CN101085865B - Substrate for heat bonding and method for producing layered product by the same - Google Patents
Substrate for heat bonding and method for producing layered product by the same Download PDFInfo
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- CN101085865B CN101085865B CN2007101270313A CN200710127031A CN101085865B CN 101085865 B CN101085865 B CN 101085865B CN 2007101270313 A CN2007101270313 A CN 2007101270313A CN 200710127031 A CN200710127031 A CN 200710127031A CN 101085865 B CN101085865 B CN 101085865B
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- Laminated Bodies (AREA)
Abstract
A layered product which is a molded object comprising a thermoset resin layer, a thermoplastic resin layer, and reinforcing fibers comprising many continuous filaments, wherein the thremoset resin layer has been united with the thermoplastic resin layer at the interface between these layers, the resin of the thermoset resin layer and the resin of the thermoplastic resin layer each having an irregular surface shape at the interface, and a group of filaments among the reinforcing fibers are in contact with at least the resin of the thermoset resin layer and the other group of filaments among the reinforcing fibers are in contact with at least the resin of the thermoplastic resin layer, that side of the thermoplastic resin layer which is opposite to the interface being a surface of the molded object.
Description
Technical field
The present invention relates to a kind of laminate that is made up of the reinforcing fibre resin, reinforcing fibre resin wherein is to be able to strengthen through the reinforcing fibre group of being made up of a large amount of continuous fibers.The invention still further relates to the method for making this laminate.The invention further relates to a kind of can with other structure unit, the structure unit mortise all-in-one-piece laminate that especially constitutes by thermoplastic resin.The invention still further relates to a kind of can being combined into one with other structure unit and form the laminate of moulding article, these moulding article are easy to decompose, and after the moulding article went out of use, its each parts can utilize separately again.
The invention still further relates to a kind of electromagnetic-shielding molded article, it is combined into one by a kind of laminate that is made up of the reinforcing fibre resin and other structure units and forms, and reinforcing fibre resin wherein is to be able to strengthen through the reinforcing fibre group of being made up of a large amount of continuous fibers.
Incorporate moulding article are preferably used as the parts or the housing of electrical equipment or electronics, office auto-plant, household electrical appliance or Medical Instruments; Automotive component; The ROV parts; Building element or the like.
Background technology
The moulding article that are made up of the reinforcing fibre resin are widely used as various parts and structure parts, and wherein the reinforcing fibre resin is to be able to strengthen through the reinforcing fibre group of being made up of a large amount of continuous fibers (FRPs).Utilizing thermosetting resin is through such as the prepreg that is marked with thermosetting resin is carried out dull and stereotyped pressing mold for the moulding article of matrix, and carries out that resin transfer moulding forming methods such as (RTM) makes.
Yet the FRP that is made up of thermosetting resin is not suitable for parts or structure through single moulding process manufacturing complicated shape.Therefore, the parts of complicated shape or structure are through making a plurality of parts from FRP, and these a plurality of parts are combined into one and make.
Integral method comprises and utilizes bolt, rivet, screw etc. and bonded mechanical bond method and the combining method that utilizes tackiness agent.The problem that the mechanical bond method exists for example has: because this step of preprocess bonded block is essential, therefore make production cost be difficult to reduce; Consider that from the angle of outward appearance this application is restricted.Adopt the existing problem of combining method of tackiness agent to be: owing to comprise that preparation tackiness agent and the integrating step of using tackiness agent are essential, thereby cause production cost to be difficult to reduce; And bonding strength does not reach gratifying degree of dependence yet.
The parts that thermoplastic resin is formed combine the all-in-one-piece method with the formed parts of the FRP that is made up of thermosetting resin can be referring to JP10-138354A.This method comprises first step, promptly at the surperficial laminated thermoplastic resin film of prepreg, thereby forms first laminate, and prepreg wherein is made up of thomel and the thermosetting resin strengthened; Second step; Promptly do not cause under the condition of membrane flow making thermosetting resin cured; First laminate that obtains is heated and pressurizes, thereby form second laminate, this second laminate is strengthened thermosetting resin by the thomel that is bonded with thermoplastic resin film on it and is constituted; And third step, promptly adopt thermoplastic resin on the surface of the thermoplastic resin film of second laminate that places mould, to carry out injection molding, so that injection molding thermoplastic parts (core component) combines with second laminate (surface elements).According to this method, combine because core component that thermoplastic resin constitutes and surface elements are thermoplastic resin films through surface elements, so the bonding strength of junction does not have problems.
Yet, still have a problem, promptly the bonding strength of junction is big not enough between thermosetting resin and surface elements thermoplastic resin formed.Reason is that the latter's junction is to be formed by the combination between thermosetting resin and the thermoplastic resin, is promptly formed by the combination between the different substances.
One object of the present invention is to provide a kind of laminate, and it can reduce traditionally the worry to the bonding strength between the different substances.
Reinforcing fibre resin (FRPs) is widely used as forming the material of various products.On the other hand, need make these products carry out loss of weight.At first, along with portable electric appts, especially notebook computer, Cell phone and portable data assistance are used more and more, and people are just increasing to demand slim, light-end products on the market.Given this, the housing and the internal part that require to constitute product will reduce on thickness and weight, and on rigidity, also need strengthen.
For satisfying above-mentioned requirements, people use magnesiumalloy.For strengthening the inflexible requirement, people study the application of high rigid metallic material such as duraluminum.Yet, still be difficult to produce complex-shaped product easily from these metallic substance with high yield.
JP2001-298277A provides a kind of housing that utilizes epoxypaint to make metal forming article and (injection molded ribs) the integrated combination of injection molding rib and make.JP06-029684A provides a kind of electromagnetic shielding shell that makes tinsel and shaping synthetic resin body carry out integrated combination and make.Yet because proportion of metal material is big, although can satisfy the little and high requirement of rigidity of thickness, these housings still can not satisfy the light-weight requirement.
Consider from the cycling and reutilization aspect of product, be difficult to product with the integrated be combined into of processing by various materials of each parts and separate and classify.The result has generated the waste that is made up of various materials, thereby has caused such problem: these parts are difficult to utilized again, and cost recovery increases.
Consider the problems referred to above of prior art, the object of the present invention is to provide a kind of laminate, a kind of method of making said product also is provided, wherein this laminate can combine so that good binding intensity and other structure unit are integrated easily.Adopt integrated molding that laminate obtains not only satisfactory mechanical property, in light weight, have a capability of electromagnetic shielding; And flexible design; Utilization more capable of circulation; Be suitable for housing as electrical equipment or electronics or portable data assistance, or as the structure unit of transportation equipment such as automobile or ROV.
Summary of the invention
First embodiment of laminate of the present invention:
Laminate of the present invention is to comprise thermoset resin layer, thermoplastic resin and the moulding article of the reinforcing fibre group be made up of continuous fibers; Wherein, Thermoset resin layer and thermoplastic resin are combined into one its interlayer at the interface, the bonded mode be make said thermoset resin layer resin and said thermoplastic resin resin become at the interface rough; Paranema in the said reinforcing fibre group keeps in touch with the resin of said thermoset resin layer at least, and all the other secondary silks contact with the resin of said thermoplastic resin at least in the reinforcing fibre group; The surface of the said thermoplastic resin opposite with said interface is positioned on the surface of said moulding article.
In the laminate of the present invention, preferred a large amount of continuous fibers are arranged with same direction, and the interface between preferred thermoset resin layer and the thermoplastic resin is present among the reinforcing fibre group.
In laminate of the present invention, the glass transition temperature that is preferably formed the resin of thermoset resin layer is 60 ℃ or higher.
In laminate of the present invention, in the preferred thermoplastic resin layer, it is 10 μ m or bigger that there is the maximum ga(u)ge in zone in continuous fibers.Preferred maximum ga(u)ge is 1000 μ m or littler.
In laminate of the present invention, the surface area of preferred thermoplastic resin layer accounts for the 0.1-50% of the surface area of laminate.
In laminate of the present invention, can on laminate is positioned at the surface of the opposite side opposite with thermoplastic resin place side, form the layer that constitutes with the reinforcing fibre group of forming by said thermosetting resin, said thermoplastic resin and a large amount of continuous fibers have same structure layer.
In laminate of the present invention, the test sample of preferred laminate bonding strength (hereinafter based on the ISO4587 definition) at room temperature is 6MPa or higher.
In laminate of the present invention, the continuous fibers that preferably constitute the reinforcing fibre group are thomels.
In laminate of the present invention, preferred thermosetting resin is the resin that mainly is made up of epoxy resin.
In laminate of the present invention, preferred thermoplastic resin is at least a following resin that is selected from: polyamide resin, vibrin, polycarbonate resin, styron, EVA resin, urethane resin, vinyl resin, polyolefin resin and PPS resin.
Second embodiment of laminate of the present invention:
Laminate of the present invention comprises the film that compositions of thermosetting resin and thermoplastic resin composition constitute; Wherein, Compositions of thermosetting resin contains the reinforcing fibre group of being made up of a large amount of continuous fibers that are arranged in the thermoset substrate resin; The film that said thermoplastic resin composition constitutes forms at least a portion surface of said compositions of thermosetting resin; Wherein, it is 10MPa 40 ℃ the time that hereinafter defined laminate and other moulding article carry out the normal bonding strength of bonded through this film, in the time of 140 ℃ less than 10MPa.
In the laminate of the present invention, the mean thickness of the film that preferably is made up of the thermoplastic resin composition is 0.1-1000 μ m.
In the laminate of the present invention, a large amount of continuous fibers that preferably constitute the reinforcing fibre group are thomel.
In laminate of the present invention, preferred thermosetting resin is the resin that mainly is made up of epoxy resin.
In laminate of the present invention, preferred thermoplastic resin is at least a following resin that is selected from: polyamide resin, vibrin, polycarbonate resin, styron, EVA resin, urethane resin, vinyl resin, polyolefin resin and PPS resin.
The present invention makes the method for laminate:
The method that the present invention makes laminate comprises the following steps: on the surface of the prepreg that is obtained by the reinforcing fibre that injects uncured thermosetting resin, to place the base material that is used for thermal bond that is made up of thermoplastic resin, and wherein reinforcing fibre is made up of a large amount of continuous fibers; In the curing reaction of thermosetting resin or in the warm before the curing reaction, the base material thermoplastic resin that will be used for thermal bond injects reinforcing fibre then.
The method of manufacturing laminate of the present invention, preferably when thermoplastic resin was injected into the reinforcing fibre group, exert pressure was 0.1MPa or higher.
Integrated molding of the present invention:
In integrated molding of the present invention, first parts that constitute by laminate of the present invention and mutually combine through the thermoplastic resin in first parts by second parts that other structure units constitute.
In integrated molding of the present invention, preferred second parts are to be selected from following at least a parts: the parts that laminate of the present invention is formed, the parts of being made up of the thermoplastic resin composition and the parts of being made up of metallic substance.
The specific examples of integrated molding of the present invention comprises the parts of electrical equipment and electronics, business automation equipment, household electrical appliance and medical facilities; And the parts of automobile, cart, bike, ROV and building, element and panel.
Make the method for integrated molding of the present invention:
The method of making integrated molding of the present invention comprises the following steps: to combine through at least a combining method with first parts that are made up of laminate with by second parts that other structure unit constitutes, and said combining method is selected from: thermo-welding, Vibration Welding, ultra-sonic welded, laser welding, inject moulding and ejection formation.
The base material that is used for thermal bond of the present invention:
The base material that is used for thermal bond of the present invention is to be used to base material that identical and/or inhomogeneous bonding parts are combined; Wherein, The bonding strength of the test sample of the laminate that defines according to ISO4587 in the specification sheets is 5.0MPa or bigger in the time of 100 ℃, in the time of 200 ℃, is 1.0MPa or littler.
The preferred bonding strength of base material that the present invention is used for thermal bond is St (MPa) in the time of t ℃, at (t+30).℃ the time be S
(t+30)(MPa), satisfy relational expression St>=3X S
(t+30)The scope of temperature t between 100 ℃ to 200 ℃.
The present invention is used for the base material of thermal bond and preferably is made up of the amide copolymer resin compsn.Preferably, the amide copolymer resin compsn comprises terpolyamide 6/66/610 as one of composition.
Be used for the base material of thermal bond in the present invention, the form that preferred the present invention is used for the base material of thermal bond is that unit weight is 1-100g/m
2Nonwoven fabric or film.
The base material that the present invention is used for thermal bond can preferably be used as the thermal bond base material of making laminate of the present invention.
Electromagnetic-shielding molded article of the present invention:
Electromagnetic-shielding molded article of the present invention are to be combined into one through first structure unit that will be made up of resin combination with by second structure unit that the thermoplastic resin composition constitutes to obtain; Wherein constitute in the resin combination of first structure unit and be arranged with the conductive fibers bundle of forming by a large amount of continuous fibers; The capability of electromagnetic shielding of said first structure unit is according to the KEC method, and measured value is 40dB or higher under the 1GHz frequency.
In the electromagnetic-shielding molded article of the present invention, first structure unit laminate preferably of the present invention, wherein, a large amount of continuous fibers that constitute the reinforcing fibre group are thomel.
In electromagnetic-shielding molded article of the present invention, be preferably based on ASTM-D790, be 8GPa or higher with the modulus in flexure of the first measured structure unit of following test sample.
The preferred mean thickness of first structure unit of electromagnetic-shielding molded article of the present invention is 1.6mm or littler.
In electromagnetic-shielding molded article of the present invention, when observing the moulding article from the outside, preferably can see pattern based on the continuous fibers arrangement mode.
In the electromagnetic-shielding molded article of the present invention, with the purposes of moulding article accordingly, preferably select thermosetting resin or thermoplastic resin resin combination as first structure unit.
In the electromagnetic-shielding molded article of the present invention, the thermoplastic resin composition of second structure unit comprises discontinuous thomel, and wherein the weight average fiber length Lw of thomel is 0.4mm or longer, and weight average fiber length is 1.3-2.0 with the ratio Lw/Ln of number average fiber length.
The specific examples of electromagnetic-shielding molded article of the present invention comprises parts, element and the housing of electrical equipment and electronics, business automation equipment, household electrical appliance and medical facilities.And, a kind of electromagnetic-shielding molded article are arranged, wherein first structure unit is placed at least a portion of any top end face of housing, and second structure unit is placed on arbitrary or a plurality of parts of the framework, projection, rib, pivot and the slideway that comprise housing.
Make the method for the electromagnetic-shielding molded article of the present invention:
The method of making the electromagnetic-shielding molded article of the present invention comprises the first step, is about to embedded in the mould by first structure unit of moulding in advance; In second step, promptly adopt the thermoplastic resin composition to carry out injection molding and on first structure unit, form second structure unit, thereby first structure unit and second structure unit are combined into one.
The method of making the electromagnetic-shielding molded article of the present invention comprises that first structure unit and injection molding in advance second structure unit with moulding in advance are combined into one through ultra-sonic welded.
Description of drawings
Fig. 1 shows the typical skeleton view of a kind of mode of laminate of the present invention.
Fig. 2 shows the local amplification sectional view of Fig. 1 laminate surface layer part.
Fig. 3 is the typical section figure that carries out testing for the first time resulting test sample for the laminate structure of the present invention of checking embodiment.
Fig. 4 is the typical section figure that carries out testing for the first time resulting test sample for the laminate structure of checking comparing embodiment.
Fig. 5 is the typical section figure that carries out testing for the second time resulting test sample for the laminate structure of the present invention of checking embodiment.
Fig. 6 is the typical section figure that carries out testing for the second time resulting test sample for the laminate structure of checking comparing embodiment.
Fig. 7 is a skeleton view of testing resulting test sample for the laminate structure of the present invention of checking embodiment for the third time.
Fig. 8 illustrates how to prepare the skeleton view that is used for carrying out according to ISO4587 the test sample of bonding strength test.
Fig. 9 is the skeleton view as the electrical equipment of integrated molding embodiment of the present invention or casting of electronic device model.
Figure 10 is the front view of an integral part of test sample that is used to test the normal bonding strength of laminate.
Figure 11 is the schema of explanation integrated molding method of manufacture of the present invention.
Figure 12 explains the schema of traditional integrated molding method of manufacture.
Figure 13 is the decomposition diagram as the electrical equipment of another embodiment of integrated molding of the present invention or casting of electronic device model.
Figure 14 is the decomposition diagram of another embodiment of laminate of the present invention.
Figure 15 is the decomposition diagram as the electrical equipment of another embodiment of integrated molding of the present invention or casting of electronic device model.
Figure 16 is the decomposition diagram as the electrical equipment of another embodiment of integrated molding of the present invention or casting of electronic device model.
Preferred forms of the present invention
First embodiment of laminate of the present invention:
Fig. 1 shows laminate 5.Laminate 5 by from bottom 4a to top layer 4b laminated successively five layers form.That is, laminate 5 is made up of the first layer 1a, second layer 2a, the 3rd layer of 3a, the 4th layer of 2b and layer 5 1b.
Fig. 2 shows the partial amplification sectional view of the first layer 1a.Fig. 2 utilizes electron microscopic scanning (SEM) to the take pictures photograph of gained of the partial xsect of the first layer 1a.
The first layer 1a is the embodiment of laminate A1 of the present invention.Laminate A1 (the first layer 1a) comprises thermoset resin layer 11, thermoplastic resin 12 and the reinforcing fibre group 13 that contains a large amount of continuous fibers 13a and 13b.Thermoset resin layer 11 is combined into one with thermoplastic resin 12, and 14 places, interface between layer 11 and 12 become rough simultaneously.Paranema 13a in the reinforcing fibre group 13 contacts with thermoset resin layer 11 at least, and all the other the paranema 13b in the reinforcing fibre group 13 contact with thermoplastic resin 12 at least.The surface that is positioned at the thermoplastic resin 12 of interface 14 opposition sides is placed on the surface of laminate A1 (the first layer 1a).
Laminate A1 (the first layer 1a) is through on prepreg (this prepreg forms through uncured thermosetting resin is injected the reinforcing fibre group 13 that contains a large amount of 13a and 13b) surface, placing the base material that is used for thermal bond that is made up of thermoplastic resin; In the curing reaction of thermosetting resin or in the warm before the curing reaction, the thermoplastic resin that will be used for the base material of thermal bond injects reinforcing fibre group 13 and makes.
In laminate A1 (the first layer 1a), thermosetting resin has formed thermoset resin layer 11, and thermoplastic resin forms thermoplastic resin 12.Thermoplastic resin is injected reinforcing fibre group 13, and promptly thermoplastic resin is penetrated among the silk 13a and 13b that constitutes reinforcing fibre group 13, causes forming between thermoset resin layer 11 and the thermoplastic resin 12 rough interface 14.
As prepreg,, can adopt wherein multi beam reinforcing fibre 13 to arrange, perhaps along the laminated prepreg of prepreg thickness direction along the prepreg width as desired.Fig. 2 shows and places the outermost reinforcing fibre group 13 of prepreg.
The reinforcing fibre group 13 of laminate A1 is that 10mm or longer continuous fibers are formed by a large amount of length along at least one direction.Entire longitudinal length or whole transverse width that reinforcing fibre group 13 extends through laminate A1 continuously there is no need, and can interrupt halfway.
The form of reinforcing fibre group 13 can for the fabric that forms by a large amount of tow of forming (fibrous bundle), fibrous bundle respectively, along a direction containing of arranging folk prescription that a large amount of tow (folk prescription is to fibrous bundle) or folk prescription form to fibrous bundle to fabric.Consider the productivity of prepreg or laminate, be preferably folk prescription to fibrous bundle or fabric.The reinforcing fibre group of laminate A1 can be by the multiple fibre bundle of same form or multi-form multiple fibre Shu Zucheng.As requested, also can adopt lamination between each layer of reinforcing fibre group that the sandwich form of another base material is arranged.
The laminate 5 of Fig. 1 is aforesaid five layers of product.The first layer 1a is identical with the structure of layer 5 1b.The surperficial 4b of layer 5 1b is corresponding with the surperficial 4a of the first layer 1a.Second layer 2a is identical with the 4th layer of 2b structure.2a and 2b layer are made up of matrix resin (like epoxy resin) and reinforcing fibre group (like the thomel group) respectively.Also form for the 3rd layer 3 by matrix resin (like epoxy resin) and reinforcing fibre group (like the thomel group).In the laminate 5 of Fig. 1, in order to control all mechanical propertys, the orientation of the reinforcing fibre group among layer 1a, 2a, 3,2b and the 1b is different.Especially in order effectively to strengthen the Young's modulus and the intensity of laminate 5, the fibrous bundle that preferably adopts single direction is as the reinforcing fibre group.Under the thin thickness and number of plies condition of limited of laminate 5, when laminate 5 vertically be 0 when spending, the reinforcing fibre group of preferred outermost layer 1a and 1b is with the direction arrangement of 45 degree.
For the moulding article that laminate 5 is constituted look like fabric, preferably the fabric with tabby weave, satin weave, twill weave etc. is used as laminate 5 outermost reinforcing fibre groups.
The number that constitutes the silk of reinforcing fibre group is generally 300-48,000.The number of preferred silk is 300-12,000, more preferably 1, and 000-6,000.The number of this scope internal thread also preferably has beautiful appearance of fabrics.
Wherein to be bonded to the lip-deep traditional laminate of the thermoset resin layer of strengthening through the reinforcing fibre group be known to thermoplastic resin.This tradition laminate combines with another bonding parts through agglutinating thermoplastic resin on the surface.Through this combination, obtain expecting the moulding article.
The tradition laminate be through tackiness agent with thermoplastic resin with the thermosetting resin laminar surface is bonding processes, wherein this thermoset resin layer has the thermosetting resin of the group of fibers of being reinforced sclerosis and reinforcement.The method of manufacture of another kind of traditional laminate is through on the uncured thermosetting resin laminar surface that contains the reinforcing fibre group, forming thermoplastic resin; Then when thermosetting resin cured; Melt thermoplastic resin; Thermoplastic resin is combined on the thermosetting resin laminar surface and forms laminate, condition is the arrangement that the molten thermoplastic resin does not disturb the reinforcing fibre group, and promptly the fused thermoplastic resin does not get in the reinforcing fibre group with this understanding.The tradition laminate is used to make laminate wherein through lip-deep thermoplastic resin and another moulding article that parts combine that bond.Yet, also have some moulding article to form through external force.In this case, possibly rupture in the junction between thermoplastic resin and the institute's bonded block, problem is that the junction between thermoset resin layer and the thermoplastic resin also phenomenon of rupture can occur.
Laminate A1 of the present invention can address the above problem.The characteristic of laminate A1 is that it is such moulding article; Wherein the resin-bonded of the resin of thermoset resin layer and thermoplastic resin is integral; On the interface, form rough shape simultaneously; And wherein the paranema in the reinforcing fibre group contacts with thermoset resin layer at least, and another mantle fiber contacts with thermoplastic resin at least.This characteristic also comprises a kind of situation, and wherein some in reinforcing fibre group silks partly keeps in touch with thermosetting resin in a longitudinal direction, and other parts also keep in touch with the resin of thermoplastic resin.This characteristic does not occur in traditional laminate.
Adopted three kinds of testing method to verify the structure of laminate A1 of the present invention and traditional laminate, Fig. 3-Fig. 7 is described these three kinds of testing method.
First testing method is to utilize scanning electron microscope (SEM) or transmission electron microscope (TEM) that the xsect of the upper layer of laminate is observed.Can observe xsect as requested based on the photo that xsect is shown.Test sample is the surface layer part thin slice that cuts down on the laminate.Preparation is during test sample, and some meetings in the reinforcing fibre group come off, as long as but the degree that comes off can not influence when observing, this coming off can not caused any problem.This test sample can also dye as required, observes contrast gradient thereby reconcile.
The xsect that constitutes the silk of reinforcing fibre group is generally circular.After silk came off, what see usually was circular cavity.Except the part that contains the silk that constitutes the reinforcing fibre group, two zones of viewed thermoset resin layer and thermoplastic resin are obviously different in other part.
Observations to laminate A1 of the present invention is seen Fig. 3.The resin that Fig. 3 shows thermoplastic resin 22 get into to constitute the state in space among a large amount of 23a and the 23b of reinforcing fibre group 23, and the interface between thermoset resin layer 21 and the thermoplastic resin 22 is rough state.Exist to comprise a large amount of rough interface 24, this has guaranteed that the brute force between thermoset resin layer 21 and the thermoplastic resin 22 combines.
Observations to traditional laminate PA is shown among Fig. 4.The resin that Fig. 4 illustrates thermoplastic resin 32 does not get into the state in space among a large amount of 33a constituting reinforcing fibre 33 and the 33b, and the interface between thermoset resin layer 31 and the thermoplastic resin 32 almost is straight state.Interface 34 is almost straight line, and on the interface a large amount of silks can not be set.Therefore, the ability of the thermoset resin layer 31 of traditional laminate PA and the bonding strength between the thermoplastic resin 32 opposing external force is much little more than the ability of laminate A1 of the present invention.
Second testing method is to utilize scanning electron microscope (SEM) or transmission electron microscope (TEM) that the xsect of the surface layer part of remaining laminate after through solvent thermoplastic resin being extracted and removes is observed.As requested, can observe xsect based on the photograph of xsect.With laminate be cut into be about 10mm, wide about 10mm fragment as test sample.In test sample, be the solvent thorough washing thermoplastic resin of good solvent for removing that thermoplastic resin adopts the resin that constitutes this layer, the test sample that is formed for observing.Observe the xsect of the test sample of preparation with SEM (or TEM).
Observations to laminate A1 of the present invention is shown among Fig. 5.There is the thermoset resin layer 41 that contains the silk 43 that is arranged in the reinforcing fibre group among Fig. 5; But the thermoplastic resin that forms uneven interface with thermoset resin layer 41 has not existed, this be since when the preparation test sample thermoplastic resin by removal of solvents.Can see rough interface 44, and, can see the silk 43b in the reinforcing fibre group 43 in the once existing position of thermoplastic resin.Hole 45 can be seen in gap among the silk 43b.This observations has proved that the silk 43b in the reinforcing fibre group 43 is present in the thermoplastic resin of laminate A1.
Traditional laminate PA is observed, and its observational technique is similar to the observational technique of test sample, and observations is seen Fig. 6.Among the tradition laminate PA, the resin of thermoplastic resin does not infiltrate among the silk 53a and the space among the 53b of the reinforcing fibre group 53 that constitutes in the thermoset resin layer 51.When the preparation test sample; Thermoplastic resin is removed; The interfaces 54 that observed and thermoset resin layer 51 forms almost are straight lines, on a side at the interface of containing thermoplastic resin 54, and silk 43b and the hole 45 not observing among Fig. 5 to be shown.
In the third testing method, through with laminate A1 with as the bonding parts another part B 1 (not shown) carry out the integrated moulding article C1 (not shown) that combines to make, make the two separation with external force, the observation crack conditions.The third testing method is at room temperature to separate through external force, ruptures between laminate A1 and bonding parts B1 to guarantee integrated molding C1.Have on the upper layer of bonding parts B1 after the separation and still have laminate A1 bonded thereto.Use the microscopic examination residue.
The situation example of the test sample of the third method test is seen Fig. 7.The joining part 61 that the surface that Fig. 7 shows laminate A1 combines with bonding parts B1 one end.In the part of joining part 61, can be observed the part residue 62 of the surface layer part of laminate A1.Can see, have a large amount of silks that from the reinforcing fibre group of laminate A1 upper layer, come off in the residue 62.On the contrary, be not attached at this type residue under the situation of bonding parts B1, perhaps in residue, can't see under the situation that silk exists, then the lip-deep resin of thermoplastic resin is not penetrated in the space in the reinforcing fibre group of laminate.Such laminate does not possess effect of the present invention.
The constitutional features of laminate of the present invention can obtain checking through above-mentioned at least a testing method.
In order to strengthen the bonding strength of laminate A1 and other bonding parts B1, the maximum ga(u)ge Tpf at continuous fibers 13b position of living in is 10 μ m or bigger in the preferred thermoplastic resin layer 12, and more preferably 20 μ m or bigger further are preferably 40 μ m or bigger.Maximum ga(u)ge Tpf-max is defined as from outermost lateral filament (face side) 13b-out to the distance the interior lateral filament 13b-in-max; Wherein, Outermost lateral filament (face side) 13b-out is along the contacted silk of the resin of the thickness direction of thermoplastic resin 12 and thermoplastic resin 12, in lateral filament 13b-in-max be meant the maximum zone of the thickness that gets into from surface seepage with thermoplastic resin 12 and the contacted silk of the resin of thermoplastic resin 12.Maximum ga(u)ge Tpf-max can measure on SEM that obtains according to first or second testing method or TEM photograph.If maximum ga(u)ge Tpf-max is 1,000 μ m, effect then of the present invention can fully be achieved.
Minimum thickness Tpf-min is defined as from outermost lateral filament (face side) 13b-out to the distance the interior lateral filament 13b-in-min; Wherein, Outermost layer silk (surface) 13b-out is along the contacted silk of the resin of the thickness direction of thermoplastic resin 12 and thermoplastic resin 12, in lateral filament 13b-in-min be meant the minimum zone of the thickness that thermoplastic resin 12 gets into from surface seepage and the contacted silk of the resin of thermoplastic resin 12.
In laminate A1, the interface 14 between preferred thermoset resin layer 11 and the thermoplastic resin 12 is present in by in the reinforcing fibre group 13 that a large amount of 13a and 13b formed that is arranged in parallel along same direction, sees Fig. 2.When reinforcing fibre group 13 is present in a plurality of layer of thickness direction of laminate A1, be enough to make interface 14 to be present in the outermost reinforcing fibre group 13 usually.
Curing reaction has taken place in the resin that is preferably formed the thermoset resin layer 11 of laminate A1 of the present invention, thereby guarantees that laminate A1 possesses good mechanical property.Preferably, the glass transition temperature of thermosetting resin is 60 ℃ or higher, more preferably 80 ℃ or higher, further is preferably 100 ℃ or higher.Glass transition temperature adopts known testing method to utilize DSC (DSC) to measure.As, the thermoset resin layer 11 from laminate A1 under the situation of not separating reinforcing fibre group 13 cuts out a test sample, sets glass transition temperature according to the endotherm(ic)peak of test sample.Along with thermosetting resin is cured reaction, glass transition temperature is to higher temperature transition, and therefore, endotherm(ic)peak is tending towards diminishing.
When laminate A1 of the present invention combines with other bonding parts B1 when making integrated molding, be to obtain the good combination effect, be necessary laminate A1 bonds parts B1 surface separately with other on, to provide under the situation of thermoplastic resin and combine.The area S of thermoplastic resin 12 carries out bonding parts B1 the bonded area by the bonding strength of predetermined requirement and determines according to guaranteeing on the laminate A1 surface.Area S need not big again.But, consider the processing characteristics of integrated molding, thermoplastic resin 12 also may reside on laminate A1 and the contacted whole interface of bonded block B1.
When dividing formation thermoplastic resin 12 in the upper surface of laminate A1, the area of preferred thermoplastic resin layer 12 accounts for the 0.1-50% of laminate A1 surface area, and more preferably 1-40% further is preferably 10-30%.And, consider and avoid laminate A1 warpage, as shown in Figure 1, can also on each surface of laminate, form thermoplastic resin 12.In this case, because the layer structure of laminate A1 is symmetric, the dimensional stability of laminate A1 is with fine.
The laminate A1 of the present invention at room temperature cohesive strength with other bonding parts B1 is not high; If but thermoplastic resin 12 is by institute's fusions such as heat; Laminate A1 will be easy to combine with other bonding parts B1, thereby laminate A1 and bonded block B1 are combined into one.
According to ISO4587, the bonding strength AS during laminate A1 room temperature of the present invention is preferably 6MPa or higher, and more preferably 8MPa or higher further is preferably 10MPa or higher.The higher limit of bonding strength AS is not special to be limited, when its during smaller or equal to 30MPa, effect of the present invention will be enough to abundant realization.
The test sample that is used to test bonding strength AS prepares through following method.
According to ISO4587, the shape and size of test sample TP1 are shown among Fig. 8.The length T P1L of test sample TP1 is 100mm, and width TP1W is 25mm.Two test sample TP1 have been prepared.If the form of laminate A1 is difficult to cut out the test sample of above-mentioned size, can be that scaled test sample replaces also with size, as shown in Figure 8.
Two test sample TP1 that prepare are relatively put, separately thermoplastic resin is combined and form junction.The length BPL of junction BP is 12.5mm.Heat two test sample TP1 to the abundant fused temperature of the resin of thermoplastic resin 12, two fragments are mutually combined and be sandwiched in together, obtain the Elongation test print that two test samples combine after the cooling.Adopt the Elongation test print to carry out Elongation test.Guarantee that (near interface) ruptures near junction, power (kN) is bonding strength (MPa) divided by the total of junction surface-area.In the process of preparation Elongation test print, combining method need not special qualification, as long as this method can combine two test sample TP1.Combining method can be Vibration Welding or ultra-sonic welded.The method of clamping two test sample TP1 also need not special qualification.For example, can be employed in the method that compresses junction BP under the pressure of 0.1-1MPa.
Second embodiment of laminate of the present invention:
Fig. 9 shows integrated molding C2.Among Fig. 9, moulding article C2 is made up of laminate A2 of the present invention that constitutes a laminate 101 and the structure unit B2 that constitutes framework 102.In moulding article shown in Figure 9, top board 101 (laminate A2) is combined into one with the top surface of framework 102 (structure unit B2) unlifted wall, and this is an instance of electromagnetic-shielding molded article C2 such as PC housing.
Among Fig. 9; An integral part as electromagnetic-shielding molded article C2; Laminate A2 of the present invention (plate 101) is by forming as the thermosetting resin of matrix resin and the continuous reinforcing fibre group of conductivity that is arranged in the resin; Its also contain hereinafter described that on the part surface at least of laminate A2 (top board 101), form, by film that the thermoplastic resin composition constituted (because this surface is the lower surface of laminate A2, Fig. 9 does not illustrate this film).
Laminate A2 is meant and be guarantees mechanical property, and the various kinds of resin compsn sheet material that wherein contains the reinforcing fibre of arranging along multiple direction is carried out laminated laminate along thickness direction.The length of conductivity reinforcing fibre in laminate A2 is 10mm or longer.But reinforcing fibre needn't run through the whole length of laminate A2 continuously, and it can be interrupted halfway.
The form of the conductive fibers folk prescription that can be the fabric that forms of tow, tow, folk prescription form to tow to tow or folk prescription is to fabric.It is suitable that what use can be that fabric or folk prescription are to tow.Reinforcing fibre can be any one or two or more use that combines of above-mentioned form.
Hope laminate A2 of the present invention guarantee with miscellaneous part; Combine when obtaining integrated molding through the film that constitutes by the thermoplastic resin composition like structure unit B2 (framework 102); These moulding article are 10MPa in the normal bonding strength of junction during at 40 ℃, in the time of 140 ℃, are lower than 10MPa.
Integrated molding is used as the housing of main placement heating installation.Therefore, about 40 ℃ is the temperature of normal operation circumstances, considers and can in this environment, use, and the normal bonding strength in the time of preferred 40 ℃ is 10MPa or higher.More preferably 13MPa or higher further is preferably 18MPa or higher.If 40 ℃ normal bonding strength is lower than 10MPa,, integrated molding C2 possibly rupture when receiving great power owing to reason such as drop in the junction between laminate A2 and the structure unit B2.Down the upper limit of normal bonding strengths is unqualified to 40 ℃, but is during smaller or equal to 30MPa when it, and effect of the present invention will be enough to abundant realization.
In addition, laminate A2 of the present invention also has a characteristic, promptly in the normal bonding strength under 140 ℃ far below the normal bonding strength under 40 ℃.Normal bonding strength under 140 ℃ is lower than 10MPa, is preferably 5MPa or lower, more preferably 1MPa or lower.
As the thermosetting resin of laminate A2, normally used is that (normal atmosphere, vitrifying transformation point (Tg) 50%RH) are 130-150 ℃ thermosetting resin in the atmosphere.Reason is that laminate A2 is mainly used in the PC, and the envrionment temperature of its use can not be higher than 150 ℃.Should be noted that a fact, the normal bonding strength of laminate A2 of the present invention under 140 ℃ keeps below 10MPa.Satisfy under the situation of this requirement at laminate A2 of the present invention; When mutually combining the moulding article C2 that constitutes when going out of use through being formed at the lip-deep thermoplastic resin composition of laminate A2 by laminate A2 and miscellaneous part B2; In the time of 140 ℃; These moulding article are easy to be disassembled into each parts, like item plate 101 and framework 102.Therefore, be easy to each parts is classified, thereby can promote each parts to be utilized again.
The measuring method of normal bonding strength will be described with reference to Figure 10.The mutually combine position cutting that is integral of laminate A2 and structure unit B2 obtains the test sample TP2 that is used to test from integrated molding C2.The top of test sample TP2 and bottom are fixed on the brake(-holder) block 111a and 111b of common stretching test machine, along pulling test sample TP2 with direction ( arrow 113a and 113b) that the connection interface 112 of test sample is vertical (90 spend).Make the maximum load that connects interface 112 fractures obtain tensile strength (T) MPa divided by the area that connects interface 112, this numerical value is defined as normal bonding strength.The stretching test machine that adopts is " Instron " (trade mark), and model is 5565Universal Testing Machine (InstronJapan Co., Ltd. makes), and the stress rate in the test is 1.27mm/ minute.
Elongation test carries out in the laboratory that envrionment temperature can be regulated, and envrionment temperature is set at 40 ℃ and 140 ℃.Before beginning test, test sample TP2 does not bear the load of Elongation test at least 5 minutes time.Preferably, a thermopair is installed on test sample TP2, is reached consistent with envrionment temperature with temperature before confirming Elongation test.
Under moulding article C2 can the situation by the brake(-holder) block 111a of stretching test machine and 111b clamping, moulding article C2 is clamped between the brake(-holder) block 111a and 111b of stretching test machine, to carry out Elongation test.Under the situation that moulding article C2 can not be held; Need with acryloid cement (Ltd. makes for Three bond 1782, ThreeBond Co.) coated molding C2; Be placed among 23 ± 5 ℃ and the 50 ± 5%RH and reach 4 hours, make moulding article and brake(-holder) block 111a and 111b bonding.About test result, only peeling off appears in the junction between laminate A2 and structure unit B2, and the junction of moulding article and any one brake(-holder) block does not all have under the situation of fracture, and this test result numerical value is just available.Because if the junction of moulding article and brake(-holder) block ruptures, then can not obtain correct bonding strength value.
The mean thickness that laminate A2 of the present invention goes up the film that forms is preferably 0.1-1000 μ m, and more preferably 1-200 μ m further is preferably 10-50 μ m.The mean thickness of film is meant maximum ga(u)ge Tpf, and is as shown in Figure 2, and the measuring method of mean thickness is identical with the method for measuring maximum ga(u)ge Tpf.If the thickness of film is not constant, then should select several TPs to carry out the test of thickness, the thickness of film then is the MV of institute's value.If mean thickness in above-mentioned preferred value scope, the normal bonding strength in the time of then obtaining 40 ℃ more reliably.
The material of used reinforcing fibre group comprises spun glass, thomel, steel fiber, aromaticity tynex (aromatic polyamide fibers), aromatic polyamide fibre (polyaramide fiber), aluminum fiber, silicon carbide fiber and boron fibre among laminate A1 of the present invention or the A2.Can use in the above-mentioned materials any one, also can unite and use two or more.The surface of fiber also can be processed.The surface-treated example comprises the metallic cover processing, utilizes coupling agent to handle, utilize adhesive treated, adds the processing of additive etc.These fibers also can comprise conductive fibers.What preferably use is thomel, because thomel proportion is little, intensity is high, modulus is high.
Used thermosetting resin is preferably and can gives the moulding article C1 that contains laminate A1 or A2 or C2 the resin with good rigidity and intensity among laminate A1 of the present invention or the A2.The example of thermosetting resin comprises undersaturated polyester, vinyl acetate, epoxide, phenol (soluble phenolic resin type), urea-melamine, polyimide and their multipolymer and modified product, and by the resin of at least two kinds of above-mentioned substance mixing gained.In order to strengthen shock resistance, can elastomerics or rubber constituent be added in the thermosetting resin.Consider the mechanical property of moulding article C1 or C2, preferably use epoxy resin.
The example that forms the thermoplastic resin of film among thermoplastic resin among the laminate A1 of the present invention 12 or the laminate A2 comprises polyamide resin, vibrin, polycarbonate resin, styrene resin, ethylene-vinyl acetate copolymer (EVA) resin, urethane resin, vinyl resin, polyolefin resin, polyphenylene sulfide (PPS) styron and their multipolymer and modified product, and by the resin of at least two kinds of above-mentioned substance mixing gained.As required, also can add such as additive and weighting agent.Consider will with the cohesive force of bonding parts B1 or B2, the composition of selected desirable thermoplastic resin and bonded part is close.For example, when laminate A1 or A2 combined with bonding parts B1 that is made up of polyamide resin or B2, the thermoplastic resin or the film that form on preferred laminate A1 or the A2 surface were polyamide resin.
Consider the practical application and the operability of making laminate of moulding article, preferred fusing point of employed thermoplastic resin or softening temperature are 50 ℃ or higher.And because under thermosetting resin cured temperature, thermoplastic resin need be melted or be softening, the fusing point of preferred thermoplastic resin or softening temperature are 300 ℃ or lower.More preferably the fusing point of thermoplastic resin or softening temperature are 100-250 ℃, further are preferably 125-220 ℃.Fusing point is to be measured under 10 ℃/minute the condition through DSC at temperature rise rate according to JIS K7121.Softening temperature is to record through measuring the Vicat softening temperature according to JIS K7206.
But for obtaining moldability, mechanical property and capability of electromagnetic shielding, the content of the continuous conductivity reinforcing fibre of laminate A1 of the present invention or A2 is preferably 5-75vol%.Preferred content range is 30-75vol%, further is preferably 50-70vol%.
As the structure unit B1 or the B2 of integrated molding C1 or C2 integral part, its material does not receive special qualification, as long as this material has the thermal caking power with laminate A1 or A2 in junction.Can also use and the surface of the alloy of aluminium, iron, magnesium, titanium or above-mentioned metal is handled and obtain the metallic substance of heat adhesiveness.
Structure unit B1 or B2 preferably are made up of the thermoplastic resin composition of containing reinforcing fibre.The example of reinforcing fibre comprises thomel based on polyacrylonitrile, based on the thomel of regenerated fiber, based on the thomel of xylogen, based on bituminous thomel, graphite fibre, spun glass, steel fiber such as aluminum fiber, copper fiber and Stainless Steel Fibre and inorganic fibre such as silicon carbide fiber and silicon nitride fiber.
The thermoplastic resin that is used for structure unit B1 or B2 does not receive special qualification.The instance of thermoplastic resin comprises polyester, like polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PTT (PTT), PEN (PEN) and liquid crystal polyester; Polyolefine such as Vilaterm (PE), Vestolen PP 7052 (PP) and polybutylenes; Styrene resin; Polyoxymethylene (POM); Polyamide (PA); Polycarbonate (PC); Polymethylmethacrylate (PMMA); SE (PVC); Polyphenylene sulfide (PPS); Ppe (PEE); Modified PE E; Polyimide (PI); Polyamidoimide (polyamideimides, PAI); Polyetherimide (PEI); Polysulfones (PSU); The PSU of modification; Polyethersulfone; Polyketone (PK); Polyetherketone (PEK); Polyetheretherketone (PEEK); PEKK (PEKK); Polyene propionic ester (PAR); Polyethers nitrile (PEN); Phenolic resin; Phenoxy resin; Fluorine resin is like tetrafluoroethylene; And based on the thermoplastic elastomer of PS, polyolefine, urethane, polyester, polymeric amide, polyhutadiene, TR 301 and fluorine etc.; And the multipolymer of above-mentioned substance and modified product, also have resin by at least two kinds of above-mentioned substance mixing gained.Also can in thermoplastic resin, add elastomerics or rubber constituent, to strengthen shock resistance.Consider that from the angle of thermotolerance and chemical resistance the PPS resin is the preferred resin that uses.Consider that from the outward appearance of moulding article and the angle of dimensional stability polycarbonate resin and styrene resin are preferred.Consider that from the intensity of moulding article and the angle of shock resistance polyamide resin is preferred.Also can add weighting agent and additive in the thermoplastic resin.One of additive is for giving conductive material.Give thomel and carbon nanotube that conductive examples of substances comprises carbon black, amorphous carbon powder, natural graphite powder, graphous graphite powder, expanded graphite powder, pitch microballon, vapor phase growth.When moulding article C1 or C2 are used as the housing of PC, give conductive material and can be preferred for improving capability of electromagnetic shielding.
The method of utilizing laminate A1 of the present invention or A2 to make integrated molding C1 or C2 does not receive special qualification.For example, this method of manufacture is included under a certain temperature of the fusing point that is higher than thermoplastic resin 12 or film or softening temperature, in conjunction with adhesive structure part B 1 or B2, refrigerative step then, thermoplastic resin wherein or film are the integral parts of laminate A1 or A2.
The method that laminate A1 or A2 and structure unit B1 or B2 are mutually combined does not receive special qualification.The example of this method comprises: (i) comprise making laminate A1 or A2 moulding in advance; Make structure unit B1 or B2 moulding then; And the method that itself and laminate are combined into one, (ii) comprise making structure unit B1 or B2 moulding in advance the method that makes laminate A1 or A2 moulding then and itself and structure unit are combined into one; (iii) comprise making laminate A1 or A2 and structure unit B1 or B2 moulding respectively, then with the two all-in-one-piece method that combines.
The example of integrated combining method comprises that thereby laminate A1 or A2 and structure unit B1 or B2 are carried out the mechanical type assembling makes the two method that is combined into one, both utilize integrated combining method, the both of mechanical bond means such as screw or screw to utilize the integrated combining method of Chemical bond means such as tackiness agent.As required, can be used in combination two or more above-mentioned combining method.
The object lesson of integrated combining method (i) is: make laminate A1 or A2 through mold pressing; Process or predetermined size that aftertreatment needs with acquisition; It is embedded in the injecting molding die, and the material that in this mould, injects acquisition structure unit B1 or B2 is to carry out injection molding.
Integrated combining method object lesson (ii) is: through injection molding manufacturing structure part B 1 or B2; Process or the predetermined size of aftertreatment to obtain to require; It is embedded in the pressing mold, heat this pressing mold then to treatment temp.Then, the base material of the prepreg that wherein contains preparation laminate A1 or A2 is inserted in the pressing mold, form thermoplastic resin on the surface of this prepreg, the conductive fibers group that prepreg is made up of uncured thermosetting resin and a large amount of continuous fibers constitutes; Under the temperature that is higher than the thermoplastic resin fusing point, carry out vacuum bag molding.
Integrated combining method object lesson (iii) is: make laminate A1 or A2 through mold pressing; Process or aftertreatment to obtain predetermined size.Obtain structure unit B1 or B2 through injection molding separately; According to through thermal bond or ultra-sonic welded etc. they being combined into one with the (ii) identical method of integrated combining method.
Consider the productivity of integrated molding C1 or C2, the preferred employing injected moulding or jet forming method in the integrated combining method (i).Consider the precision of shape stability and junction, can preferably adopt integrated combining method (iii), and preferably adopt thermo-welding, Vibration Welding, ultra-sonic welded and laser welding.
Carry out moulding article C1 or the C2 that integrated combination obtains through above-mentioned any one method, its weight is lighter, and traditional all-in-one-piece method that combines with metallic substance can't obtain light like this weight at all.Above-mentioned any one integrated combining method can make the intensity of sticking between laminate A1 or A2 and structure unit B1 or the B2 reach good, and can solve with compositions of thermosetting resin and carry out the problem of peeling off that occurs between each parts in integrated the combination.
For keeping the form of moulding article C1 or C2, on the part interface between laminate A1 or A2 and structure unit B1 or the B2, contain bonded areas (tack coat) at least.The preferred area of bonded areas (tack coat) for connect the interface 50% or bigger.More preferably 70% or bigger, further be preferably the gross area that connects the interface.
Integrated molding C1 or C2 combine to be integral through laminate A1 or A2 and structure unit B1 or B2 to make, and the shape of moulding article C1 or C2 does not receive special qualification.Its shape also can have curved surface, rib, pivot, projection or cavity district.Modes such as the surface of bonded moulding article C1 or C2 can be through plating, coating, gas deposition, inlay, impression or laser radiation are carried out modification.
The range of application of moulding article C1 or C2 comprises that requirement has the product of capability of electromagnetic shielding.The parts that the example of these products comprises, element and housing, for example various gears, various cabinet, transmitter, LED lamp, junctor, socket, resistance, relay cabinet, switch, coil axes, electrical condenser, optical pick-up, vibrator, various end plaste, X-former, plug, PC board, tuner, speaker, Mike, earphone, small engine, head hold, power module, semi-conductor, indicating meter, FDD bracing frame, chassis, HDDs, MOs, automobile brush support, teledish, notebook computer, Cell phone, digital camera, PDAs, portable MDs and plasma display; The parts of family expenses or office appliance, element and housing are like telephone installation, facsimile equipment, VTRs, duplicating machine, TV, electriciron, device for colouring hair, electric cooker, electric oven, stereo set, suction cleaner, toilet apparatus, CD-ROM device, small-sized video disc player, head light, refrigerator, air-conditioning, type-writer and WP; Parts, element and the housing of recreation and amusing products are like pinball machine, slot machine and game machine; Parts, element and the housing relevant with opticinstrument and precision instrument are like microscope, binoculars, pick up camera and clock; Medical facilities are like X-ray box; Parts, part and the exterior panel relevant with automobile and cart are like engine parts, alternator terminals, alternator junctor, IC setter, taillight (light-reer) potentiometer, suspension member, vent valve and other various valves, pipeline, exhaust system and inlet system that various and fuel are relevant, inlet mouth ventpipe, intake manifold, various arm, various framework, various pivot, various bearing, petrolift, fuel tank, CNG case, component cooling water junctor, vaporizer main body, vaporizer container, exhaust sensor, water coolant transmitter, oil temperature sensor, brake pad wear sensor, throttle valve position sensor, arbor position transducer, anemometer, air-conditioner temperature setter base plate, indoor heated air stream valve, scatterer phonomoter brush holder, water pump impeller, turbine blade, wiper motor parts, sparger, starter power switch, starter rly., conveyer line group, window brush nozzle, air-conditioning panel switching circuit plate, the electromagnetic valve coil relevant with fuel, insure junctor, storage battery combination box, AT support, head light support, running-board bracket, bearing circle, door pillar, protector, chassis, framework, handrail, loudspeaker terminal, stepping mover rotating shaft, lamp socket, lamp projector, lamp cover, brake piston, noise isolation device, radiator bearer, spare tire covering members, sheet frame, solenoid coil bobbin, engine oil filter, portfire case, coverture, friction plate, edge list, drive shaft, wheel, splash pan, test board, snubber, snubber post, engine shield, flight parts, platform, headstock cap, ceiling, instrument panel, spoiler and various module; Parts, element and external plates that aviation aircraft is relevant are like gear, wing, spoiler, side, ladder, elevating rudder and rib; Parts and element that sports goods is relevant are like various bars, golf club, ship, plate, graspen, Veronicastrum Herb and bike; The parts that man-made satellite is relevant; Building component such as panel.Integrated molding C1 or C2 can be used in the above-mentioned various application.
Wherein, Integrated molding C1 or C2 needing can be preferred in the application of lightweight, high rigidity, complex-shaped and capability of electromagnetic shielding; Like electrical equipment and electronics, business automation equipment, household electrical appliance and medical facilities, for example PC, indicating meter, Cell phone and portable data assistance.
In addition, in big moulding article, make the complex-shaped parts with excellent mechanical properties at an easy rate, integrated molding also is suitable in parts, element and the external plates of automobile, cart, bike, ROV and building.
The electromagnetic-shielding molded article that made by laminate of the present invention have good capability of electromagnetic shielding; Therefore these moulding article are applicable to the housing and the external component of electrical equipment or electronics, and are applicable to shadow area that needs are big and the very thin notebook computer or the housing of portable data assistance.If the moulding article of electromagnetic shielding are used as such housing, consider that from capability of electromagnetic shielding laminate A2 should occupy the part as the moulding article C2 end face of housing at least.Laminate A2 preferably occupy moulding article C2 top surface area 50% or more, more preferably occupy 70% or more.
The method of laminate A1 or A2 of making is described with reference to Figure 11 and 12, the for example clear method of making as the casting of electronic device of integrated molding C1 or C2 advantageous applications of Figure 11 and 12.
Figure 11 shows a method instance making laminate of the present invention 5 shown in Figure 1.
The manufacturing of laminate A is described below.Prepreg 60 is cut into predetermined size (step 71), and the reinforcing fibre bundle of being made up of a large amount of continuous fibers in the described prepreg 63 has been injected into the thermosetting resin 61 as matrix resin.Lamination step 72 is: the sheet to prepreg 60 carries out lamination at a predetermined angle; As 5 sheets with 0 degree angle ,+miter angle, 90 the degree ,-45 the degree and 0 degree angle carry out lamination, the base material of then thermal bond being used, be made up of the thermoplastic resin composition 62 covers on whole surface or the part surface.Next; Be used in thermal bond base material thermoplastic resin composition's fusion and to its pressurization; And carry out the curing reaction of compositions of thermosetting resin simultaneously; Or before curing reaction, carry out preheating, so that thermoplastic resin and the moulding of thermoplastic fat tunic, this is thermoforming step 73 (a laminate moulding substep 70).Just; After thermoplastic resin composition 62 is arranged on as film on, under the temperature that is higher than thermoplastic resin composition's 62 fusing points, compositions of thermosetting resin is solidified by the upper layer of the prepreg 60 of also uncured compositions of thermosetting resin and reinforcing fibre Shu Zucheng.Therefore, obtain compositions of thermosetting resin 61 and thermoplastic resin composition's 62 mortise and wherein contain the laminate A of reinforcing fibre bundle.The reason that cohesive strength is high is that the thermoplastic resin composition is in molten state; Its infiltration runs through the reinforcing fibre bundle that a large amount of continuous fibers constitute; Arrive the compositions of thermosetting resin that just is being cured; Thereby form the uneven interface between compositions of thermosetting resin and the thermoplastic resin composition, contain a large amount of silks among thermosetting resin and the thermoplastic resin composition.Therefore, even the thermoplastic resin composition is melted and lamination again after compositions of thermosetting resin solidifies, all be difficult to obtain laminate of the present invention.
The concrete grammar of making laminate A does not receive special qualification.Can adopt the currently known methods that utilizes thermosetting resin to carry out moulding; Like the manual twisting method of forming (hand paid-up molding method), spray-up moulding method (spray-up molding method), vacuum-bag molding, pressure moulding method, autoclave molding method (autoclave molding method), compression moulding and transfer moudling (transfer molding method); And the known method that utilizes thermoplastic resin, like simple compression moulding and process for stamping.Consider operability and mechanical property, suitable have vacuum-bag molding, compression moulding and a transfer moudling.
In order to strengthen the bonding strength between the laminate A and structure unit B among the integrated molding C; When permeating between the silk of fused thermoplastic resin composition 62 in reinforcing fibre group 63; Preferably apply 0.1Mpa or higher; More preferably 0.5Mpa or higher further is preferably 1Mpa or higher pressure.
For the laminate A that utilizes preparation makes integrated molding C, laminate A is cut into predetermined size, this is called as aftertreatment (step 74), for example makes the laminate A that is used to make integrated molding C through punching press.
Then laminate A is embedded into (step 81) in the injecting molding die; Thermoplastic resin composition 83 is injected in the mould and carries out ejection formation (step 82); Wherein this thermoplastic resin composition is used to form structure unit B, like the material of projection, rib, pivot or framework.The moulding article C that utilizes this simple integrated zygote method 80 to make repairs to obtain goods 92 (post-processing step 90) in repairing step 91 as required.Resulting product 92 is exactly complete integrated molding C.
Figure 12 shows the method that adopts traditional laminate to make integrated molding PC.According to the forming method identical with laminate moulding submethod shown in Figure 11 70, the preimpregnation material sheet lamination that compositions of thermosetting resin and reinforcing fibre group are formed gets laminate PA.The thermoplastic resin composition 62 who does not have Figure 11 among this laminate PA.Because gained laminate PA is not a heat adhesiveness,, then must in integrated integrating step, use sticker for obtaining moulding article PC.
Structure unit PB carries out independent moulding like projection, rib, pivot or framework.The method of manufacture of structure unit PB for example is to obtain profiled part 123 (injection molding submethod 120) through injection molding (step 122) thermoplastic resin composition 121.As required, resulting structures parts PB is handled (step 131), use again sticker is coated in the zone (step 133) that needs to combine laminate PA with priming paint.Make laminate PA combine with the structure unit PB that is coated with sticker (step 133).At the instrument of employing fixed simultaneously, make the two combine (step 134).Then with laminate PC long-time dry (step 135).Remove instrument then, obtain product (integrated zygote method 130).Product 136 integrated moulding article PC as required, also can further repair in repairing step 141 and obtain product 142 (aftertreatment submethod 140).This product 142 is final integration product PC.As stated, compare with making laminate A of the present invention, making traditional laminate PA needs a large amount of work, time and cost.Compare with moulding article of the present invention, laminate PA and the bonding strength between the structure unit PB of this integrated molding PC are lower.
The embodiment that is used for the base material of thermal bond among the present invention:
The base material that is used for thermal bond among the present invention is meant the base material that is used for identical or different bonding parts are carried out each other thermal bond.Just, the base material that is used for thermal bond mutually combines two or more bonding parts, adopts any heat-supplying mode between the bonding component interface, to form by being used for the tack coat that base material that thermal bond uses constitutes.
The bonding strength S that is used for the base material of thermal bond shears the adhesive strength performance test methods according to ISO04587 (JIS K6850) through tension load to measure (cohesive strength that this method is particularly useful for measuring rigidity bonding parts); Under 100 ℃ measurement temperature, bonding strength is 5.0Mpa.Preferred cohesive strength S is 7Mpa or higher, further is preferably 8Mpa or higher.
Measure temperature and be meant when the bonding strength of parts of thermal bond is carried out in measurement through the base material that is used for thermal bond, as the envrionment temperature when measuring normal bonding strength.Test sample is placed thermostatic chamber, when temperature to be determined equates with envrionment temperature, adopt anchor clamps clamping test print section to carry out stretching experiment.
If bonding strength S is less than 5.0Mpa under 100 ℃ measurement temperature, when bonded products was used under hot environment, pressure can cause boning and occur the phenomenon that is easy to peel off between the parts.
And when the measurement temperature was 200 ℃, the bonding strength S that is used for the base material of thermal bond was 1.0Mpa or littler, is preferably 0.8Mpa or littler, further is preferably 0.7Mpa or littler.
If the bonding strength S under 200 ℃ of measurement temperature is greater than 1.0Mpa; Then separate and dismantle the bonding parts work and cost will increase; Or make more difficulty of recycling classification, or in materials classification, particularity is reduced owing to sneaking into different substances, thus cause polluting.
The method that the test sample of bonding strength S is measured in preparation is described below.Form the bonded test sample according to ISO4587, and make it have certain size, as shown in Figure 8.Test sample should meet shear through tension load according to JIS K6850 in the adhesive strength performance test methods, this method is particularly useful for testing the intensity of rigidity bonding parts.Test sample is from prepreg, to obtain, and this prepreg is through making as injecting thermosetting resin in the single direction carbon fiber bundle of reinforcing fibre.Test sample carries out lamination with 0 °/90 °/90 °/0 ° direction and obtains two second test samples.The base material that will be used for thermal bond places one second test sample to desire to carry out the surf zone of thermal bond.On veneer sheet, another second test sample is placed on it, make precast body with the specified form of ISO4587.Place mould to carry out pressing mold this precast body, if desired, tool using and pad are to keep shape, so that pressing mold.When preheating and compacting, the used pressure of hot-die machine is 1Mpa, exerts pressure 5 minutes, and applying pressure 1Mpa pressurizeed 30 minutes under the solidification value of the resin that injects prepreg subsequently, to accomplish curing reaction.Preheating temperature is the melt temperature of staple thermoplastic resin that is used for the base material of thermal bond.Especially suitable preheating temperature is that fusing point or the softening temperature of thermoplastic resin is to the TR that is higher than 30 ℃ of fusing point or softening temperatures.This fusing point and softening temperature are measured through above-mentioned measuring method.
Used prepreg does not receive special qualification; But the preferred prepreg that uses is the prepreg that epoxy resin (thermosetting resin) injects carbon fiber bundle; Wherein carbon fiber content (wf) is 70wt%; Thickness is 0.11mm (Toray Industries, the Torayca UD prepreg 3053S-12 that Inc. makes).When using this prepreg, solidification value is 130 ℃ to 150 ℃.The test sample of gained is used to estimate bonding strength S.
From the purpose that the identical or different bonding parts that make through thermal bond are easy to dismantle, the bonding strength S that the present invention is used for the base material of thermal bond preferably has specific temperature dependency.That is to say, if given probe temperature t (℃) under, bonding strength is S
t, probe temperature (t+30) (℃) under, bonding strength is S
(t+30), then preferably satisfy relational expression St>=3xS
(t+30)The TR of probe temperature t be 100 ℃ to 200 ℃, more preferably 120 ℃ to 180 ℃, further be preferably 130 ℃ to 170 ℃.
The base material that the present invention is used for thermal bond obtains through the form that the thermoplastic resin composition is processed into base material.Used thermoplastic resin composition need not special qualification; But have temperature dependency and at room temperature have the purpose of high bond strength from acquisition, the preferred thermoplastic resin compsn is to contain to be selected from following at least a resin: polyamide resin, vibrin, polycarbonate resin.Especially preferred polyamide resin.Polyamide resin is a kind ofly to contain amino acid, lactan or diamines and dicarboxylicacid is the polymkeric substance of staple, and is the moity that is used for the base material of thermal bond, and its homopolymer or multipolymer all can use.Consider the temperature dependency of bonding strength S, more preferably the polyamide copolymer resin.
The representative instance of the suitable polyamide resin that uses comprises polymeric amide 11, polymeric amide 12, polyamide 6 10, polyamide 6 12, polyamide 66/6, polyamide 6/66/610, polyamide 6/66/612, polyamide 6/66/610/612 and polyamide 6/6I.Also but two or more are used in combination.What especially be suitable for is to contain terpolyamide 6/66/610 to use base material for the thermal bond of component.
From the purpose that is applied to require fire-retardant parts, the thermoplastic resin composition is preferably contained flame-retardant composition.As flame-retardant composition, can use any known fire retardant, like halogen contained compound, antimony containing compounds, P contained compound, nitrogenous compound, silicon-containing compound, fluorochemicals, phenolic cpd and metal hydroxides.In view of environmental factors, preferably adopt P contained compound, like ammonium polyphosphate, poly phosphazene, SULPHOSUCCINIC ACID ESTER, phosphonic acid ester, phosphinate, phosphine oxide and red phosphorus.The thermoplastic resin composition can comprise weighting agent, additive, other thermoplastic resins etc., and its add-on does not influence product of the present invention and is advisable.
The available additive comprises crystal nucleating agent, UV light absorber, inhibitor, sound-proof material, biocide, sterilant, reodorant, anti-staining agent, thermo-stabilizer, release agent, static inhibitor, softening agent, lubricant, tinting material, pigment, dyestuff, skimmer, coupling agent etc.
The form that the present invention is used for the base material of thermal bond need not special qualification, as, it can be nonwoven fabric, film or sheet.In view of convenient processing, preferred nonwoven fabric or film.
When combining complex-shaped bonding parts with the base material that is used for thermal bond, the base material that requires to be used for thermal bond can be formed neatly.In this case, the base material that is used for thermal bond is preferably nonwoven fabric.Nonwoven fabric is according to its type of service, through known preparing method's preparation.
For be provided with more equably with the base material of bonding parts thermal bond with, the base material that is preferred for thermal bond is a film.The performance of film need not special qualification, and the preparation of film also can be adopted known method.Consider the handiness that is adapted to complicated shape, preferred thickness is 0.01-0.5mm, more preferably 0.03-0.2mm.
For convenient processing, the unit weight that is preferred for the base material of thermal bond is 1-100g/m
2, 3-80g/m more preferably
2, further be preferably 5-60g/m
2
Thermal bond among the present invention can be used for combining the bonding parts with base material, and these bonding parts are selected from the very big material of scope, like thermosetting resin, thermoplastic resin, metallic substance, carbonaceous material, fiber, timber and paper.The laminate of a kind of preferred form of the parts that bond for being made up of compositions of thermosetting resin wherein is arranged in each layer by the reinforcing fibre group of being made up of a large amount of continuous fibers.The instance of thermosetting resin comprises epoxy resin, maleimide resin, phenolic resin, vinylester resin, unsaturated polyester resin, have the terminal resin of cyanate, have the allyl group end group resin, have the acetylene end group resin, have the terminal resin of interior methyne tetrahydrochysene phthalic acid (nadic acid), have the resin of benzocyclobutene end.In view of the mechanical property of bonding parts, preferably use epoxy resin.
The instance of used reinforcing fibre comprise thomel, steel fiber, spun glass, organic fibre, inorganic fibre, with and go up the above-mentioned fiber that applies conductive of material.Wherein, the lightweight and the mechanical property of bonding parts are taken all factors into consideration, preferably used thomel.
The base material that the present invention is used for thermal bond make laminate preferably conduct be used for the base material 62 of thermal bond.
Electromagnetic-shielding molded article of the present invention:
With reference to Figure 13 electromagnetic-shielding molded article of the present invention are described.Among Figure 13; Electromagnetic-shielding molded article C3 obtains through the first structure unit A3 and the second structure unit B2 are combined into one; Wherein, The first structure unit A3 is made up of the resin combination that is arranged with in each layer by a large amount of continuous transmission property the led group of fibers of forming, and the second structure unit B3 is made up of the thermoplastic resin composition.
The instance of used conductive fibers comprises itself having conductive fiber among the first structure unit A3; Like steel fibers such as aluminum fiber, copper fiber and Stainless Steel Fibres, based on the thomel of polyacrylonitrile, based on the thomel of regenerated fiber, based on the thomel of xylogen, based on bituminous thomel and graphite fibre, and the fiber that on these fibers, further applies conductive metal.Also can adopt non-conductive fibre, comprise spun glass; Organic fibre is like aromatic polyamide fibre, pbo fiber, polyphenylene sulfide, trevira, acryloyl fibrid, tynex and wynene; And inorganic fibre, like silicon carbide fiber and silicon nitride fiber, be coated with conductive material on these fibers respectively.Conductive of material the method on the fiber of being coated in is comprised plating method that metal such as nickel, ytterbium, gold and silver, copper and aluminium are carried out (electrolytic or do not have electricity), CVD method, PVD method, ion plating and vapour deposition process.Above-mentioned arbitrary method is used to form one deck conducting stratum at least.
Can use above-mentioned any Conductive fiber or use two kinds at least.Take all factors into consideration each factor of specific tenacity, specific rigidity and lightweight, preferably use thomel.From consideration to lower production cost, the especially preferred thomel that uses based on polyacrylonitrile.
For the resinous principle that is used for the first structure unit A3, thermosetting resin or thermoplastic resin all can use.If the use thermosetting resin, rigidity and the intensity of moulding article C3 are then fine; If the use thermoplastic resin, resistance to impact shock and the recycling performance of moulding article C3 are then fine.
The instance of thermosetting resin comprises unsaturated polyester, vinyl acetate, epoxide, phenol (resol resin type), urea/melamine, polyimide, its multipolymer and modified product, and with above-mentioned at least two kinds of resins that mix gained.For strengthening shock resistance, also can add elastomerics or rubber constituent.
The instance of thermoplastic resin comprises polyester, like polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PTT (PTT), PEN (PEN) and liquid crystal polyester; Polyolefine is like Vilaterm (PE), Vestolen PP 7052 (PP) and polybutylenes; Styrene resin; Polyoxymethylene (POM); Polyamide (PA); Polycarbonate (PC); Polymethylmethacrylate (PMMA); SE (PVC); Polyphenylene sulfide (PPS); Ppe (PEE); Modified PE E; Polyimide (PI); Polyamidoimide (polyamideimides, PAI); Polyetherimide (PEI); Polysulfones (PSU); The PSU of modification; Polyethersulfone; Polyketone (PK); Polyetherketone (PEK); Polyetheretherketone (PEEK); PEKK (PEKK); Polyene propionic ester (PAR); Polyethers nitrile (PEN); Phenolic resin; Phenoxy resin; Fluorine resin is like tetrafluoroethylene; And based on the thermoplastic elastomer of PS, polyolefine, urethane, polyester, polymeric amide, polyhutadiene, TR 301 and fluorine etc.; And the multipolymer of above-mentioned substance and modified product, the resin of above-mentioned at least two kinds of material mixing gained in addition.Also can in thermoplastic resin, add elastomerics or rubber constituent, to strengthen shock resistance.
Consider from formability, mechanical property and capability of electromagnetic shielding factor, constitute preferably that conductive fibers content is 20% to 90% in the resin combination of the first structure unit A3, more preferably 30% to 80%.
The form of the first structure unit A3 can for example be: laminate, and wherein conductive fibers is laminated in each layer; Sandwich type, the core material that the resin of wherein being strengthened by resin combination, discontinuous fiber, metal, foams etc. are formed are positioned in the middle of the skin-material, and it makes by in each layer, arranging conductive fibers; Perhaps sandwich type wherein places the core material that is arranged with conductive fibers in each layer between the skin-material.Because need be convenient to make electromagnetic-shielding molded article C3, the first structure unit A3 is preferably laminate.
Be the electromagnetic-shielding molded article C3 of the housing form that obtains to be suitable for electrical equipment or electronics, the needs first structure unit A3 have at least one hither plane part.It is desirable to, it all is hither plane that the surface that has maximum area among the first structure unit A3 has more than 50%.
As the housing of electrical equipment or electronics, consider that from the angle of lightweight and thin thickness the preferred mean thickness of structure unit A3 is 1.6mm or littler, more preferably 1.2mm or littler further is preferably 1.0mm or littler, especially is preferably 0.8mm or littler.The mean thickness of the first structure unit A3 is at least 5 thickness average value that the some place measures that on average are scattered in the hither plane part.When measuring mean thickness, got rid of the special shape district, like rib, pivot and sunk part/protuberance.
The shadow area of the first structure unit A3 need not special qualification, as long as structure unit can be suitable for electromagnetic-shielding molded article C3.But, consider the capability of electromagnetic shielding that improves integration product, the shadow area of first structure unit preferably is suitable for the top end face desired size of casting of electronic device.Consider the housing as notebook personal computer, the shadow area of first structure unit is preferably 200cm
2Or bigger, 400cm more preferably
2Or bigger, further be preferably 600cm
2Or it is bigger.Shadow area is the observed value of the expression moulding article surface size that obtains of the outside dimension according to moulding article C3.
Electromagnetic-shielding molded article C3 of the present invention has good capability of electromagnetic shielding.The capability of electromagnetic shielding value of the first structural unit A3 that under the frequency of 1GHz, records through the KEC method is 40dB or bigger, is preferably 45dB or bigger, more preferably 50dB or bigger.
The KEC method is a Kansai Electronic Industry Development Center appointed method, test sample is placed in the shielding box of horizontal or vertical symmetry separation, tests attenuation of Electromagnetic with spectrum analyzer.For carrying out this test, cut the suitable flat board of a part of area as test sample from the first structure unit A3.
Consider that electromagnetic shielding China ink plastid C3 is used for the housing of electrical equipment or electronics; Break for avoiding being installed in parts on the moulding article C3, deflection, distortion; The bending elastic modulus of at least one hither plane part is 8Gpa or bigger in first structure unit that preferably records according to the method for ASTM D790; More preferably 10Gpa or bigger further is preferably 12Gpa or bigger.Usually, the housing of electrical equipment or electronics is in order to protect the responsive circuit of inner impact, load and short circuit, fragile part etc., can to think that this housing receives than heavy load.In this purposes, because no matter breaking or deflection or distortion that load caused can both cause internal circuit and parts by havoc.
The bending elastic modulus of the first structure unit A3 is different and different according to the orientation of conductive fibers (reinforcing fibre) wherein, and bending elastic modulus is meant the minimum value of bending elastic modulus in this specification sheets.Usually, the test sample of measuring bending elastic modulus is prepared 4, preferred 6 at least.During preparation, from the hither plane part of the first structure unit A3, with different angles, promptly 0 degree, 45 degree, 90 degree, 135 degree with respect to the first structure unit A3 longitudinal direction cut.The gained test sample is used to measure the bending elastic modulus value according to ASTMD790.Preferred test sample is taken from the special shape zone, like the part beyond rib, pivot and the depression/protuberance.If test sample comprises these special shape parts, then the position of the thickness of test sample beyond will be at these positions measured.Minimum value in the measured bending elastic modulus of above-mentioned test specimens fragment is a said bending elastic modulus in this specification sheets.
Among the integral part second structure unit B3 of electromagnetic-shielding molded article C3, the thermoplastic resin composition can be identical with the thermoplastic resin composition of the first structure unit A3.Preferably contain discontinuous reinforcing fibre among the employed thermoplastic resin composition.
Used reinforcing fibre need not special qualification, can be identical with used reinforcing fibre among the laminate A of the present invention.Reinforcing fibre among the second structure unit B3 is preferably conductive fibers.Consider that from lightweight and the mechanical property angle of prepared electromagnetic-shielding molded article C3 conductive fibers is preferably thomel.Reinforcing fibre also can be made up of at least two kinds of reinforcing fibres.
In the second structure unit B3, preferred reinforcing fibre is dispersed among the thermoplastic resin composition.Ratio about thermoplastic resin composition and reinforcing fibre; Consider that from each combined factors of formability, intensity and lightweight thermoplastic resin composition's content is preferably 25-95%, more preferably 35-85%; The content of reinforcing fibre is preferably 5-75%, more preferably 15-65%.
If the length of discontinuous reinforcing fibre is long more, it is just big more to strengthen intensity and inflexible effect, and the effect that especially improves resistance to impact shock is just obvious more, and this is known.In containing the resin combination of discontinuous reinforcing fibre, the length that is included in the discontinuous reinforcing fibre in the resin combination is also inequality, but divides fabric in the scope of different lengths.Adopt number average fiber length Ln and weight average fiber length Lw to represent the staple length of reinforcing fibre.
Number average fiber length Ln is that it has reflected the contribution of staple fibre with the simple average value of the metric staple length of surveyed fiber number.With the growth of staple length, be enhanced based on the stiffening effect of staple length.Because the effect of macrofiber and section fibre is different, does not think preferably that they are equivalent.When considering long stapled stiffening effect, need to consider weight average fiber length Lw.When passing judgment on the mechanical property of moulding article C3, preferably adopt the weight average fiber length Lw of the discontinuous reinforcing fibre among the second structure unit B3.
According to the ratio Lw/Ln of weight average fiber length Lw and number average fiber length Ln, just can know the branch fabric of staple length.If greater than 1, then meaning, Lw/Ln comprised more macrofiber.Discontinuous reinforcing fibre length among the preferred second structure unit B3 is longer, and the macrofiber that comprises is many more.
The preferred weight average fiber length Lw of discontinuous reinforcing fibre of the second structure unit B3 is 0.4mm or longer, and the ratio Lw/Ln of weight average fiber length Lw and number average fiber length Ln is 1.3-2.0.Weight average fiber length Lw is 0.4-1.0mm more preferably.
Number average fiber length Ln, weight average fiber length Lw and Lw/Ln can obtain through following method.Just, from second structure unit B3, partly cutting a sheet that 10mm is long, 10mm is wide adopts as coupons.The coupons of preparing is immersed and can reach 24 hours in the solvent of solution heat plastic resin, with the dissolving resin component.Residue sample after using the microscopic examination resin Composition that amplifies 10-100 times dissolved.In field of view, optional 400 reinforcing fibres are observed.According to the staple length Li that is surveyed, number average fiber length Ln and weight average fiber length Lw can calculate through formula:
Number average fiber length Ln=(∑ Li)/(N)
Wherein, N by the quantity (400) of survey fiber.
Weight average fiber length Lw=(∑ Li
2)/(∑ Li).
For the second structure unit B3 that contains reinforcing fibre through method of forming manufacturing, wherein weight average fiber length Lw is 0.4mm or bigger, and Lw/Ln is 1.3-2.0, disclosed macrofiber grain among the JP63-37694B capable of using.The length of each macrofiber grain basically with the granule equal in length, and form by the reinforcing fibre and the thermoplastic resin composition that arrange along the granule longitudinal direction.Also can use among the JP60-62912U disclosed by the granule of coating.Each coating granule is through the thermoplastic resin composition being coated on the continuous reinforcing fibre group, and then is cut into predetermined length and makes.The second structure unit B3 can be that fiber and the resin combination granule of 1-20mm mixes mutually and carry out injection molding and get through being cut into length.This forming method is a preferred method.
With compare through the moulding article that the moulding of staple fibre grain is made, better through the mechanical property that makes the moulding article that the moulding of macrofiber grain makes, this is owing to contain macrofiber in the moulding article, also contains more macrofiber because of in the moulding article.The length of macrofiber grain is preferably 1-20mm, obtains long stapled stiffening effect thus and avoid fiber to be entangled in to be used for the screw rod of the forcing machine of moulding.The length of macrofiber grain is 3-10mm more preferably.
Be the characteristic that acquisition needs, comprise weighting agent and additive as the thermoplastic resin composition of the second structure unit B3 composition.Weighting agent and additive comprise inorganic filler, fire retardant, give conductive material, crystal nucleating agent, UV light absorber, inhibitor, sound-proof material, biocide, sterilant, reodorant, anti-staining agent, thermo-stabilizer, release agent, static inhibitor, softening agent, lubricant, tinting material, pigment, pore forming material, coupling agent etc.
The instance of giving conductive material comprises carbon black, amorphous carbon powder, natural graphite powder, graphous graphite powder, expanded graphite powder, pitch microballon, from the thomel and the carbon nanotube of vapor phase growth.These can be preferred for further strengthening the effectiveness of electromagnetic-shielding molded article C3.
Electromagnetic-shielding molded article C3 of the present invention makes through the first structure unit A3 and the second structure unit B3 are carried out integrated combination.The first structure unit A3 and the second structure unit B3 carry out integrated bonded method and need not special qualification.One of method is in advance with the first structure unit A3 moulding, in the time of again with the second structure unit B3 moulding, itself and the first structure unit A3 is combined into one.Another method is in advance with the second structure unit B3 moulding, again with the first structure unit B3 moulding, itself and the second structure unit B3 is combined into one.Another method is to make laminate A3 and structure unit B3 moulding in advance respectively, then the two is combined into one.The method that two structure units are combined into one comprises bonding, welding, assembling, embedding etc.Especially preferred integrated combining method embeds in the mould for the first structure unit A3 with moulding in advance; Injection will be formed as the thermoplastic resin composition of second structure unit then, thereby the second structure unit B3 and the first structure unit A3 are combined into one.Another preferred integrated combining method is to utilize the method for ultra-sonic welded to carry out integrated combination first structure unit A3 of moulding in advance and the second structure unit B3 of moulding in advance.If the first structure unit A3 is laminate A of the present invention, then can obtain good bonding strength.
Another kind of integrated combining method is; To obtain by injection molding in advance; And in the second structure unit B3 embedding pressing mold through aftertreatment; Put into the prepreg that is used to form the first structure unit A3 then above that, said prepreg contains the base material of being made up of the continuous conductive fibers of injecting resin combination.Then, adopt vacuum-bag molding that the first structure unit A3 and the second structure unit B3 are combined into one.
Another integrated combining method is, for processing through pressing mold in advance, and through aftertreatment with the first structure unit A3, and process by injection molding in advance, and, use known sticker that the two is combined through the second structure unit B3 of aftertreatment.
Prepare the first structure unit A3 method and need not special qualification; The example comprises the well-known process of utilizing compositions of thermosetting resin, can be by preferred use like the manual twisting method of forming, spray-up moulding method, vacuum-bag molding, pressure moulding method, autoclave molding method, compression moulding and transfer moudling.
Prepare the second structure unit B3 method and need not special qualification, the example comprises well-known process, like injection moulding, extrusion moulding and compression moulding.The suitable method of using is an injection moulding, and reason is that its productivity is high, can make the second structure unit B3 with pivot section 151 and the such complicated shape of jut 152 (shown in Figure 13) carry out scale operation.
The first structure unit A3 and the second structure unit B3 are combined into one and the electromagnetic-shielding molded article C3 that the obtains integral structure after must keeping combining.Therefore, the bonding interface of part at least of the preferred first structure unit A3 and the second structure unit B3 contains tack coat.More than 50% of bonding interface area that preferred tack coat covers is more preferably more than 70%.Preferred especially tack coat covers the surface of whole bonding interface.
The material of tack coat can be by with constitute the first structure unit A3 and constitute with the different or similar material of the second structure unit B3.Consider and the bonding strength of the second structure unit B3 that matrix material is preferably and the similar resin of thermoplastic resin composition that constitutes one of second structure unit B3 parts.
The form of electromagnetic forming article need not special qualification.Electromagnetic-shielding molded article C3 can have curved surface, rib, pivot, projection or emptying aperture.Electromagnetic-shielding molded article C3 also can decorate from the teeth outwards, can adopt methods such as plating, coating, vapour deposition, embedding, punching press or laser radiation to handle.If the pattern of reinforcing fibre can be seen from the outside among the first structure unit A3, will produce design effect to electromagnetic-shielding molded article C3.
Electromagnetic-shielding molded article C3 can be used to as among the laminate A of the present invention.Suitable purposes comprises: the housing of electrical equipment and electronics; Such as PC, indicating meter, business automation equipment, Cell phone, portable data assistance, facsimile recorder, CD, portable MDs, portable radio, PDAs (portable data assistance is like electronic memo), pick up camera, digital camera, opticinstrument, stereo set, sky wither, the housing of set lights, amusement equipment, toy and other household electrical appliances; Internal part is like support and chassis; Their casing; Mechanical part; Electricity equipment unit and automobile and ROV internal part etc.
Owing to have a good capability of electromagnetic shielding, electromagnetic-shielding molded article C3 can be aptly as the housing or the external component of electrical equipment or electronics, also can be aptly as the housing of the notebook personal computer of slim, big shadow area, portable data assistance etc.When electromagnetic-shielding molded article C3 is used as this shells, consider that from the angle of capability of electromagnetic shielding at least a portion of the top end face of preferred housing is the first structure unit A3.More preferably to surpass 50% shadow area be that the first structure unit A3 forms to top end face, and further preferred top end face is that the first structure unit A3 forms above 70% shadow area.When electromagnetic-shielding molded article C3 requires one more during complex inner structure, preferred framework, projection, rib, pivot, slipper and to comprise above-mentioned parts one of arbitrarily be in second structure unit B3, to form.
Embodiment
Describe the present invention in conjunction with embodiment and comparative example.Except as otherwise noted, all mixture ratios (%) are based on the numerical value of weight percent among embodiment and the comparative example.
Embodiment 1: laminate and integrated molding:
Embodiment 1-1: laminate A4
From the prepreg of the reinforcing fibre group that contains epoxy resin (thermosetting resin) and form with a large amount of carbon filaments that direction is arranged, cut out six rectangle prepregs with predetermined size as matrix resin; Wherein the weight content of reinforcing fibre group (Wf) remains on 70%; Volume content (Vf) remains on 61% (Toray Industries, the Torayca Prepreg P6053-12 that Inc. makes).In Figure 14, these 6 161-166 illustrate with skeleton view.The two ends of these sheets are bent to form shortwall.
With rectangular long side direction is 0 °, and six prepreg 161-166 are from beginning respectively with 45 ° ,-45 °, 90 °, 90 ° ,-45 ° and 45 ° according to carrying out lamination from order (shown in the arrow 160) (not shown) the master tooling of stamper that begins down.
On the other hand, having base material band preset width, that be used for thermal bond is to make from the base material that is used for thermal bond, described in following embodiment 3-1.Spread two base material bands 171 that are used for thermal bond, on prepreg 166, carry out lamination, thereby width is part and two bent ends (shown in the arrow 170) covering of about 20mm on every side.
Then, the male mould (not shown) is installed and carries out pressing mold.160 ℃ of following preheatings 5 minutes, make base material 171 fusings to carry out thermal bond in the pressing mold machine, applied pressure is 6Mpa, and veneer sheet heated 30 minutes down at 150 ℃, made thermosetting resin cured.After solidifying completion, veneer sheet is cooled off under room temperature, from mould, shift out then, thereby obtain laminate A4, its mean thickness is 0.7mm.
The lamination position that from laminate A4, is used for the base material 171 of thermal bond cuts out test sample, with methyl alcohol supersound washing 30 minutes, removes the thermoplastic resin of the base material 171 that is used for thermal bond.Observation post gets test sample under SEM.On the surface of test sample, can see the state that exposes fibrous bundle.And, on the xsect of test sample, can see a double-layer structure, wherein one deck is made up of the group of fibers layer that the surface direction along laminate A4 contains the cavity, and another layer is made up of the group of fibers layer that the internal direction along laminate A4 does not contain the cavity.This double-layer structure is as shown in Figure 5.The interface 44 that can find out thermoset resin layer and thermoplastic resin is rough.Layer with the group of fibers 43b in cavity 45 is arranged with the zone of continuous fibers in thermoplastic resin.In this zone, measured the maximum ga(u)ge TPf-max and the minimum thickness TPf-min in the zone of wherein containing a 43b.Minimum thickness TPf-min is 30 μ m, and maximum ga(u)ge is 50 μ m.
Cut away be used for thermal bond among the laminate A4 the base material band not by laminated part, the DSC that makes through PerkinElmer measures the glass transition temperature of thermoset resin layer resin.The glass transition temperature of surveying is 130 ℃.
For the bending elastic modulus of measuring 0 °, 45 °, 90 ° and 135 ° direction (rectangular vertically be 0 °), from laminate A4 rectangle bottom respectively with respective angles cutting test sample.Institute's lateral bending modulus in elasticity in bending is maximum in the time of 45 °, and promptly maximum on the outermost fibers direction, its value is 116Gpa.The bending elastic modulus of being measured is minimum in the time of 135 °, and is minimum when promptly becoming 90 ° direction with outermost fibers, and its value is 25Gpa.
From laminate A4 incised layer pressing plate, its form meets the bonding parts of ISO04587.The bind mode of veneer sheet is that the part that has the base material band that is used for thermal bond among the laminate A4 mutually combines, and veneer sheet pressurizeed 5 minutes down at 180 ℃, to make test sample with the pressure of 6Mpa.The gained test sample is used to measure the bonding strength under the room temperature, and its value is 20Mpa.The test intensity after, the bonding interface of observation test print, can see the silk separate from bonded laminate A4.
Embodiment 1-2: integrated molding C5
Make integrated molding C5 shown in Figure 15.Laminate (1-1) embeds in the mould it to carry out the injection molding (not shown) as laminate A5.Arranged the macrofiber grain in advance, it is 20% thomel (TorayIndustries, the TLP1146 that Inc. makes) that the macrofiber grain contains as the polyamide resin of matrix resin and weight percent (Wf).Granule injection molding is become bonding parts B5, and these bonding parts have outside framework, projection and pivot so that laminate A5 embeds, thus preparation integrated molding C5.The base material band that will be used for thermal bond is bonded in the laminate A5 and bonding parts B5 bonding interface place of embedding, and the said base material band that is used for thermal bond will be made by the thermal bond base material described in the embodiment 3-1.During injection molding, use Japan Steel Works, the J350EIII injection moulding machine (J350EIII InjectionMolding Machine) that Ltd. makes, the temperature of cylinder is 280 ℃.
Embodiment 1-3: laminate A6
At first the particle (180 ℃ of fusing points, by Ube Industries, Ltd. produces) to polymeric amide 12 resins carries out hot pressing, makes the base material that is used for thermal bond, and it is the thick films of 70 μ m.Then,, prepreg is carried out lamination, and of will the make base material film that is used for thermal bond places and carries out lamination on the whole veneer sheet according to the same procedure of embodiment 1-1.
Subsequently, adopt hot plate to carry out preheating, make temperature reach 190 ℃, preheating 5 minutes is used in the base material fusion of thermal bond, heats 30 minutes at 150 ℃ with stamper, and pressure is 3Mpa, and to make laminate A6, its mean thickness is 0.8mm.
Remove the thermoplastic resin among the laminate A6 make with formic acid, measure the thickness that is arranged with the zone of continuous fibers in the thermoplastic resin.Minimum thickness Tpf-min is 20 μ m, and maximum ga(u)ge Tpf-max is 30 μ m.The resin glass invert point of thermoset resin layer is 134 ℃.
The bending elastic modulus of laminate A6 is minimum in 135 ° direction, and its value is 26Gpa.
According to the described method of embodiment 1-1, be pressurization 5 minutes under the 6Mpa at 195 ℃, pressure, make test sample.According to ISO04587, measure the bonding strength under the room temperature with test sample, its value is 14Mpa.After the test bonding strength, the bonding interface of observation test print can see that silk separates from bonded laminate A6.
Embodiment 1-4: integrated molding C7
According to the method for embodiment 1-2, laminate A6 is embedded in the mould to make integrated molding C7.
Embodiment 1-5: laminate A7
Except that following step, all the other prepare laminate A7 according to the described method of embodiment 1-1.Before the lamination prepreg, will place on the whole laminate surface of master tooling as the polyamide 6 film (the Rayfan NO1401 that Toray Gosei FilmK.K. makes, thickness is 50 μ m, 210 ℃ of fusing points) of the base material that is used for thermal bond.Then; The braided fabric prepreg is laminated into 0 °/90 °; Wherein this prepreg contains the epoxy resin as matrix resin; The weight content (Wf) that is the thomel group (Toray Industries, the Torayca prepreg F6343B-05P that Inc. makes) of same direction arrangement in the epoxy resin is 60%.Again with unidirectional 4 prepreg (Toray Industries; Inc. the Torayca prepreg F6053B-12 that makes) be laminated into 45 ° ,-45 ° ,-45 ° and 45 °; And then braided fabric prepreg (F6343B-05P) is laminated into 0 °/90 °; Wherein this prepreg contains the epoxy resin as matrix resin, and the weight content (Wf) that is the thomel group of single direction arrangement in the epoxy resin is 60%.At last, polyamide 6 film (RayfanNO1401) is laminated to the whole veneer sheet as the prepreg of the base material that is used for thermal bond.
Then, before carrying out pressing mold, earlier carry out preheating with hot plate, make temperature reach 225 ℃, preheating 3 minutes is used in the base material fusion of thermal bond, and 150 ℃ of heating 30 minutes down, pressure is 6Mpa, thereby makes laminate A7 with stamper, and its mean thickness is 0.9mm.
Be arranged with the thickness in the zone of continuous fibers in the thermoplastic resin of the laminate A7 that measurement makes according to the method for embodiment 1-3.Minimum thickness Tpf-min is 10 μ m, and maximum ga(u)ge Tpf-max is 40 μ m.
With two lip-deep thermoplastic resin excisions, measure the glass transition temperature of thermoset resin layer.The resin glass invert point of thermoset resin layer is 132 ℃.
Be to measure the bending elastic modulus of all directions 0 °, 22.5 °, 45 °, 90 °, 112.5 ° and 135 ° (the rectangle longitudinal direction is 0 °), from the test sample of each angle of Bottoming of gained laminate A7.The bending elastic modulus of laminate A7 is minimum in 22.5 ° direction, and its value is 20Gpa.
According to the described method of embodiment 1-1, be pressurization 5 minutes under the 6Mpa at 225 ℃, pressure, make test sample.According to ISO04587, measure the bonding strength under the room temperature with test sample, its value is 16Mpa.After the test bonding strength, the bonding interface of observation test print can see that silk separates from bonded laminate A7.
Embodiment 1-6: integrated molding C8
According to the described method of embodiment 1-2, laminate A7 is embedded in the mould, make integrated molding C8.
Macrofiber grain (Toray Industries, the TLP1146 that Inc. makes) injection molding is become bonding parts B8, and it is similar with bonding parts B5 shown in Figure 15.Adopt the ultra-sonic welded parts B8 that will bond to combine with integrated molding C8.For ultra-sonic welded, adopted Seidensha Electronics Co., ultrasonic living welding machine SONOPET Σ-1200S/R that Ltd. makes, operating frequency is 19kHz, pressure is 1kN.
Embodiment 1-7: laminate A9
According to the described method of embodiment 1-1, prepreg is carried out lamination, at last polycarbonate membrane (Bayer AG makes for polycarbonate membrane, thickness 50 μ m) is laminated to as the whole prepreg veneer sheet that is used for the base material of thermal bond.
Then, carry out preheating with hot plate, make temperature reach 260 ℃, preheating 3 minutes is used in the base material fusion of thermal bond, and 150 ℃ of heating 30 minutes down, pressure is 6Mpa, thereby makes laminate A9 with stamper, and its mean thickness is 0.7mm.
Remove the thermoplastic resin among the laminate A9 with methylene dichloride, measure the thickness that is arranged with the zone of continuous fibers in the thermoplastic resin.Minimum thickness Tpf-min is 10 μ m, and maximum ga(u)ge Tpf-max is 20 μ m.
Remove two lip-deep thermoplastic resins through excision, measure the glass transition temperature of thermoset resin layer.The resin glass invert point of thermoset resin layer is 134 ℃.
Measure the bending elastic modulus of laminate A9, bending elastic modulus is minimum in 135 ° direction, and its value is 25Gpa.
According to the described method of embodiment 1-1, be pressurization 3 minutes under the 6Mpa at 260 ℃, pressure, make test sample.According to ISO04587, measure the bonding strength under the room temperature with test sample, its value is 11Mpa.After the test bonding strength, the bonding interface of observation test print can see that silk separates from bonded laminate A9.
Embodiment 1-8: integrated molding C10
With two spiral shell forcing machine (Japan Steel Works; Ltd. thomel (the Toray Industries that the two spiral shell forcing machine TEX-30 α that make) makes polycarbonate resin (the polycarbonate resin Lexan121R that GE Plastics Japan ltd. makes) and shred; The thomel TS-12 of the chopping of Inc. making) combines, make fibre content and be 30% injection molding and use granule.
Laminate A9 is embedded in the injecting molding die, utilize prepared injection molding to make integrated molding C10 with granule.
In each integrated molding of embodiment 1-2,1-4,1-6,1-8; Laminate with good rigidity and the injection molded article structure unit mortise that is beneficial to the complicated shape moulding are together; Applicable to electrical equipment and electronics, like the housing of notebook computer, and; The pattern of the reinforcing fibre the laminate can be seen from the outside, its commercial value can be further promoted.
Comparing embodiment 1-1: laminate PA1
According to the method for embodiment 1-1, except that the base material that is used for thermal bond not by the lamination, prepreg is carried out lamination.
Then, for carrying out pressing mold, pressurize under 30 minutes the condition of heating down at 150 ℃, pressure is 6Mpa, thereby makes laminate PA1, and its mean thickness is 0.7mm.
Between the laminate PA1 that obtains and another parts PB1 heat bonding does not take place, reason is not have thermoplastic resin on the surface of moulding article PC1.The incised layer pressing plate, the structural similitude of the bonding parts of the structure of this veneer sheet and ISO04587.Pressurizeed 24 hours down at 25 ℃; Pressure is 1Mpa; Utilize two subsides epoxy adhesives (two-pack epoxy adhesive, the SwanBond4000 that Takada chemical Products Mfg.Co. makes) that laminate PA1 and another parts PB1 are mutually combined in junction, make test sample.At room temperature, the bonding strength of test test sample.Bonding strength is 4Mpa.
Comparing embodiment 1-2: integrated molding PC2
According to the described method of embodiment 1-2, the laminate PA1 of comparing embodiment 1-1 is embedded in the injecting molding die, and macrofiber grain (Toray Industries, the TLP1146 that Inc. makes) injection molding is become shell, projection and pivot.But,, product immediately laminate PA1 and injection-molded parts PB1 are separated from each other after shifting out, and do not carry out bonding strength and measure.
Comparing embodiment 1-3: laminate PA3
Make the laminate PA3 that mean thickness is 0.9mm according to the said method of embodiment 1-5, used pressure is 6Mpa, but without preheating, the temperature during pressing mold is 150 ℃, suppresses 30 minutes.
According to the said method of embodiment 1-3,, but can't see the group of fibers layer that contains the cavity with formic acid washing gained laminate PA3.Observe xsect with SEM, do not arrange continuous fibers in the thermoplastic resin.Confirm that this state and situation shown in Figure 6 are similar.
Remove two lip-deep thermoplastic resins through excision, measure the glass transition temperature of thermoset resin layer.The resin glass invert point of thermoset resin layer is 130 ℃.
According to the described method of embodiment 1-1, be under the 6Mpa at 225 ℃, pressure, pressurizeed 5 minutes, make test sample.According to ISO04587, measure the bonding strength under the room temperature with test sample, its value is 0.6Mpa.Find that test sample is easy to be separated from each other.
Comparing embodiment 1-4: integrated molding PC4
According to the method for embodiment 1-6, laminate PA4 is embedded in the mould, make integrated molding PC4.
Measure the laminate PA4 of gained integrated molding PC4 and the normal bonding strength between the injection molding parts PB4.Near the bonding interface between laminate PA4 and the injection molding parts PB4, separate integrated molding PC4, record normal bonding strength and be lower than 1Mpa.After the separation, observe the adhesive surface of injection molding parts PB4, do not see the silk that breaks away from from laminate PA4.
The bonding strength of the integrated molding of comparing embodiment 1-2 and 1-4 between laminate and injection molding parts is big inadequately, has the isolating problem that is easy to.Therefore, different with the laminate of embodiment is, adopts any method that makes things convenient for high productivity or big throughput, all is difficult to the laminate of comparing embodiment is processed integrated molding.
Embodiment 2: laminate and integrated molding:
The skeleton view of the model housing C2 of electrical equipment that following reference is shown in Figure 9 or electronics launches to describe to embodiment.
With reference to embodiment 2-1: be used for injection molding material
With two spiral shell forcing machine (Japan Steel Works; Ltd. the TEX-30 α that makes) with polyamide 6 resin (Toray Industries; Inc. the polyamide 6 resin CM1001 that makes) with the thomel (TorayIndustries that shreds; The thomel TS-12 of the chopping of Inc. making) combine, the fiber granule is used in the injection molding that makes content and be 30wt%.
Embodiment 2-1: laminate A21
With prepreg (Toray Industries; Inc. the Torayca prepreg 3051S-12 that makes) be cut into predetermined size; This prepreg contains the epoxy resin (thermoplastic resin) as matrix resin; The weight content of thomel group (Wf) is 63% in the matrix resin, processes long 350mm, the laminate of wide 300mm.
The prepreg of 6 cuttings is carried out lamination on stamper mould, fiber direction is from beginning to be respectively 45 ° ,-45 °, 90 °, 90 ° ,-45 ° and 45 ° (longitudinal direction of rectangle prepreg is 0 °).At last, will be pressed onto the lamination prepreg like described two substrate layers that are used for thermal bond of following embodiment 3-1.
Then, be preheated to 160 ℃ with stamper, preheating 5 minutes is used in the base material fusion of thermal bond, and the pressure that adopts 6Mpa again makes thermosetting resin cured 150 ℃ of pressurizations 30 minutes down.After the curing, at room temperature the cooling layer pressing plate makes the laminate that thickness is 0.7mm.Observe the xsect of this laminate with SEM, thermoplastic resin fusion film forming and being attached on the surface, the thickness of film is 10 μ m.This laminate perforation to be processed into the structure of laminate A2 (top board) shown in Figure 9, is used as laminate A21.
Embodiment 2-2: integrated molding C22
The laminate A21 that embodiment 2-1 is made is used as laminate A22, and it is embedded in injecting molding die, will obtain structure unit B22 with reference to the injection molding granule injection molding that makes among the embodiment 2-1, and it is similar to structure unit B2 shown in Figure 9.In the integrated molding C22 that obtains, laminate A22 and structure unit B22 are combined into one each other securely.This integrated molding C22 can be used as housing.
From laminate A22 and structure unit B22 combining site cutting integrated molding C22, obtain the test sample of 10mmx10mm, directly measure normal bonding strength.(Three Bond1782) bonds together brake(-holder) block and test sample with sticker, measures normal bonding strength.Test result is, under 40 ℃, do not rupture between laminate and the injection molding parts, but fracture appears in laminate and brake(-holder) block bonding part.Under 140 ℃, normal bonding strength is 4Mpa.
Embodiment 2-3: laminate A23
According to the said method of embodiment 2-1; Prepreg (TorayIndustries with the carbon fibre fabric that contains the braiding of pigtail shape; Inc. the Torayca braided fabric CO6343 that makes) preparation laminate A23 wherein is marked with epoxy resin in the thomel, and the content of thomel is 57vol%.Structure about veneer sheet; 4 prepregs are laminated into 0 °/90 ° (longitudinal direction of rectangle prepreg is 0 °); At last; Will (unit weight be 50g/m for Kureha Chemical Industry Co., the nonwoven polyamide fabric Dynac LNS-0050 that Ltd. makes as the nonwoven polyamide fabric of the base material that is used for thermal bond
2, 135 ℃ of fusing points) be laminated on the laminated prepreg.
Then, adopt vacuum-bag molding under 140 ℃, to be heating and curing 1 hour, obtain the laminate that thickness is 0.9mm.On the surface of laminate A23, nonwoven fabric is melted to film bonds, and the thickness of film is 25 μ m.This laminate perforation to be processed into the structure of laminate A2 shown in Figure 9, is used as laminate A23 (top board).
Embodiment 2-4: integrated molding C24
According to the described method of embodiment 2-2, laminate A23 is used as laminate A24, and it is embedded in mould, utilize injection moulding to prepare structure unit B24.Measure the laminate A24 of integrated molding C24 and the normal bonding strength between the structure unit B24, measuring method is with the anchor clamps method of clamping by force.Test result is, under 40 ℃, normal bonding strength is 21Mpa.Under 140 ℃, normal bonding strength is 2Mpa.
Embodiment 2-5 laminate A25
According to the said method of embodiment 2-3; Prepreg (TorayIndustries with the carbon fibre fabric that contains the braiding of pigtail shape; Inc. the preparation laminate A25 Torayca braided fabric CO6343 that makes); Wherein be marked with 180 ℃ of epoxy resin in the curing in the thomel, the content of thomel is 57vol%.PA membrane (PA membrane that TorayGosei Film K.K. makes, model NO1401, thickness are 80 μ m, 215 ℃ of fusing points) is as the base material that is used for thermal bond.
Then, adopt vacuum-bag molding to be preheated to 220 ℃, preheating 5 minutes is used in the base material fusion of thermal bond, reaches 45 minutes at 180 ℃ of following solidification heat plastic resins, obtains the thick laminate A25 of 0.9mm.On the surface of laminate A25, nonwoven fabric is melted to film bonds, and the thickness of film is 65 μ m.This laminate A25 perforation to be processed into the structure of laminate A2 shown in Figure 9, is used as laminate A25 (plate).
Embodiment 2-6: integrated molding C26
According to the described method of embodiment 2-2, laminate A25 is used as laminate A26, and it is embedded in mould, utilize injection molding to prepare structure unit B26.According to the method for embodiment 2-4, measure the laminate A26 of integrated molding C26 and the normal bonding strength between the structure unit B26.Test result is, under 40 ℃, normal bonding strength is 15Mpa.Under 140 ℃, normal bonding strength is 8Mpa.
Comparing embodiment 2-1: laminate PA21
According to the method for embodiment 2-1, except that the base material that is used for thermal bond not by the lamination, prepreg is carried out lamination.
Comparing embodiment 2-2: integrated molding PC22
According to the described method of embodiment 2-2, in the laminate PA21 embedding mould with comparing embodiment 2-1, prepare structure unit PB22 through injection molding.According to the method for embodiment 2-2, measure the laminate PA22 of integrated molding PC22 and the normal bonding strength between the structure unit PB22.Test result is, under 40 ℃, normal bonding strength is 0.2Mpa.Under 140 ℃, normal bonding strength is 0.1Mpa.
In each integrated molding of embodiment 2-2,2-4,2-6; Laminate with good rigidity be beneficial to injection molded article structure unit mortise that moulding processes complicated shape together; Applicable to electrical equipment and electronics, like the housing of notebook personal computer, and; The pattern of the reinforcing fibre of lamination kind can be seen from the outside, its commercial value can be further promoted.
The laminate of comparing embodiment 2-1 does not have thermal caking, even make integrated molding by it, can not make useful especially product.
In the moulding article of comparing embodiment 2-2, the combination between laminate and the injection molding product is firm inadequately, if as product, then has the isolating problem that is easy to.Therefore, different is with the laminate of embodiment, adopts any method that makes things convenient for high productivity or big throughput, all is difficult to the laminate of comparing embodiment is made integrated molding.
Embodiment 3: the base material that is used for thermal bond
Embodiment 3-1
Through meltblown, adopt to comprise terpolyamide resin granule (terpolyamide resin CM4000, polyamide 6/66/610,150 ℃ of fusing points, Toray Industries, Inc. manufacturing) the wide base material of manufacturing 1000mm, this base material is similar to nonwoven fabric.The unit weight that is used for the base material of thermal bond is 30g/m
2
According to ISO4587, estimate the base material the be used for thermal bond bonding strength S under 160 ℃ of the press temperatures of preheating.
Comparing embodiment 3-1
Utilize acrylic resin (Chisso Corp. makes for acrylic resin, 170 ℃ of fusing points) to make the base material (being similar to nonwoven fabric) that is used for thermal bond.According to the method for embodiment 3-1, estimate the base material the be used for thermal bond bonding strength S under 180 ℃ of the press temperatures of preheating.
Comparing embodiment 3-2
Granule (polyamide 6 resin, 215 ℃ of fusing points, Toray Industries, Inc. manufacturing) with the polyamide 6 resin is made the base material (being similar to nonwoven fabric) that is used for thermal bond.According to the method for embodiment 3-1, estimate the base material the be used for thermal bond bonding strength S under 220 ℃ of the pressed temperatures of preheating.
The evaluation result of the foregoing description is seen table 1.
Table 1
Table 1 result is following.The base material that is used for thermal bond among the embodiment 3-1 has presented good bonding strength when being higher than 130 ℃, when being lower than 160 ℃, be easy to separate, and is suitable for recycling.And the bonding strength of base material in the time of 100 ℃ that is used for thermal bond among the comparing embodiment 3-1 is big inadequately, when reality is used, can go wrong.And be used for the base material of thermal bond among the comparing embodiment 3-2, even in the time of 200 ℃, all be difficult to separate, be unfavorable for recycling.
Embodiment 4: electromagnetic-shielding molded article C41:
Embodiment 4-1
A kind of mode of electromagnetic-shielding molded article C41 of the present invention is described with reference to embodiment 2-2.Electromagnetic-shielding molded article C41 of the present invention makes through the first structure unit A3 is combined with the second structure unit B3 that is made up of thermoplastic resin, and is shown in figure 13.The capability of electromagnetic shielding of the first structure unit A3 that measures through the KEC method is greater than 50dB.
Embodiment 4-2
The laminate of comparing embodiment 2-1 is used as the first structure unit A3.Then, use the mould of embodiment 2-2, be not that laminate is embedded wherein, but insert pad.To become the second structure unit B3 with granule injection molding with reference to injection molding among the embodiment 2-1.
With the mating surface of the alcohol washing first structure unit A3 and the second structure unit B3, use Three BondCo., the two subsides stickers 3921/3926 that Ltd. makes are bonding with the two, obtain integrated molding C3.After the bonding, at room temperature left standstill this integrated molding 24 hours.
The capability of electromagnetic shielding of the first structure unit A3 that measures through the KEC method is greater than 50dB.
Embodiment 4-3
Figure 16 is a decomposition diagram, and showing by the double-deck first structure unit A43 is top board and the electromagnetic-shielding molded article C43 that forms with its structure combining part B 43.
Heated prepreg 30 minutes down at 150 ℃, apply the pressure of 6MPa simultaneously by stamper, make thermosetting resin cured; Prepreg wherein contains Toray Industries; Inc. the Torayca braided fabric CO6343 that makes is marked with epoxy resin in the fabric, the content of thomel is 57vol%.After the curing, cooling at room temperature obtains the first thick structure unit A43 of 0.2mm.
Then, carry out injection molding, obtain the second structure unit B43 with macrofiber granule (Inc. makes for macrofiber granule TLP1146, Toray Industries).
With first structure unit A43 of alcohol washing gained and the mating surface of the second structure unit B43, with Three Bond Co., the two subsides stickers 3921/3926 that Ltd. makes are bonding with the two, obtain integrated molding C43.After the bonding, at room temperature left standstill this integrated molding 24 hours.
The item plate 181 of the integrated molding C43 of gained has bilayer structure.Its thickness is 1.4mm, and capability of electromagnetic shielding is greater than 50dB.Along 0 ° of all directions, 45 °, 90 ° (longitudinal direction of top board is 0 °) cutting test sample, measure bending elastic modulus respectively.To contain projection, rib, pivot or weld seam position gets rid of.The bending elastic modulus of the test sample of 45 ° of directions is minimum, and its value is 15Gpa.
Going up cut lengths from the second structure unit B43 is the test sample of 3mmx3mm, is immersed in the solvent (formic acid) of about 100ml to reach 24 hours, and resinous principle is dissolved.Then, with filter paper filtering reinforcing fibre composition, examine under a microscope the filter paper trapped substance.Select 400 reinforcing fibres at random, measure the length (mm) of fiber.Weight average fiber length Lw is 0.48mm, and the ratio (Lw/Ln) of weight average fiber length Lw and number average fiber length Ln is 1.8.
Comparing embodiment 4-1
To be molded into the model housing with reference to the thermoplastic injection that makes among the embodiment 1.Prepared moulding article top plate thickness is 1.2mm, and capability of electromagnetic shielding is 23dB.Along 0 ° of all directions, 30 °, 60 °, 90 ° (longitudinal direction of top board is 0 °) cutting test sample, measure bending elastic modulus respectively.To contain projection, rib, pivot or weld seam position gets rid of.The bending elastic modulus of the test sample of 45 ° of directions is minimum, and its value is 6Gpa.
The integrated molding of embodiment 4-1,4-2,4-3 is formed by having good electric magnetic shield performance and rigid structural body and being beneficial to the injection molding product structure that is shaped to complicated shape respectively; Therefore, be suitable as the housing of electrical equipment and electronics such as notebook personal computer.
In contrast; The capability of electromagnetic shielding of comparing embodiment 4-1 integrated molding and rigidity are all good inadequately; When it being installed on electrical equipment or the electronics; Such moulding article are difficult to satisfy as as electrical equipment or casting of electronic device, protect internal circuit and prevent these strict demands that propose in recent years of EMI.
Industrial applicibility
Laminate of the present invention can be easy to be combined into one with other structure units, and the bonding strength between the bonded block is very big.The integrated molding that utilizes laminate of the present invention to make shows good aspect mechanical property and lightweight, and when going out of use, can be easy to dismounting.Electromagnetic-shielding molded article of the present invention not only have good capability of electromagnetic shielding, and have thin thickness, light weight and high inflexible advantage, suitable housing as electrical equipment or electronics such as PC, indicating meter or portable data assistance.The base material that the present invention is used for thermal bond has good bonding strength, and is suitable to the matrix material that laminate is combined with other parts.
Claims (5)
1. laminate, it comprises through uncured thermosetting resin being injected the prepreg that the reinforcing fibre group that contains a large amount of continuous fibers forms, and is arranged on said prepreg surface and is used for base material identical and/or different types of bonding parts thermal bond,
Said base material is the copolyamide resin combination as thermoplastic resin; Its fusing point or softening temperature are 100-250 ℃; In the curing reaction of thermosetting resin or in the warm before the curing reaction; Said base material injects the reinforcing fibre group; Said reinforcing fibre group is combined into one with thermoset resin layer that is formed by said thermosetting resin and the thermoplastic resin that is formed by said thermoplastic resin, wherein between thermoset resin layer and thermoplastic resin, form rough interface, and the paranema in the said reinforcing fibre group contacts with the resin of thermoset resin layer at least; All the other paranema in the reinforcing fibre group contact with the resin of thermoplastic resin at least
Wherein, the bonding strength that the adhesive strength performance test methods was measured during said base material was sheared through tension load according to ISO4587 is 7.0MPa or higher in the time of 100 ℃, is 1.0MPa or lower in the time of 200 ℃.
2. laminate according to claim 1, wherein, said bonding strength is St (MPa) in the time of t ℃, when (t+30) ℃, is S
(t+30)(MPa), satisfy relational expression St>=3X S
(t+30)The scope of temperature t between 100 ℃ to 200 ℃.
3. laminate according to claim 1, wherein, said copolyamide resin combination comprises terpolyamide 6/66/610 composition.
4. laminate according to claim 1, wherein, the form of said base material is nonwoven fabric or film, its unit weight is 1-100g/m
2
5. make the method for each described laminate in the claim 1～4; Be included in the described base material that is used for thermal bond is set on the prepreg surface; And between the said thermosetting resin cured reaction period or in the warm before the curing reaction, the said thermoplastic resin that is configured for the base material of thermal bond is injected said reinforcing fibre group.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
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| JP2002-379832 | 2002-12-27 | ||
| JP2002379832 | 2002-12-27 | ||
| JP2002379832 | 2002-12-27 | ||
| JP2003-43920 | 2003-02-21 | ||
| JP2003043920 | 2003-02-21 | ||
| JP200343920 | 2003-02-21 | ||
| JP2003121379 | 2003-04-25 | ||
| JP2003121379 | 2003-04-25 | ||
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| CNB200380107484XA Division CN100421924C (en) | 2002-12-27 | 2003-12-25 | Layered product, electromagnetic-shielding molded object, and processes for producing these |
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| CNB200380107484XA Expired - Lifetime CN100421924C (en) | 2002-12-27 | 2003-12-25 | Layered product, electromagnetic-shielding molded object, and processes for producing these |
| CN2007101270313A Expired - Lifetime CN101085865B (en) | 2002-12-27 | 2003-12-25 | Substrate for heat bonding and method for producing layered product by the same |
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Families Citing this family (58)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090304962A1 (en) * | 2006-02-17 | 2009-12-10 | William Rodgers | Articles of Composite Construction and Methods of Manufacture Thereof |
| CN101746063B (en) * | 2008-12-09 | 2012-05-30 | 和硕联合科技股份有限公司 | Housing and method for manufacturing the same |
| EP2537603A1 (en) * | 2010-02-15 | 2012-12-26 | Tanaka Manufacturing Co. Ltd. | Method for manufacturing component, and component |
| KR20120034538A (en) * | 2010-08-26 | 2012-04-12 | 제일모직주식회사 | High modulus composition for emi shielding and molded articles thereof |
| US20130280479A1 (en) * | 2010-12-13 | 2013-10-24 | Toray Industries, Inc. | Carbon-fiber-reinforced plastic molded article |
| JP5694386B2 (en) * | 2011-01-28 | 2015-04-01 | 帝人株式会社 | Bonded carbon fiber reinforced composite material |
| CN102418232B (en) * | 2011-09-27 | 2014-05-28 | 东华大学 | Wave-absorbing weaving piece of compound bar with carbon filaments arranged in buckling and extending manner and preparation method thereof |
| CN102427713B (en) * | 2011-09-27 | 2015-02-25 | 东华大学 | Wave adsorption sheet formed by carbon fiber endless tows in flexural arrangement form and preparation method thereof |
| WO2013093071A1 (en) * | 2011-12-23 | 2013-06-27 | Hexcel Composites Limited | A method for on-line control of a manufacturing process for a multicomponent sheet material |
| WO2014103658A1 (en) * | 2012-12-26 | 2014-07-03 | 東レ株式会社 | Fiber-reinforced resin sheet, integrated molded product and process for producing same |
| ES2732811T3 (en) * | 2013-04-02 | 2019-11-26 | Toray Industries | Sandwich laminate, sandwich structure and unified molded product that uses them and processes to produce them |
| JP6137300B2 (en) * | 2014-02-03 | 2017-05-31 | 東レ株式会社 | FIBER-REINFORCED MULTILAYER PELLET, MOLDED ARTICLE FORMED BY THE SAME, AND METHOD FOR PRODUCING FIBER-REINFORCED MULTILAYER PELLET |
| CN105313393A (en) * | 2014-05-28 | 2016-02-10 | 青岛顺益新材料科技有限公司 | Novel composite material and production method thereof |
| DE102014008815A1 (en) * | 2014-06-11 | 2016-01-21 | Albis Plastic Gmbh | Method for producing a composite material of metal and plastic to a plastic-metal hybrid component |
| CN104125762B (en) * | 2014-06-12 | 2017-05-17 | 吉林大学 | Z type longitudinal groove type mixed metal alloy electromagnetic shielding composite material and preparation method thereof |
| CN104185410B (en) * | 2014-09-12 | 2017-09-01 | 苏州大学 | Electro-magnetic shielding cover based on micro- metal grill and preparation method thereof |
| CN104320733A (en) * | 2014-09-30 | 2015-01-28 | 陈正盛 | Structure body, earphones using the structure body, and sound box using the structure body |
| TWI573468B (en) * | 2014-10-02 | 2017-03-01 | Cheng Sheng Chen | A structure for an audio device |
| TWI628960B (en) * | 2014-10-02 | 2018-07-01 | 陳正盛 | Audio equipment |
| CN104480572B (en) * | 2014-11-03 | 2016-10-19 | 安徽蓝翔电器成套设备有限公司 | Fiber composition and the preparation method and application of fiber |
| CN105818323A (en) * | 2016-05-03 | 2016-08-03 | 嘉瑞科技（惠州）有限公司 | Process for attaching plastic film layer to carbon fiber surface layer |
| JP6729000B2 (en) * | 2016-06-02 | 2020-07-22 | 株式会社リコー | Image forming device member |
| ITUA20164429A1 (en) * | 2016-06-16 | 2017-12-16 | Luca Alessandrini | PROCEDURE FOR THE REALIZATION OF MUSICAL INSTRUMENTS, HARMONIC BOXES AND ACOUSTIC BOXES, MANUFACTURED WITH THIS PROCEDURE OBTAINED |
| WO2017216203A1 (en) * | 2016-06-16 | 2017-12-21 | Luca Alessandrini | Method for manufacturing musical instruments, sound boxes and acoustic boxes products obtained with such method |
| TWI642309B (en) * | 2016-08-25 | 2018-11-21 | Preheat forming horn vibrating piece manufacturing method | |
| EP3518634B1 (en) * | 2016-09-26 | 2024-11-06 | Toray Industries, Inc. | Electronic device housing |
| CN109691248B (en) * | 2016-09-26 | 2021-07-30 | 东丽株式会社 | Electronic equipment shell and manufacturing method thereof |
| CN106363712A (en) * | 2016-11-15 | 2017-02-01 | 苏州亨达尔工业材料有限公司 | Multifunctional fire retardant panel |
| US11678445B2 (en) * | 2017-01-25 | 2023-06-13 | Apple Inc. | Spatial composites |
| KR20240027150A (en) | 2017-03-29 | 2024-02-29 | 애플 인크. | Device having integrated interface system |
| CN114161783A (en) | 2017-04-26 | 2022-03-11 | 博爱（中国）膨化芯材有限公司 | Thermal composite rapid-infiltration flow guide material and application thereof |
| CN107498881A (en) * | 2017-08-15 | 2017-12-22 | 成都新柯力化工科技有限公司 | A kind of carbon fibre reinforced plastic thermoplastic laser heats welding technology |
| WO2019067772A1 (en) | 2017-09-29 | 2019-04-04 | Mikael Silvanto | Multi-part device enclosure |
| US11364690B2 (en) * | 2018-02-08 | 2022-06-21 | Giant Manufacturing Co., Ltd. | Resin-based composite structure and method for forming resin-based composite structure |
| WO2019226191A1 (en) | 2018-05-25 | 2019-11-28 | Apple Inc. | Portable computer with dynamic display interface |
| US11175769B2 (en) | 2018-08-16 | 2021-11-16 | Apple Inc. | Electronic device with glass enclosure |
| US11189909B2 (en) | 2018-08-30 | 2021-11-30 | Apple Inc. | Housing and antenna architecture for mobile device |
| US10705570B2 (en) | 2018-08-30 | 2020-07-07 | Apple Inc. | Electronic device housing with integrated antenna |
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| CN114399015A (en) | 2019-04-17 | 2022-04-26 | 苹果公司 | Wireless locatable tag |
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| US12009576B2 (en) | 2019-12-03 | 2024-06-11 | Apple Inc. | Handheld electronic device |
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| CN112799230A (en) * | 2020-09-30 | 2021-05-14 | 歌尔光学科技有限公司 | Shell preparation method, shell and head-mounted display device |
| CN112521743A (en) * | 2020-11-12 | 2021-03-19 | 国网山西省电力公司电力科学研究院 | Composite material of electromagnetic shielding layer of power frequency electric field probe |
| CN112680864B (en) * | 2020-12-11 | 2022-05-10 | 江苏恒力化纤股份有限公司 | Fabric-enhanced rearview mirror and preparation method thereof |
| CN113635621A (en) * | 2021-07-30 | 2021-11-12 | 歌尔光学科技有限公司 | Laying method of carbon fiber prepreg, carbon fiber preform and wearable equipment |
| CN115972635B (en) * | 2022-12-14 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic electromagnetic shielding prepreg production device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4604319A (en) * | 1984-06-01 | 1986-08-05 | American Cyanamid Company | Thermoplastic interleafed resin matrix composites with improved impact strength and toughness |
| US4957801A (en) * | 1989-05-17 | 1990-09-18 | American Cyanamid Company | Advance composites with thermoplastic particles at the interface between layers |
| CN1336867A (en) * | 1999-11-22 | 2002-02-20 | 住友化学工业株式会社 | Easily delaminatable laminate and resin composition for use therein |
| CN1362326A (en) * | 2000-12-27 | 2002-08-07 | 三井化学株式会社 | Laminated product with surface protective layer |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3314788A1 (en) * | 1983-04-23 | 1984-10-25 | Basf Ag, 6700 Ludwigshafen | MULTI-STAGE PROCESS FOR PRODUCING HEXAMETHYLENE DIISOCYANATE-1,6 AND / OR ISOMERIC ALIPHATIC DIISOCYANATES WITH 6 CARBON ATOMS IN THE ALKYLENE RESIDUE |
| US4758924A (en) * | 1986-05-29 | 1988-07-19 | Honeywell Bull Inc. | Electronic equipment housing |
| JP3357167B2 (en) * | 1993-05-26 | 2002-12-16 | 松下電工株式会社 | Manufacturing method of fiber reinforced plastic |
| JPH0747152A (en) * | 1993-08-06 | 1995-02-21 | Asahi Chem Ind Co Ltd | Fiber-reinforced resin racket frame |
| JP2000165056A (en) * | 1998-11-30 | 2000-06-16 | Koyo Electronics Ind Co Ltd | Casing of electronic unit |
| TW539614B (en) * | 2000-06-06 | 2003-07-01 | Matsushita Electric Works Ltd | Laminate |
-
2003
- 2003-12-25 CN CNB2007101270328A patent/CN100546443C/en not_active Expired - Lifetime
- 2003-12-25 CN CNB200380107484XA patent/CN100421924C/en not_active Expired - Lifetime
- 2003-12-25 CN CN2007101270313A patent/CN101085865B/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4604319A (en) * | 1984-06-01 | 1986-08-05 | American Cyanamid Company | Thermoplastic interleafed resin matrix composites with improved impact strength and toughness |
| US4604319B1 (en) * | 1984-06-01 | 1995-07-04 | American Cyanamid Co | Thermoplastic interleafed resin matrix composites with improved impact strength and toughness |
| US4957801A (en) * | 1989-05-17 | 1990-09-18 | American Cyanamid Company | Advance composites with thermoplastic particles at the interface between layers |
| CN1336867A (en) * | 1999-11-22 | 2002-02-20 | 住友化学工业株式会社 | Easily delaminatable laminate and resin composition for use therein |
| CN1362326A (en) * | 2000-12-27 | 2002-08-07 | 三井化学株式会社 | Laminated product with surface protective layer |
Non-Patent Citations (1)
| Title |
|---|
| JP昭63-57006A 1988.03.11 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100421924C (en) | 2008-10-01 |
| CN101087500A (en) | 2007-12-12 |
| CN100546443C (en) | 2009-09-30 |
| CN1732083A (en) | 2006-02-08 |
| CN101085865A (en) | 2007-12-12 |
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