molecular weight of the main chain composed of these vinyl monomer units is from 5,000 to 400,000, preferably from 10,000 to 200,000. This value is appropriately selected depending on the type of side chain. This molecular weight affects the physical properties of the laminate and impregnating properties, and
If it is less than 0, the mechanical properties of the cured laminate will be insufficient, and if it exceeds 400,000, the resin impregnation into the base material (paper etc.) will be poor, both of which are not preferred.

The amount of monomer units having functional groups in the main chain is related to the density of the side chains, and since it affects the curing reactivity between the side chains, an appropriate ratio is selected, but the side chain density in the main chain 10001H is 0. 1
-2 mol is preferable, and 0.4-1.5 mol is more suitable.

The side chain referred to in the present invention refers to a chain that has a >C-C double bond at the end or in the middle, and that forms a chain in the main chain via its functional group, but typical As a matter of fact, (blank space below)
l C.J.
+1
u=o l engineering E
Ol O:
Engineering U-0100-CJ I Q=Ol
1 etc. can be exemplified as a general formula.

(I) In the formula, R1 to R3 are hydrogen or a methyl group, n represents an integer of 0 to 5, (II) In the formula, R4 is hydrogen or a methyl group, and Ll and L2 are 10- or -NH -, Xl and X2 represent a C2 to 01B hydrocarbon group or a hydrocarbon group connected by an ether bond, and in parentheses X and X2, the carbon atom bonded to the oxygen between X and X2 and I is a primary or secondary carbon, and B
is an aliphatic, alicyclic or aromatic hydrocarbon group up to C2o.

(III) In the formula, R5 is hydrogen or a methyl group.

Note that the side chains of the side chain double bond type resin according to the present invention are not limited to these, and any type of side chain that can form a crosslink between side chains by a radical reaction using a crosslinking vinyl monomer can be used.

In the present invention, various methods can be employed to introduce a side chain having a double bond at the end of the side chain into the polymer constituting the main chain. Some examples are as follows.

(1) One epoxy group of a compound having a jepoxy group such as bisphenol diglycidyl ether type epoxy group is reacted with the carboxyl group of the functional group of the main chain, and the remaining epoxy group is reacted with (meth)acrylic acid. let

(2) React the carboxyl group of the main chain functional group with glycidyl (meth)acrylate.

(3) React the epoxy group of the main chain functional group with (meth)acrylic acid.

(4) A diisocyanate compound is reacted with hydroxyethyl (meth)acrylate to prepare a reaction product containing monoisocyanate as the main component and almost no diisocyanate compound, and the isocyanate groups contained in this reaction product are combined with the hydroxyl groups of the main chain polymer. Make it react.

In the exemplified method, the main chain was copolymerized first, but in the present invention, of course, the reaction to form the side chain is carried out first, and such monomers are finally copolymerized to form the side chain terminal (method). ) A side chain double bond type resin containing an acryloyl group may be produced.

The side chain double bond type resin in the present invention is diluted with a crosslinking monomer such as styrene, and a polymerization initiator is added before use. Furthermore, it can also be used as a flame-retardant composition by adding a known halogen flame retardant and/or inorganic flame retardant as necessary.

The crosslinking vinyl monomer is not particularly limited, but among the monomers, monofunctional hydrocarbon monomers include styrene, vinyltoluene, chlorostyrene, methyl acrylate, ethyl acrylate, butyl acrylate,
Included are 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, benzyl methacrylate, dibutyl maleate, dioctyl maleate, vinyl acetate, vinyl propionate, and the like. These monomers may be used in combination of two or more.

Among the vinyl monomers for crosslinking, polyfunctional hydrocarbon monomers include divinylbenzene and derivatives thereof, diene compounds such as cyclopentadiene and butadiene, divinyl ester compounds, divinyl urethane compounds, and the like.

These polyfunctional hydrocarbon monomers must be compounds that can be copolymerized with the above-mentioned monofunctional derivatives, and those that form a uniform copolymer are particularly preferred.

Using an impregnating resin solution containing the above-mentioned side chain double bond type resin and the crosslinking vinyl monomer as main components, a laminate was continuously manufactured using the apparatus and process shown in FIG. 1.

The paper base material 1 passes through a device 2 for dehumidification treatment or pretreatment with melamine resin, etc., and a resin impregnation device 3 consisting of a side chain double bond type resin and a crosslinking vinyl monomer supplies enough resin liquid into the base material. be done. The resin liquid-impregnated paper base materials 6 are combined on a roller 7 to be overlapped, a desired amount of the impregnated resin liquid is removed, and the overlapping resin liquid-impregnated base materials are immediately immersed in an impregnating liquid bath 8a. The laminate A is introduced into the submerged squeezing roller 8 provided, pressurized in the impregnating liquid, and extracted. The resulting laminate A is passed over the roller 7 and sent into the heating oven 9. In the oven, pressure is applied using pressure rolls 11.degree. 11 and other commonly used pressure devices, and the laminate 13 is heated and cured while removing a desired amount of the impregnating liquid. In addition,
When the laminate A is sent into a heating oven, a metal foil can also be drawn in at the same time to create a metal-clad laminate.

Next, the present invention will be explained with reference to Examples.

[Example] Using the side chain double bond type resin having the type (1) type side chain produced by the method (1) above as the resin impregnating liquid,
Use kraft paper with a thickness of 300μ and a surface roughness of about 20μRMS and an impregnated resin liquid with a viscosity of 50 centipoise.After impregnation, 5 sheets are stacked to form a laminate, and the weight is approximately 5 kg/c.
It was pressurized under rnO linear pressure through an impregnating bath containing a solid liquid and a squeezing roll with a diameter of 150 mm immersed in the liquid, and then taken out and placed in a heating oven at a weight of about 1.0 kg/kg.
A laminate was obtained by passing through a group of pressurizing rollers (10 pairs) with cm line pressure and curing while removing the impregnating liquid in the first half. The molding speed is 3 m/min.

As a result of observing the cross section of the obtained laminate, it was observed that although the impregnated resin was present in the base material, there was hardly any between the resins.

[Comparative Example] An attempt was made to create a laminate under the same conditions as in Example except that an unsaturated polyester resin was used instead of the side chain double bond type resin, but the impregnating resin liquid was removed from the base material due to the pressure in the heating oven. It flowed out and a laminate could not be obtained.

As described above, the present invention has been widely used in the past.

For example, the continuous production method that was impossible due to the inability to secure the appropriate pressure for laminates and metal foil-clad laminates produced by a batch method using a hot press using phenolic resin, has been made possible by the above-mentioned suitable hardening properties. By using a resin liquid and a base material, it is possible to continuously produce laminates and metal foil-clad laminates with high efficiency and good quality using an industrially feasible molding method.
Its industrial value is extremely large.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an example of an apparatus and process for manufacturing a metal foil-clad laminate according to the present invention. 1 is a paper base material, 2 is a dehumidification pre-treatment device for paper base materials, 3 is an impregnation device, 4 is a curable resin liquid tank, 5 is a resin liquid transfer pump,
6 is a paper base material impregnated with resin liquid, 7 is a guide roll, 8 is a submerged squeezing roll, 9 is a heating oven, 10 is a metal foil for lamination, 11 is a pressurized multi-roll, 12 is a cutting machine, 13 is a It is a laminated board.

Claims (1)

[Claims] After continuously impregnating a paper base material with a resin composition whose main component is a side chain double bond type resin, multiple sheets are stacked and introduced into the same impregnated resin solution again, and the aqueous squeezing process is carried out. A continuous method for manufacturing a laminate, in which it is passed through a roller, pulled out, and heated and cured while draining excess impregnated resin liquid under pressure.