CN104669727B - Composite bed lamination and its manufacture method - Google Patents
Composite bed lamination and its manufacture method Download PDFInfo
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- CN104669727B CN104669727B CN201410680088.6A CN201410680088A CN104669727B CN 104669727 B CN104669727 B CN 104669727B CN 201410680088 A CN201410680088 A CN 201410680088A CN 104669727 B CN104669727 B CN 104669727B
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- curable composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
Abstract
The present invention provides a kind of composite bed lamination and its manufacture method.The composite bed lamination (1) of the present invention possesses two surface material layers (2) and core layer (3), and the state that they are clipped in core layer (3) between two surface material layers (2) is laminated.Two surface material layers (2) include the solidfied material of the first heat-curable composition containing free-radical polymerised compound respectively.Core layer (3) includes the solidfied material of the second heat-curable composition containing epoxy resin and free-radical polymerised compound.
Description
Technical field
The present invention relates to a kind of composite bed lamination, and it possesses the core layer comprising non-woven fabrics and comprising the surface material layer weaved cotton cloth.
Background technology
Composite bed lamination is generally configured with the core layer comprising non-woven fabrics and comprising the surface material layer weaved cotton cloth, and they are according to core
The mode that layer is clipped between two surface material layers is laminated.Composite bed lamination is for example by making non-woven fabrics and weaving cotton cloth to be impregnated with heat cure respectively
They are laminated after property composition, and then solidifies heat-curable composition, so as to manufacture.It is combined with heat-curable composition
Epoxy resin, free-radical polymerised compound etc. (reference Japanese patent application publication No. JP 2013-10344).
The content of the invention
The invention problem to be solved
When being combined with epoxy resin in the heat-curable composition used in the manufacture of composite bed lamination, composite laminate
The characteristics such as the heat resistance of plate, toughness improve.But because the heat cure reaction speed of epoxy resin is than free-radical polymerised chemical combination
Thing is slow, therefore using epoxy resin the manufacture efficiency of composite bed lamination can be caused to reduce.
It is that the present invention is in view of the foregoing and made, and it is an object of the present invention to provide a kind of composite bed lamination and its manufacture method,
Although containing epoxy resin in its raw material, the manufacture efficiency reduction due to the epoxy resin can be suppressed.
Means for solving the problems
The composite bed lamination of 1st mode possesses two surface material layers and core layer, and they are clipped in foregoing two with foregoing core layer
State stacking between individual surface material layer,
Both of the aforesaid surface material layer includes consolidating for the first heat-curable composition containing free-radical polymerised compound respectively
Compound,
Foregoing core layer includes the second heat-curable composition containing epoxy resin and free-radical polymerised compound
Solidfied material.
The composite bed lamination of 2nd mode is：In the 1st mode, the aforementioned epoxy in foregoing second heat-curable composition
The mass ratio of resin and foregoing free-radical polymerised compound is in the range of 15: 85~55: 45.
The composite bed lamination of 3rd mode is：In the 1st or the 2nd mode, foregoing second heat-curable composition contains imidazoles
It is curing agent, foregoing imidazoles system curing agent is relative to the ratio of aforementioned epoxy resins in the range of 0.1~1.0 mass %.
The feature of the manufacture method of the composite bed lamination of 4th mode is：Methods described is according to containing being soaked with the second heat cure
Property composition non-woven fabrics be clipped in respectively containing be soaked with two of the first heat-curable composition weave cotton cloth between mode, stacking is foregoing
Weave cotton cloth and non-woven fabrics, make foregoing first heat-curable composition and foregoing second heat-curable composition heat cure, thus manufacture
Composite bed lamination,
First heat-curable composition is contained free-radical polymerised compound, and make the second Thermocurable group
Compound contains epoxy resin and free-radical polymerised compound.
The manufacture method of the composite bed lamination of 5th mode is：In the 4th mode, make foregoing second heat-curable composition
In aforementioned epoxy resins and the mass ratio of foregoing free-radical polymerised compound be set in the range of 15: 85~55: 45.
The manufacture method of the composite bed lamination of 6th mode is：In the 4th or the 5th mode, make foregoing second Thermocurable group
Compound contains imidazoles system curing agent, and foregoing imidazoles system curing agent is set to 0.1~1.0 matter relative to the ratio of aforementioned epoxy resins
In the range of amount %.
The effect of invention
According to the present invention, the second heat-curable composition as the raw material of core layer contains epoxy resin, therefore core
Layer has high glass-transition temperature and high tenacity.It thus ensure that the overall high heat resistance and toughness of composite bed lamination.Enter
And the second heat-curable composition is also containing the fast free-radical polymerised compound of heat cure reaction speed, therefore when the second heat
When solidification compound carries out heat cure, reduce containing the reaction speed caused by epoxy resin and be also suppressed.And then second
The free-radical polymerised chemical combination in free-radical polymerised compound and the first heat-curable composition in heat-curable composition
Reaction heat caused by thing progress heat cure promotes the solidification of the epoxy resin in the second heat-curable composition.Therefore ensure that
The high manufacture efficiency of composite bed lamination.
Brief description of the drawings
Fig. 1 is the summary section for representing the composite bed lamination in one embodiment of the present invention.
Fig. 2 is the skeleton diagram for the manufacturing process for representing foregoing composite bed lamination.
Embodiment
As shown in figure 1, the composite bed lamination 1 of present embodiment possesses two surface material layers 2 and core layer 3.These surface material layers 2
And the state that core layer 3 is clipped in core layer 3 between two surface material layers 2 is laminated.Two surface material layers 2 contain free radical respectively
The solidfied material of first heat-curable composition of polymerizable compound.Core layer 3 contains epoxy resin and radical polymerization
The solidfied material of second heat-curable composition of property compound.
The second heat-curable composition as the raw material of core layer 3 contains epoxy resin, therefore core layer 3 has high glass
Glass transition temperature and high tenacity.It thus ensure that the overall high heat resistance and toughness of composite bed lamination 1.Therefore, when to multiple
When closing plywood 1 and implementing punch process, Drilling operation, the machining such as cutting off processing, the generation of crackle and section it is coarse
Change is suppressed.And then second heat-curable composition also containing the fast free-radical polymerised compound of heat cure reaction speed,
Therefore when the second heat-curable composition carries out heat cure, reduce containing the reaction speed caused by epoxy resin and also pressed down
System.And then the freedom in the second free-radical polymerised compound and the first heat-curable composition in heat-curable composition
Reaction heat caused by the progress heat cure of base polymerizable compound promotes the epoxy resin in the second heat-curable composition
Solidification.It thus ensure that the high manufacture efficiency of the composite bed lamination 1 of present embodiment.
The mass ratio of epoxy resin and free-radical polymerised compound in second heat-curable composition is preferably 15: 85
In the range of~55: 45.Now, the high heat resistance and toughness and high manufacture effect of composite bed lamination 1 are ensure that particularly well
Rate.
It is preferred that the second heat-curable composition contains imidazoles system curing agent, and the imidazoles system in the second heat-curable composition
Curing agent is relative to the ratio of epoxy resin in the range of 0.1~1.0 mass %.Consequently, it is possible to even if imidazoles system curing agent
Ratio than generally it is few, due to manufacture composite bed lamination 1 when the second heat-curable composition in free-radical polymerised compound
And the first free-radical polymerised compound in heat-curable composition carries out reaction heat caused by heat cure, epoxy resin
Heat cure also can be carried out efficiently.And then because the amount of the imidazoles system curing agent in the second heat-curable composition is few, therefore
The gelation of the second heat-curable composition is not easy to carry out under normal temperature.The preservation for thus providing the second heat-curable composition is steady
It is qualitative.
When manufacturing the composite bed lamination 1 of present embodiment, according to containing the non-woven fabrics 6 for being soaked with the second heat-curable composition
It is clipped in respectively containing being soaked with two of the first heat-curable composition modes weaved cotton cloth between 9, stacking is weaved cotton cloth 9 and non-woven fabrics 6, makes the
Heat cure occurs for one heat-curable composition and the second heat-curable composition, thus, it is possible to manufacture composite bed lamination 1.As above institute
State, make to contain free-radical polymerised compound in the first heat-curable composition and make to contain ring in the second heat-curable composition
Oxygen tree fat and free-radical polymerised compound.
Illustrate the composite bed lamination 1 and its manufacture method of present embodiment in further detail below.
First, core layer 3 is illustrated.In present embodiment, core layer 3 includes the Thermocurable of non-woven fabrics 6 and second
The solidfied material of composition.
Non-woven fabrics 6 is made by being selected from least one of materials described below above material, and the material is：Glass fibers
The synthetic resin fibers such as dimension, aramid fibre, polyester fiber, Fypro (nylon)；And paper.The thickness of non-woven fabrics 6
Degree is preferably in the range of 0.20~1.0mm, further preferably in the range of 0.3~0.9mm.By the fiber in non-woven fabrics 6
The epoxides such as the excellent epoxy silane of calorific intensity are preferably comprised in the binding agent being bonded to each other.Relative in non-woven fabrics 6
The mass parts of fiber 100, the amount of binding agent is preferably in the range of 5~25 mass parts.
Core layer 3 both can only include a piece of non-woven fabrics 6, can also include more nonwoven fabric cloth 6.When core layer 3 is comprising more
During piece non-woven fabrics 6, more nonwoven fabric cloth 6 stackeds in the internal layer of core layer 3.
As described above, the second heat-curable composition contains epoxy resin and free-radical polymerised compound.Epoxy resin
With the compound that free-radical polymerised compound is Thermocurable.Second heat-curable composition is except epoxy resin and free radical
Beyond polymerizable compound can also the compound containing Thermocurable, but be preferably free of epoxy resin and free-radical polymerisedization
The mode of the compound of Thermocurable beyond compound.
Epoxy resin in second heat-curable composition, which can contain, is selected from bisphenol A type epoxy resin, bisphenol-f type
Epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene type ring
One in oxygen tree fat, fluorenes type epoxy resin, xanthene type epoxy resin, dicyclopentadiene-type epoxy resin and anthracene type epoxy resin
Kind above resin.It is particularly preferred that epoxy resin contains bisphenol A type epoxy resin.
Second heat-curable composition preferably comprises the curing agent of epoxy resin.Curing agent, which can contain, is selected from amine system
One or more of curing agent, phenol system curing agent, acid anhydrides system curing agent and imidazoles system curing agent compound.It is particularly preferred that
Curing agent contains imidazoles system curing agent.When curing agent contains imidazoles system curing agent, the second heat-curable composition is being heated
When curing rate accelerate and under normal temperature the second heat-curable composition stability improve.Imidazoles system curing agent can contain example
Such as it is selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, trimellitic acid 1- cyano ethyls -2- undecyl imidazoles salt and ring
One or more of epoxide-ifyzidazole adduct compound.
In present embodiment, when manufacturing composite bed lamination 1, the solidification of the epoxy resin in the second heat-curable composition is anti-
Should be due to the free-radical polymerised compound in the second heat-curable composition and the free radical in the first heat-curable composition
The reaction heat of polymerizable compound and be promoted, therefore even if the amount of the curing agent in the second heat-curable composition is few, epoxy
The curing reaction of resin is also promoted.As described above, the second heat-curable composition contains imidazoles system curing agent, the solidification of imidazoles system
Agent is particularly preferred in the range of 0.1~1.0 mass % relative to the ratio of epoxy resin.By making the ratio be 0.1
More than quality %, the heat cure of the second heat-curable composition are particularly efficiently carried out.In addition, by making the ratio be 1.0 matter
Below % is measured, the gelation of the second heat-curable composition at normal temperatures is especially suppressed, thus, the second heat-curable composition
Storage stability become good.More preferably the ratio of the imidazoles system curing agent enters one in the range of 0.2~0.8 mass %
Step is preferably in the range of 0.2~0.6 mass %.
Free-radical polymerised compound in second heat-curable composition, which can contain, is selected from unsaturated polyester (UP) tree
One or more of fat, vinyl ester resin, epoxy vinyl ester resin and free-radical polymerised unsaturated monomer compound.It is special
It is not preferably, free-radical polymerised compound contains epoxy vinyl ester resin and free-radical polymerised unsaturated monomer.
Epoxy vinyl ester resin is by synthesizing epoxy resin and ethene unsaturation unitary acid reaction.
Epoxy resin as the raw material of epoxy vinyl ester resin is not particularly limited, and can contain and be selected from bis-phenol
Type epoxy resin, phenolic resin varnish type epoxy resin, alicyclic epoxy resin, glycidol esters, glycidol amine, hetero ring type
One or more of epoxy resin and brominated epoxy resin resin.As bisphenol-type epoxy resin, bisphenol-A type ring can be enumerated
Oxygen tree fat, bisphenol f type epoxy resin, bisphenol-s epoxy resin etc..As phenolic resin varnish type epoxy resin, phenol can be enumerated
Phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bicyclopentadiene
Phenolic resin varnish type epoxy resin etc..As alicyclic epoxy resin, 3,4- epoxy -6- methylcyclohexylmethyl -3 can be enumerated,
4- epoxy -6- methylcyclohexyls methyl esters, 3,4- epoxycyclohexyl-methyls -3,4- epoxycyclohexanecarboxylate, 1- epoxy ethyls -3,4-
7-oxa-bicyclo[4.1.0 etc..As glycidol esters, o-phthalic acid diglycidyl ester, tetrahydrophthalic acid two can be enumerated
Ethylene oxidic ester, dimer acid glycidyl ester etc..As glycidol amine, four glycidyl group diaminourea hexichol can be enumerated
Methylmethane, triglycidyl group para-aminophenol, N, N- diglycidylanilines etc.., can be with as hetero ring type epoxy resin
Enumerate 1,3- 2-glycidyls -5,5- dimethyl hydantoin, triglycidyl group isocyanuric acid ester etc..As brominated oxygen tree
Fat, tetrabromobisphenol A type epoxy resin, tetrabromobisphenol F types epoxy resin, bromination cresol novolak type epoxy tree can be enumerated
Fat, brominated phenol phenolic resin varnish type epoxy resin etc..In order to improve the anti-flammability of composite bed lamination 1, as epoxy vinyl ester
The epoxy resin of the raw material of resin preferably comprises brominated epoxy resin.
Epoxy resin as the raw material of epoxy vinyl ester resin can be modified by carboxy-containing rubber shaped polymer.That is,
Can be by making a part for the epoxy radicals in epoxy resin be reacted with carboxy-containing rubber shaped polymer to be modified.If ring
Oxygen tree fat is modified by carboxy-containing rubber shaped polymer, then the impact resistance of composite bed lamination 1, punch process, interlayer adaptation
Deng raising.
Carboxylic rubber-like polymer for example makes carboxylic monomer, conjugated diene monomer and appointing beyond them
Meaning monomer copolymerization and obtain.In addition, carboxylic rubber-like polymer can also by make conjugated diene monomer and its beyond
Any monomer copolymerization after into its product import carboxyl and obtain.Carboxyl can be imported into the molecular end of product, side chain
Any position.It is 1~5, more preferably 1.5~3 in every 1 molecular product that the carboxyl number importeding into product, which is preferably,.
Conjugated diene monomer, which can contain, is selected from one or more of butadiene, isoprene and chlorobutadiene compound.Appoint
Meaning monomer, which can contain, is selected from one or more of acrylonitrile, styrene, methyl styrene and halogenated styrenes chemical combination
Thing.
Ratio for the acrylonitrile in whole monomers of carboxylic rubber-like polymer synthesis is preferably in 10~40 matter
In the range of measuring %, further preferably in the range of 15~30 mass %.
Ethene unsaturation monoacid as the raw material of epoxy vinyl ester resin, which can contain, to be selected from (methyl)
One kind in acrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl maleate, butyl maleate and sorbic acid
Above compound.It is particularly preferred that ethene unsaturation monoacid contains (methyl) acrylic acid.
In synthesizing epoxy vinyl ester resin, epoxy resin, carboxylic rubber-like polymer and ethene can be made
Unsaturated monoacid simultaneous reactions.In addition, in synthesizing epoxy vinyl ester resin, epoxy resin and carboxylic can also be made
Rubber-like polymer reaction after, then with ethene unsaturation unitary acid reaction.
The ratio of epoxy resin, carboxylic rubber-like polymer and ethene unsaturation monoacid is not particularly limited,
Preferably with respect to the epoxy radicals of the epoxy resin of 1 equivalent, carboxylic rubber-like polymer and ethene unsaturation monoacid
Total carboxyl is in the range of 0.8~1.1 equivalent, further preferably in the range of 0.9~1.0 equivalent.
Free-radical polymerised unsaturated monomer has the free-radical polymerised unsaturated group of at least one in 1 molecule.Free radical
Polymerism unsaturated monomer, which can contain, is selected from diallyl phthalate, styrene, methyl styrene, benzene halide second
Alkene, (methyl) acrylic acid, methyl methacrylate, EMA, butyl acrylate, divinylbenzene, ethylene glycol two
(methyl) acrylate, propane diols two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three
One or more of (methyl) acrylate and pentaerythrite four (methyl) acrylate compound.It is particularly preferred that freely
Base polymerism unsaturated monomer contains styrene.
It is free-radical polymerised relative to the mass parts of free-radical polymerised compound 100 in the second heat-curable composition
The amount of unsaturated monomer is preferably in the range of 25~45 mass parts.When the amount of free-radical polymerised unsaturated monomer is in 25 mass
During part above, impregnation of second heat-curable composition in non-woven fabrics 6 uprises.In addition, when the amount is below 45 mass parts
When, the dimensional stability and heat resistance of composite bed lamination 1 uprise.The amount of free-radical polymerised unsaturated monomer further preferably exists
In the range of 25~40 mass parts.
Second heat-curable composition preferably comprises radical polymerization initiator.Radical polymerization initiator can contain suitable
When organic peroxide.The organic peroxide, which can contain, is selected from methyl-ethyl-ketone peroxide, methyl-isobutyl
The ketone peroxide class such as ketone peroxide, Cyclohexanone peroxides；The acyl of benzoyl peroxide, isobutyl peroxide etc. two
Base peroxide；The hydroperoxide types such as cumene hydroperoxide, tert-butyl hydroperoxide；Dicumyl peroxide, two-
The dialkyl peroxide class such as tert-butyl ester peroxide；1,1- bis--tert-butyl ester peroxidating -3,3,5- trimethylcyclohexanones, 2,2-
Ketal peroxide class, peroxidized t-butyl perbenzoate, the tertiary fourths of peroxidating -2 ethyl hexanoic acid such as two-(tert-butyl ester peroxidating)-butane
The alkyl peroxyesters class such as ester；And double (4- tert-butylcyclohexyls) peroxy dicarbonates, peroxidating isobutyl group t-butyl carbonate
Etc. one or more of peroxycarbonates class compound.
Relative to the mass parts of free-radical polymerised compound 100 in the second heat-curable composition, radical polymerization is drawn
Send out agent amount preferably in the range of 0.5~5.0 mass parts, further preferably 0.9~2.0 mass parts ratio scope
It is interior.
As described above, the mass ratio of the epoxy resin and free-radical polymerised compound in the second heat-curable composition is excellent
It is selected in the range of 15: 85~55: 45.Now, ensure that particularly well composite bed lamination 1 high heat resistance and toughness, with
And high manufacture efficiency.The mass ratio is more preferably in the range of 35: 65~55: 45, further preferably 45: 55~55: 45
In the range of.
Second heat-curable composition preferably comprises inorganic filler.Inorganic filler can contain be selected from talcum, silica,
One or more of carbon black, mica, aluminium hydroxide, aluminum oxide, clay, titanium oxide and barium titanate material.Relative to the second thermosetting
The mass parts of total amount 100 of epoxy resin and free-radical polymerised compound in the property changed composition, the amount of inorganic filler are preferred
In the range of 100~250 mass parts, further preferably in the range of 150~200 mass parts.
Second heat-curable composition can be as needed and then containing curing catalysts, solvent, viscosity reductant, coupling agent etc.
Additive.
But the second heat-curable composition is preferably free of solvent.That is, the second heat-curable composition is preferably so-called
The composition of no-solvent type.Now, make the second heat-curable composition containing be dipped into after non-woven fabrics 6 solidified during not
Solvent must be removed from the second heat-curable composition.It is therefore prevented that the environmental degradation caused by solvent volatilization.Further, since not
The process for removing solvent is needed, therefore the manufacture efficiency of composite bed lamination 1 improves, and is also easy to carry out composite bed using series-operation
The manufacture of lamination 1.
Second heat-curable composition is the composition of no-solvent type, therefore the second heat-curable composition preferably comprises often
The lower free-radical polymerised unsaturated monomer for liquid of temperature.Now, by making the radical polymerization in the second heat-curable composition
Composition beyond conjunction property unsaturated monomer is dissolved or dispersed in the free-radical polymerised unsaturated monomer of liquid, can be easily
Obtain the second heat-curable composition of liquid or pulp-like.
Second heat-curable composition is modulated by appropriate method.For example, can be by by the second Thermocurable group
The composition of compound disperser (デ ィ ス パ mono-), ball mill, roller etc. mix, so as to modulate the second heat-curable composition.
Then surface material layer 2 is illustrated.In present embodiment, surface material layer 2 contain weave cotton cloth 9 and first heat-curable composition consolidate
Compound.
Weave cotton cloth 9 can select from such as glass cloth and synthetic resin cloth.Synthetic resin cloth can be by such as aromatics polyamides
The synthetic resin fibers such as amine fiber, polyester fiber, Fypro (nylon) make.Weave cotton cloth 9 thickness preferably at 50~500 μm
In the range of.
First heat-curable composition contains free-radical polymerised compound.Free-radical polymerised compound is Thermocurable
Compound.First heat-curable composition can also the chemical combination containing Thermocurable in addition to free-radical polymerised compound
Thing.However, it is preferred to the free-radical polymerised compound in the second heat-curable composition relative to the change of whole Thermocurables
The quality ratio of compound is compared, and the free-radical polymerised compound in the first heat-curable composition is relative to whole Thermocurables
Compound quality ratio it is higher.It is particularly preferred that the first heat-curable composition is free of free-radical polymerised compound
The compound of Thermocurable in addition.
Free-radical polymerised compound in first heat-curable composition, which can contain, is selected from unsaturated polyester (UP) tree
One or more of fat, vinyl ester resin, epoxy vinyl ester resin and free-radical polymerised unsaturated monomer compound.
It is particularly preferred that free-radical polymerised compound contains epoxy vinyl ester resin and free-radical polymerised unsaturated monomer.
It is identical when the details of epoxy vinyl ester resin and free-radical polymerised unsaturated monomer is with the second heat-curable composition.
It is free-radical polymerised relative to the mass parts of free-radical polymerised compound 100 in the first heat-curable composition
The amount of unsaturated monomer is preferably in the range of 25~45 mass parts.When the amount of free-radical polymerised unsaturated monomer is in 25 mass
During part above, the first heat-curable composition uprises in the impregnation weaved cotton cloth in 9.In addition, when the amount is below 45 mass parts,
The dimensional stability and heat resistance of composite bed lamination 1 uprise.The amount of free-radical polymerised unsaturated monomer is further preferably 25
In the range of~40 mass parts.
First heat-curable composition preferably comprises radical polymerization initiator.The details of radical polymerization initiator and the
It is identical during two heat-curable compositions.Relative to the mass of free-radical polymerised compound 100 in the first heat-curable composition
Part, the amount of radical polymerization initiator is preferably in the range of 0.5~5.0 mass parts, further preferably in 0.9~2.0 mass
In the range of the ratio of part.
First heat-curable composition preferably comprises inorganic filler.The details of inorganic filler and the second heat-curable composition
Shi Xiangtong.It is inorganic to fill out relative to the mass parts of total amount 100 of the free-radical polymerised compound in the first heat-curable composition
The amount of material is preferably in the range of 100~250 mass parts, further preferably in the range of 150~200 mass parts.
First heat-curable composition can be as needed and then containing curing catalysts, solvent, viscosity reductant, coupling agent etc.
Additive.
But the first heat-curable composition is preferably free of solvent.That is, the first heat-curable composition is preferably so-called
The composition of no-solvent type.Now, make the first heat-curable composition containing be dipped into weave cotton cloth solidified after 9 during need not
Solvent is removed from the first heat-curable composition.It is therefore prevented that the environmental degradation caused by solvent volatilization.Further, since it is not required to
The process for removing solvent, therefore the manufacture efficiency of composite bed lamination 1 improves, and is also easy to carry out composite laminate using series-operation
The manufacture of plate 1.
First heat-curable composition is the composition of no-solvent type, therefore the first heat-curable composition preferably comprises often
The lower free-radical polymerised unsaturated monomer for liquid of temperature.Now, by making the radical polymerization in the first heat-curable composition
Composition beyond conjunction property unsaturated monomer is dissolved or dispersed in the free-radical polymerised unsaturated monomer of liquid, can be easily
Obtain the first heat-curable composition of liquid or pulp-like.
First heat-curable composition is modulated by appropriate method.For example, can be by by the first Thermocurable group
The composition of compound disperser (デ ィ ス パ mono-), ball mill, roller etc. mix, so as to modulate the first heat-curable composition.
Composite bed lamination 1 can also possess one or two conductor layer 4.Conductor layer 4 is by the metal foil such as copper foil, nickel foil
Formed.Conductor layer 4 overlap it is in surface material layer 2, with the face of 3 opposite side of core layer.Possess one in composite bed lamination 1 to lead
When 4, two surface material layer 2 of body layer and a core layer 3, composite bed lamination 1, which has, is sequentially laminated with conductor layer 4, surface material layer 2, core
The structure of material layer 3 and surface material layer 2.Possess two conductor layers, 4, two surface material layers 2 and a core layer 3 in composite bed lamination 1
When, composite bed lamination 1 has the structure for being sequentially laminated with conductor layer 4, surface material layer 2, core layer 3, surface material layer 2 and conductor layer 4.
The thickness of conductor layer 4 is not particularly limited, in the range of such as 0.012~0.07mm.
The composite bed lamination 1 of present embodiment manufactures as described above by following manner：According to containing being soaked with the second heat cure
Property composition non-woven fabrics 6 be clipped in respectively containing two of the first heat-curable composition modes weaved cotton cloth between 9 are soaked with, stacking is knitted
Cloth 9 and non-woven fabrics 6, make the first heat-curable composition and the second heat-curable composition heat cure, so as to manufacture.
Reference picture 2 illustrates a concrete mode of the manufacture method of composite bed lamination 1.It is explained, is manufactured in this method
Possess two conductor layers, 4, two surface material layers 2 and the composite bed lamination 1 of a core layer 3.
In this method, the non-woven fabrics 6 of side continuous conveying strip, the metal foil 12 of weave cotton cloth 9 and the strip of strip, make non-woven fabrics
6 the second heat-curable compositions of impregnation and make 9 the first heat-curable compositions of impregnation of weaving cotton cloth, so by non-woven fabrics 6, weave cotton cloth 9 and
Metal foil 12 heats after being laminated, so that the second heat-curable composition and the first heat-curable composition heat cure.Thus, make
Composite bed lamination 1 is made.The composite bed lamination 1 of acquisition is cut into defined size as needed.Thus, manufactured with series-operation
Composite bed lamination 1.
More specifically manufacture method is illustrated.
Prepare the volume 5 of the non-woven fabrics 6 of strip, extract non-woven fabrics 6 from the volume 5 and conveyed.On the conveying way of non-woven fabrics 6
Feedway 7 is configured on footpath, is supplied the second heat-curable composition to non-woven fabrics 6 by the feedway 7.Thus, in nothing
Spin in cloth 6 and be impregnated with the second heat-curing resin.Feedway 7 in Fig. 2 is roll coater, but feedway 7 is not particularly limited,
As long as it is configured to by supplying the second heat-curing resin to non-woven fabrics 6 so that non-woven fabrics 6 is impregnated with the second heat-curing resin
Form.
It is explained, in this method, a nonwoven is only used in order to form the core layer 3 for including a non-woven fabrics 6
The volume 5 of cloth 6, but when forming the core layer 3 comprising multiple non-woven fabrics 6, correspondingly using the volume of multiple non-woven fabrics 6.
In addition, prepare two strips weave cotton cloth 9 volume 8, extract to weave cotton cloth from each volume 8 and 9 and conveyed.Respectively weaving cotton cloth 9
Feedway 10 is configured on transport way, first heat-curable composition is applied to by the feedway 10 and weaves cotton cloth 9.Fig. 2
In feedway 10 be roll coater, feedway 10 is not particularly limited, as long as being configured to 9 the first heat cures of supply of weaving cotton cloth
Property resin is so that 9 the first heat-curing resins of impregnation of weaving cotton cloth.
In addition, preparing the volume 11 of the metal foil 12 of two strips, metal foil 12 is conveyed by each volume 11.
Side conveying containing be soaked with the non-woven fabrics 6 of above-mentioned second heat-curable composition, containing being soaked with the first heat-curable composition
Two weave cotton cloth 9 and two metal foils 12, while entering according to the order of metal foil 12,9, non-woven fabrics 6 of weaving cotton cloth, 9, metal foil 12 of weaving cotton cloth
Row stacking, so as to make sandwich 16, the sandwich 16 is imported between two volumes 13,13.Thus sandwich 16 is carried out
Thickness adjustment and the adjustment of the amount of resin in sandwich 16.
The sandwich 16 is continuously conveyed in heating furnace 14, thus heated.Thus, the first Thermocurable group is made
Compound and the second heat-curable composition heat cure.Heating-up temperature and heat time can according to the first heat-curable composition and
Composition of second heat-curable composition etc. is suitably set, such as model of the heating-up temperature (maximum temperature reached) at 140~190 DEG C
The interior, heat time is enclosed in the range of 40~80 minutes.
The composite bed lamination 1 pulled out from heating furnace 14 is cut into defined size with cutting machine 15.Thus, provided
The composite bed lamination 1 of size.Solidify afterwards (after cure) can also be carried out by further heating the composite bed lamination 1.
If manufacturing composite bed lamination 1 with this method, although the second heat-curable composition of the raw material as core layer 3
Containing epoxy resin, but free-radical polymerised compound also fast containing reaction speed, therefore the second heat-curable composition enters
During row heat cure, reduce containing the reaction speed caused by epoxy resin and be also suppressed.And then second heat-curable composition
In free-radical polymerised compound and the first heat-curable composition in free-radical polymerised compound carry out heat cure when
Caused reaction heat promotes the solidification of the epoxy resin in the second heat-curable composition.It thus ensure that composite bed lamination 1
High manufacture efficiency.Therefore expeditiously manufacture has the composite bed lamination 1 of high tenacity and high glass-transition temperature.In addition,
If using above-mentioned such continuous engineering method, composite bed lamination 1 can be extremely efficiently manufactured.In addition, the drop of manufacture efficiency
It is low to be suppressed, therefore manufacturing equipment when can also will use only free-radical polymerised compound as Thermocurable composition is straight
Connect the manufacture of the composite bed lamination 1 for present embodiment.
In addition, even if the second heat-curable composition is not easy to gelation containing epoxy resin as described above, therefore manufacture
During composite bed lamination 1, the character and viscosity of the second heat-curable composition not malleable.Therefore, can stably manufacture compound
Plywood 1.
It is explained, the manufacture method of composite bed lamination 1 is not limited to above-mentioned continuous engineering method.For example, it is also possible to according to making to contain
Be soaked with the second heat-curable composition non-woven fabrics be clipped in respectively containing be soaked with two of the first heat-curable composition weave cotton cloth between
Mode make sandwich, to the sandwich carry out hot pressing, thus manufacture composite bed lamination.
Embodiment
[making of composite bed lamination]
Coordinate the composition shown in aftermentioned table, modulate the second heat-curable composition of no-solvent type.Make second thermosetting
The property changed composition (thickness 0.6mm glass non-woven fabric, Vilene Company.Ltd. Co. Ltd. systems, glues containing non-woven fabrics is dipped into
Knot agent contains epoxy silane, and the ratio of binding agent is 5~25 mass parts relative to the mass parts of glass fibre 100).
In addition, coordinating the composition shown in table described later, the first heat-curable composition of no-solvent type is modulated.Make this
One heat-curable composition, which contains, to be dipped into weave cotton cloth (Co. Ltd. system, product number 7628 are spun in thickness 0.18mm glass cloth, day east).
Then, it is clipped in respectively according to containing the non-woven fabrics for being soaked with the second heat-curable composition containing being soaked with the first Thermocurable group
Two of compound weave cotton cloth between mode will weave cotton cloth and non-woven fabrics stacking, and then both sides outermost layer configure copper foil, thus obtain
Obtain sandwich.
The sandwich is heated according to following conditions.
Condition 1：180 DEG C of maximum heating temperature, 40 minutes heat times.
Condition 2：180 DEG C of maximum heating temperature, 60 minutes heat times.
Condition 3：180 DEG C of maximum heating temperature, 80 minutes heat times.
[evaluation of composite bed lamination]
(1) evaluation of manufacture efficiency
Etching process is implemented to the composite bed lamination obtained under the conditions of each in condition 1~3, so as to remove the copper of both sides
Paper tinsel.Then, based on composite bed lamination, caused weight change confirms the curing degree of the compound plywood afterwards before heating.
As a result in, by situation about being fully cured under the either case of condition 1~3 be evaluated as " A ", by condition 2,3 times completely
Solidification but situation about not being fully cured under condition 1 are evaluated as " B ", will be fully cured under condition 3 but incomplete under condition 1,2
The situation of solidification is evaluated as " C ".The evaluation result is shown in aftermentioned form.
Be explained, in the following evaluation test, manufacture efficiency when being evaluated as A by the compound of 1 time acquisition of condition
Plywood is for experiment；When being evaluated as B by the composite bed lamination of 2 times acquisitions of condition for experiment；When being evaluated as C by condition
The composite bed lamination of 3 times acquisitions is for experiment.
(2) glass transition temperature determines
After by implementing the copper foil that etching process removes both sides to composite bed lamination, composite laminate is determined by TMA methods
The glass transition temperature of plate.The evaluation result is shown in aftermentioned form.
(3) bending strength test
The bending strength of composite bed lamination is determined based on IPC-TM650.The evaluation result is shown in aftermentioned form.
(4) drill processability
4 composite bed laminations are overlapping, Drilling operation is implemented with diameter 0.4mm bore cutter to these composite bed laminations.
The inner face in the hole being consequently formed is observed, the smooth situation of the inner face is evaluated as " A ", the inner face is locally attached with due to cutting
And the situation of caused powder is evaluated as " B ", is entirely attached with the inner face due to cutting and the evaluation of the situation of caused powder
For " C ".The evaluation result is shown in aftermentioned form.
(5) storage stability is evaluated
At a temperature of second heat-curable composition is placed on into 30 DEG C, the second heat-curable composition gelation institute is determined
The time needed.As a result, the situation by also non-gelation in 3 days is evaluated as " A ", evaluates the situation of 1~3 day inner gel
For " B ", " C " will be evaluated as, by the gelation before 12 hours more than 12 hours, less than the situations of 24 hours inner gels
Situation is evaluated as " D ".The evaluation result is shown in aftermentioned form.
Table 1
Table 2
Claims (2)
1. a kind of composite bed lamination, it possesses two surface material layers and core layer, and they are clipped in described two tables with the core layer
State stacking between material layer,
Described two surface material layers include the solidfied material of the first heat-curable composition containing free-radical polymerised compound respectively,
First heat-curable composition is free of the compound of the Thermocurable beyond free-radical polymerised compound, the core layer
Include the solidification of the second heat-curable composition containing epoxy resin, free-radical polymerised compound and imidazoles system curing agent
Thing,
And the quality of the epoxy resin and the free-radical polymerised compound in second heat-curable composition
Than in the range of 15: 85~55: 45, imidazoles system curing agent is relative to the ratio of the epoxy resin in 0.1~1.0 matter
In the range of amount %.
2. a kind of manufacture method of composite bed lamination, it is characterised in that methods described is：According to containing being soaked with the second Thermocurable group
The non-woven fabrics of compound be clipped in respectively containing be soaked with two of the first heat-curable composition weave cotton cloth between mode, stacking is described two
Weave cotton cloth and the non-woven fabrics, and make first heat-curable composition and second heat-curable composition that thermosetting occur
Change, thus manufacture composite bed lamination,
Make to contain free-radical polymerised compound in first heat-curable composition, and combine first Thermocurable
Thing is free of the compound of the Thermocurable beyond free-radical polymerised compound, contains ring in second heat-curable composition
Oxygen tree fat, free-radical polymerised compound and imidazoles system curing agent, and the ring in second heat-curable composition
The mass ratio of oxygen tree fat and the free-radical polymerised compound is in the range of 15: 85~55: 45, the imidazoles system curing agent
Relative to the ratio of the epoxy resin in the range of 0.1~1.0 mass %.
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|---|---|---|---|---|
| CN1608100A (en) * | 2001-08-31 | 2005-04-20 | 住友电木株式会社 | Resin composition, prepreg, laminate, and semiconductor package |
| CN102695612A (en) * | 2009-11-25 | 2012-09-26 | 松下电器产业株式会社 | Laminate plate, use therefor, and production method thereof |
| CN102958984A (en) * | 2010-07-01 | 2013-03-06 | 住友电木株式会社 | Prepreg, wiring board, and semiconductor device |
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| US4954304A (en) * | 1988-04-04 | 1990-09-04 | Dainippon Ink And Chemical, Inc. | Process for producing prepreg and laminated sheet |
| JPH08118542A (en) * | 1994-10-28 | 1996-05-14 | Matsushita Electric Works Ltd | Manufacture of copper clad laminated sheet |
| JP4707981B2 (en) * | 2004-08-06 | 2011-06-22 | 昭和電工株式会社 | Manufacturing method of molded product |
| JP4964722B2 (en) * | 2007-09-21 | 2012-07-04 | パナソニック株式会社 | Continuously produced thermosetting resin composition for copper-clad laminate, copper-clad laminate production method, and copper-clad laminate |
| WO2012164997A1 (en) * | 2011-05-30 | 2012-12-06 | パナソニック株式会社 | Laminate sheet, application therefor, and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1608100A (en) * | 2001-08-31 | 2005-04-20 | 住友电木株式会社 | Resin composition, prepreg, laminate, and semiconductor package |
| CN102695612A (en) * | 2009-11-25 | 2012-09-26 | 松下电器产业株式会社 | Laminate plate, use therefor, and production method thereof |
| CN102958984A (en) * | 2010-07-01 | 2013-03-06 | 住友电木株式会社 | Prepreg, wiring board, and semiconductor device |
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