WO2015093261A1 - Composition de résine thermodurcissable et composite métal-résine - Google Patents

Composition de résine thermodurcissable et composite métal-résine Download PDF

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Publication number
WO2015093261A1
WO2015093261A1 PCT/JP2014/081627 JP2014081627W WO2015093261A1 WO 2015093261 A1 WO2015093261 A1 WO 2015093261A1 JP 2014081627 W JP2014081627 W JP 2014081627W WO 2015093261 A1 WO2015093261 A1 WO 2015093261A1
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WIPO (PCT)
Prior art keywords
resin composition
thermosetting resin
metal
stainless steel
resin
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PCT/JP2014/081627
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English (en)
Japanese (ja)
Inventor
吉広 瀧花
浩二 小泉
佑典 渡邉
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住友ベークライト株式会社
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Priority to JP2015553453A priority Critical patent/JP6468197B2/ja
Publication of WO2015093261A1 publication Critical patent/WO2015093261A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14795—Porous or permeable material, e.g. foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/02—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0017—Heat stable

Definitions

  • the present invention relates to a thermosetting resin composition and a metal resin composite.
  • thermosetting resin composition As a method for joining a resin member and a metal member, fine irregularities are formed on the surface of the metal member, and after the thermosetting resin composition has entered the fine irregularities, the thermosetting resin composition is cured.
  • a method of joining a resin member made of a thermosetting resin composition and a metal member has been proposed (for example, Patent Documents 1 and 2).
  • Metal resin composites formed by joining a resin member and a stainless steel metal member are used in various product parts. Products using such parts are used for a long time under various temperature atmospheres. According to the study by the present inventors, when a metal resin composite in which the bonding strength between the resin member and the stainless steel metal member is higher than the conventional level is exposed to a high temperature for a long time, the dimensions may change. It became clear that there was. A product using such a metal-resin composite as a component causes problems such as a gap due to dimensional changes.
  • thermosetting resin composition capable of realizing a metal resin composite having excellent dimensional stability at high temperatures, and a metal resin composite having excellent dimensional stability at high temperatures. Is to provide.
  • the present inventors have improved the elastic modulus and mechanical strength of the resin member in order to suppress the dimensional change at high temperature of the metal resin composite, and the relationship between the resin member and the metal member. Adjustment of the linear expansion coefficient was studied. However, simply increasing the elastic modulus and mechanical strength of the resin member or simply adjusting the linear expansion coefficient between the resin member and the metal member sufficiently suppresses the dimensional change of the metal-resin composite at a high temperature. I could't.
  • the present inventors have further intensively studied design guidelines for realizing a metal resin composite having excellent dimensional stability at high temperatures.
  • the inventors have found that the measure of the warpage change rate of the thermosetting resin composition devised by the present inventors is effective as such a design guideline, and reached the present invention.
  • thermosetting resin composition used for forming the resin member, A thermosetting resin; Filling material, Including Using a molding machine, the thermosetting resin composition has a thickness of 1 mm and a maximum height (Rz) of 15 ⁇ 1 ⁇ m under the conditions of an effective pressure of 20 MPa, a mold temperature of 175 ° C., and a curing time of 3 minutes.
  • the sheet-like metal resin composite having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm is produced by injection molding into a mold in which a stainless steel sheet is placed, and then the sheet-like metal resin composite is 150 ° C.
  • the distance from the laser head when the laser is perpendicularly applied to the surface on the stainless steel sheet side of the sheet-like metal resin composite is the longest distance from the laser head.
  • thermosetting resin composition having a warpage change rate calculated by (X2-X1) / X1 ⁇ 100 of ⁇ 35% or more and 35% or less.
  • a metal resin composite comprising a resin member made of the thermosetting resin composition and a stainless metal member bonded to the resin member is provided.
  • thermosetting resin composition capable of realizing a metal resin composite excellent in dimensional stability at high temperatures and a metal resin composite excellent in dimensional stability at high temperatures.
  • FIG. 1 is a cross-sectional view showing an example of the structure of a metal resin composite 100 according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram for explaining the warpage change rate of the embodiment according to the present invention.
  • the metal resin composite 100 includes a resin member 101 and a stainless steel metal member 102 joined to the resin member 101.
  • the resin member 101 is formed of a thermosetting resin composition (P).
  • the thermosetting resin composition (P) includes a thermosetting resin (A) and a filler (B).
  • the thermosetting resin composition (P) has a warpage change rate calculated in the following (1) to (4) of ⁇ 35% or more and 35% or less.
  • the thermosetting resin composition (P) has a thickness of 1 mm and a maximum height (Rz) under the conditions of an effective pressure of 20 MPa, a mold temperature of 175 ° C., and a curing time of 3 minutes.
  • Rz is measured according to JIS-B0601.
  • the thickness of the resin member is 3 mm.
  • the obtained sheet-like metal resin composite is stored at 150 ° C. for 250 hours.
  • the warpage change rate is more preferably ⁇ 30% or more and 30% or less, It is particularly preferably from ⁇ 25% to 25%.
  • the warpage amount X1 before storage is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.01 mm or more, particularly preferably 0.00 mm or more, and preferably 0.50 mm or less, more preferably Is 0.25 mm or less.
  • the warpage amount X2 after storage is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.01 mm or more, particularly preferably 0.00 mm or more, and preferably 0.65 mm or less, more preferably Is 0.30 mm or less.
  • the bonding strength with the resin member can be increased more than the conventional standard by providing a specific roughened layer described later on the surface of the stainless steel metal member.
  • the resin member side thermally shrinks, so it is clear that the size of the metal resin composite changes due to the heat shrinkage stress. became.
  • the bonding strength between the resin member and the stainless steel metal member is strong, even if the resin member side is thermally contracted, the resin member and the stainless steel metal member do not peel off, so that the resin member and the stainless steel metal member may be deformed to the stainless steel metal member side. Became clear.
  • the present inventors have studied to improve the elastic modulus and mechanical strength of the resin member in order to suppress the dimensional change of the metal resin composite at a high temperature.
  • merely increasing the elastic modulus and mechanical strength of the resin member cannot sufficiently suppress the dimensional change of the metal resin composite at a high temperature.
  • the present inventors have further intensively studied a design guideline for realizing a metal resin composite excellent in dimensional stability at high temperatures.
  • the measure of the warpage change rate of the thermosetting resin composition devised by the present inventors is effective as such a design guideline, and reached the present invention.
  • the warpage change rate represents an index of expansion and contraction stress of the thermosetting resin composition. The more the warp change rate is positively increased, the stronger the contraction stress is, and the stronger the force for deforming the stainless steel metal member is. On the other hand, the more negative the warp change rate, the stronger the expansion stress.
  • thermosetting resin composition having a warpage change rate within the above range has an appropriate expansion / contraction stress and a low ability to deform a stainless steel metal member. Therefore, a thermosetting resin composition having a warpage change rate within the above range can realize a metal resin composite having excellent dimensional stability at high temperatures.
  • the warpage change rate of the thermosetting resin composition can be controlled by appropriately adjusting the type and blending ratio of each component constituting the thermosetting resin composition (P).
  • FIG. 3 is a schematic diagram for explaining an example of a cross-sectional shape of the recess 201 constituting the roughened layer 104 on the surface of the stainless steel metal member 102 according to the embodiment of the present invention.
  • the stainless steel metal member 102 preferably has a roughened layer 104 made of fine irregularities on the bonding surface 103 thereof.
  • the roughened layer 104 refers to a region having a plurality of recesses 201 provided on the surface of the stainless steel metal member 102.
  • the thickness of the roughened layer 104 is preferably 3 ⁇ m or more and 40 ⁇ m or less, more preferably 4 ⁇ m or more and 32 ⁇ m or less, and particularly preferably 4 ⁇ m or more and 30 ⁇ m or less.
  • the thickness of the roughening layer 104 represents the depth D3 of the largest depth among the plurality of recesses 201, and can be calculated from an electron microscope (SEM) photograph.
  • the cross section of the recess 201 has a shape having a cross section width D2 larger than the cross section width D1 of the opening 203 in at least a part between the opening 203 and the bottom 205 of the recess 201.
  • the cross-sectional shape of the recess 201 is not particularly limited as long as D2 is larger than D1, and can take various shapes.
  • the cross-sectional shape of the recess 201 can be observed with, for example, an electron microscope (SEM).
  • the cross-sectional shape of the concave portion 201 is the above shape, the resin member 101 is caught between the opening 203 and the bottom portion 205 of the concave portion 201, so that the anchor effect works effectively. Therefore, it is considered that the bonding strength between the resin member 101 and the stainless steel metal member 102 is improved.
  • the average depth of the recess 201 is preferably 0.5 ⁇ m or more and 40 ⁇ m or less, and more preferably 1 ⁇ m or more and 30 ⁇ m or less.
  • the thermosetting resin composition (P) can sufficiently enter the depth of the recess 201, so that the resin member 101 and the stainless steel metal member 102 are mutually It is possible to further improve the mechanical strength of the region that has penetrated into. If the average depth of the recess 201 is equal to or greater than the above lower limit value, the ratio of the filler (B) present in the recess 201 can be increased, so that the resin member 101 and the stainless steel metal member 102 penetrate each other.
  • the mechanical strength of the region can be improved. Therefore, when the average depth of the recesses 201 is within the above range, the bonding strength with the resin member 101 can be further improved.
  • the average depth of the recess 201 can be measured from a scanning electron microscope (SEM) photograph as follows, for example. First, a cross section of the roughened layer 104 is photographed with a scanning electron microscope. From the observation image, 50 concave portions 201 are arbitrarily selected and their depths are measured. The average depth is obtained by integrating all the depths of the recesses 201 and dividing the sum by the number.
  • the average cross-sectional width of the opening 203 of the recess 201 is preferably 2 ⁇ m or more and 60 ⁇ m or less, more preferably 3 ⁇ m or more and 50 ⁇ m or less, and further preferably 3 ⁇ m or more and 30 ⁇ m or less.
  • the anchor effect between the resin member 101 and the stainless steel metal member 102 can be expressed more strongly.
  • the average cross-sectional width of the opening 203 is equal to or greater than the above lower limit value, the ratio of the filler (B) present in the recess 201 can be increased, so that the resin member 101 and the stainless steel metal member 102 are mutually The mechanical strength of the intruded area can be improved. Therefore, when the average cross-sectional width of the opening 203 is within the above range, the bonding strength with the resin member 101 can be further improved.
  • the average cross-sectional width of the opening 203 can be measured from an SEM photograph as follows, for example. First, a cross section of the roughened layer 104 is photographed with a scanning electron microscope. From the observation image, 50 concave portions 201 are arbitrarily selected, and their cross-sectional widths D1 are measured. The average cross-sectional width is obtained by integrating all the cross-sectional widths D1 of the openings 203 and dividing the sum by the number.
  • the surface roughness Ra of the joining surface 103 of the stainless steel metal member 102 is preferably 0.5 ⁇ m or more and 40.0 ⁇ m or less, more preferably 1.0 ⁇ m or more and 20.0 ⁇ m or less, and particularly preferably 1.0 ⁇ m or more. 10.0 ⁇ m or less.
  • the bonding strength with the resin member 101 can be further improved.
  • the maximum height Rz of the joining surface 103 of the stainless steel metal member 102 is preferably 1.0 ⁇ m or more and 40.0 ⁇ m or less, and more preferably 3.0 ⁇ m or more and 30.0 ⁇ m or less. When the maximum height Rz is within the above range, the bonding strength with the resin member 101 can be further improved.
  • Ra and Rz can be measured according to JIS-B0601.
  • the ratio of the actual surface area by the nitrogen adsorption BET method to the apparent surface area of the joint surface 103 to be joined to at least the resin member 101 is preferably 100 or more. Preferably it is 150 or more.
  • the specific surface area is preferably 400 or less, more preferably 380 or less, and particularly preferably 300 or less. When the specific surface area is not more than the upper limit, the bonding strength with the resin member 101 can be further improved.
  • the apparent surface area in the present embodiment means a surface area when it is assumed that the surface of the stainless steel metal member 102 is smooth without unevenness.
  • the surface shape is a rectangle, it is represented by vertical length ⁇ horizontal length.
  • the actual surface area by the nitrogen adsorption BET method in the present embodiment means the BET surface area obtained from the adsorption amount of nitrogen gas.
  • BELSORPmini II manufactured by Nippon Bell Co., Ltd.
  • the specific surface area is within the above range, the reason why the metal-resin composite 100 having further excellent bonding strength can be obtained is not clear, but the surface of the bonding surface 103 with the resin member 101 is the same as that of the resin member 101. This is probably because the anchor effect between the stainless steel metal member 102 and the stainless steel metal member 102 can be expressed more strongly.
  • the specific surface area is equal to or greater than the lower limit, the contact area between the resin member 101 and the stainless steel metal member 102 is increased, and the area where the resin member 101 and the stainless steel metal member 102 enter each other increases. As a result, the area where the anchor effect works increases, and it is considered that the bonding strength between the resin member 101 and the stainless steel metal member 102 is further improved.
  • the specific surface area is too large, the ratio of the stainless steel metal member 102 in the region where the resin member 101 and the stainless steel metal member 102 have entered each other decreases, so that the mechanical strength of this region decreases. Therefore, when the specific surface area is less than or equal to the upper limit value, the mechanical strength of the region where the resin member 101 and the stainless steel metal member 102 have entered each other is further improved. As a result, the resin member 101 and the stainless steel metal It is considered that the bonding strength with the member 102 can be further improved. From the above, when the specific surface area is within the above range, the surface of the joint surface 103 with the resin member 101 can exhibit an anchor effect between the resin member 101 and the stainless steel metal member 102 more strongly. It is assumed that the structure is good.
  • the stainless steel metal member 102 is not particularly limited, but the glossiness of at least the joint surface 103 to be joined to the resin member 101 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1. That's it.
  • the glossiness is preferably 30 or less, more preferably 20 or less.
  • the glossiness in the present embodiment indicates a value at a measurement angle of 60 ° measured in accordance with ASTM-D523.
  • the glossiness can be measured using, for example, a digital glossiness meter (20 °, 60 °) (GM-26 type, manufactured by Murakami Color Research Laboratory).
  • a digital glossiness meter (20 °, 60 °) (GM-26 type, manufactured by Murakami Color Research Laboratory).
  • the stainless steel metal material constituting the stainless steel metal member 102 is not particularly limited as long as it is a metal belonging to the category of stainless steel metal.
  • ferritic stainless steel examples include SUS430, SUS430LX, and SUS405.
  • martensitic stainless steel examples include SUS403 and SUS420.
  • austenitic stainless steel examples include SUS201, SUS202, SUS301, SUS302, SUS303, SUS304, SUS305, SUS316, and SUS317.
  • Examples of the austenitic / ferritic duplex stainless steel include SUS329J1.
  • precipitation hardening stainless steel examples include SUS630.
  • the shape of the stainless steel metal member 102 is not particularly limited as long as it has a joint surface 103 that joins the resin member 101.
  • the stainless steel metal member 102 has a sheet shape, a flat plate shape, a curved plate shape, a rod shape, a cylindrical shape, a lump shape, and the like. be able to.
  • the structure which consists of these combination may be sufficient.
  • the stainless steel metal member 102 having such a shape can be obtained by processing the above-described stainless steel metal material by a known processing method.
  • the shape of the joint surface 103 joined to the resin member 101 is not particularly limited, and examples thereof include a flat surface and a curved surface.
  • the thickness of the stainless steel metal member 102 is not particularly limited because it is appropriately set depending on the use of the metal resin composite 100, but is usually 0.01 mm or more, preferably 0.1 mm or more.
  • the upper limit value of the thickness of the stainless steel metal member 102 is not particularly limited, but is, for example, 50 mm or less.
  • the roughened layer 104 can be formed, for example, by chemically treating the surface of the stainless steel metal member 102 using a surface treatment agent.
  • a surface treatment agent for example, the chemical treatment of the surface of the stainless steel metal member 102 using the surface treatment agent itself has been performed in the prior art.
  • the present inventors have (1) a combination of a stainless steel metal member and a surface treatment agent, (2) temperature and time of chemical treatment, (3) post-treatment of the stainless steel metal member surface after chemical treatment, It has been found that the roughened layer 104 excellent in the bonding property with the resin member 101 can be obtained by controlling the factors such as the above.
  • the roughened layer 104 In order to obtain the roughened layer 104 that can further improve the bonding strength with the resin member 101, it is particularly important to control these factors to a high degree.
  • a method for forming the roughened layer 104 on the surface of the stainless steel metal member 102 will be described.
  • the method for forming the roughened layer 104 according to the present embodiment is not limited to the following example.
  • a surface treatment agent is selected.
  • the surface treatment agent it is preferable to select an aqueous solution in which an inorganic acid, a chlorine ion source, a cupric ion source, and a thiol compound are combined as necessary.
  • the processing temperature is, for example, 30 ° C.
  • the treatment time is appropriately determined depending on the material and surface state of the stainless steel metal member to be selected, the type and concentration of the surface treatment agent, the treatment temperature, etc., and is, for example, 30 to 300 seconds.
  • the etching amount in the depth direction of the stainless steel metal member is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more.
  • the etching amount in the depth direction of the stainless steel metal member can be evaluated by calculating from the weight, specific gravity and surface area of the dissolved stainless steel metal member.
  • the etching amount in the depth direction can be adjusted by the type and concentration of the surface treatment agent, the treatment temperature, the treatment time, and the like.
  • the thickness of the roughened layer 104, the average depth of the concave portion 201, the specific surface area, the glossiness, Ra, Rz, and the like can be adjusted by adjusting the etching amount in the depth direction.
  • the resin member 101 is formed by curing a thermosetting resin composition (P) containing a thermosetting resin (A) and a filler (B).
  • thermosetting resin composition (P) is, for example, in the form of powder, granules, or tablets.
  • thermosetting resin (A) examples include phenol resin, epoxy resin, unsaturated polyester resin, diallyl phthalate resin, melamine resin, oxetane resin, maleimide resin, urea (urea) resin, polyurethane resin, silicone resin, and benzoxazine.
  • a resin having a ring, a cyanate ester resin, or the like is used. These may be used alone or in combination of two or more.
  • thermosetting resin (A) is preferably 10% by mass or more and 43% by mass or less, more preferably 15%, when the total solid content of the thermosetting resin composition (P) is 100% by mass.
  • the content is not less than 38% by mass and more preferably not less than 15% by mass and less than 30% by mass.
  • phenol resin examples include novolak phenol resins such as phenol novolak resin, cresol novolak resin, and bisphenol A type novolak resin; Examples thereof include resol type phenol resins such as oil-melted resol phenol resin; aryl alkylene type phenol resins and the like. These may be used alone or in combination of two or more. Among these, a novolak type phenol resin is preferable because it is easily available, inexpensive, and has good workability by roll kneading.
  • hexamethylenetetramine is usually used as a curing agent.
  • hexamethylenetetramine is not particularly limited, it is preferably used in an amount of 10 to 25 parts by weight, more preferably 13 to 20 parts by weight, based on 100 parts by weight of the novolac type phenol resin.
  • the amount of hexamethylenetetramine used is not less than the above lower limit, the curing time during molding can be shortened.
  • the external appearance of a molded article can be improved as the usage-amount of hexamethylenetetramine is below the said upper limit.
  • the thermosetting resin composition (P) contains the filler (B) from the viewpoint of improving the mechanical strength of the resin member 101.
  • the shrinkage inhibitor (D) described later is excluded from the filler (B).
  • the content of the filler (B) is preferably 55% by mass or more and 85% by mass or less, more preferably 60% by mass, when the total solid content of the thermosetting resin composition (P) is 100% by mass. It is 80 mass% or less, More preferably, it is 65 mass% or more and 75 mass% or less.
  • Examples of the filler (B) include a fibrous filler, a granular filler, and a plate-like filler.
  • the fibrous filler is a filler whose shape is fibrous.
  • the plate-like filler is a filler whose shape is plate-like.
  • the granular filler is a filler having a shape other than a fibrous filler or a plate-like filler including an indefinite shape.
  • fibrous filler examples include glass fiber, carbon fiber, asbestos fiber, metal fiber, wollastonite, attapulgite, sepiolite, rock wool, aluminum borate whisker, potassium titanate fiber, calcium carbonate whisker, and titanium oxide whisker.
  • fibrous inorganic fillers such as ceramic fibers; and fibrous organic fillers such as aramid fibers, polyimide fibers, and polyparaphenylene benzobisoxazole fibers. These may be used alone or in combination of two or more.
  • Examples of the plate-like filler and granular filler include talc, kaolin clay, calcium carbonate, zinc oxide, calcium silicate hydrate, mica, glass flakes, glass beads, magnesium carbonate, silica, titanium oxide, Alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride, silicon nitride, the above fibers
  • a pulverized product of a filler may be used alone or in combination of two or more.
  • the filler (B) preferably has an average particle size of 0.1 ⁇ m or more in a weight-based particle size distribution measured by a laser diffraction / scattering particle size distribution measurement method. Thereby, the mechanical strength of the resin member 101 obtained can be further improved while improving the workability of the thermosetting resin composition (P).
  • the upper limit of the average particle diameter of a filler (B) is not specifically limited, For example, it is 100 micrometers or less.
  • the filler (B) more preferably includes a fibrous filler or a plate-like filler having an average major axis of 5 ⁇ m to 50 mm and an average aspect ratio of 1 to 1000.
  • the average major axis and average aspect ratio of the filler (B) can be measured from the SEM photograph as follows, for example. First, a plurality of fibrous fillers or plate-like fillers are photographed with a scanning electron microscope. From the observation image, 50 fibrous fillers or plate-like fillers are arbitrarily selected, and their major diameters (fiber length in the case of fibrous fillers, planar major dimension in the case of plate-like fillers) and The short diameter (in the case of a fibrous filler, the fiber diameter, in the case of a plate-like filler, the dimension in the thickness direction) is measured. The average major axis is obtained by integrating all major axes and dividing by the number. Similarly, the average minor axis is obtained by integrating all minor axes and dividing by the number. The average major axis with respect to the average minor axis is defined as the average aspect ratio.
  • filler (B) wollastonite, kaolin clay, talc, mica, glass beads, titanium oxide, alumina, silica, calcium carbonate, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium sulfate, calcium sulfite, boric acid
  • One or more selected from the group consisting of zinc, barium metaborate, aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride, silicon nitride, carbon fiber, and glass fiber are preferred, glass fiber, One or more selected from the group consisting of carbon fiber, glass beads, calcium carbonate, wollastonite, silica, and kaolin clay are more preferable.
  • the mechanical strength of the resin member 101 can be particularly improved.
  • the filler (B) may be subjected to a surface treatment with a coupling agent such as a silane coupling agent (C) described later.
  • a coupling agent such as a silane coupling agent (C) described later.
  • the thermosetting resin composition (P) may further contain a silane coupling agent (C).
  • a silane coupling agent (C) By including the silane coupling agent (C), the adhesion to the stainless steel metal member 102 can be improved. Further, by including the silane coupling agent (C), the affinity between the thermosetting resin (A) and the filler (B) is improved, and as a result, the mechanical strength of the resin member 101 is further improved. be able to.
  • the content of the silane coupling agent (C) is not particularly limited because it depends on the specific surface area of the filler (B), but is preferably 0.01 parts by mass or more and 4 parts by mass with respect to 100 parts by mass of the filler (B). 0.0 part by mass or less, and more preferably 0.1 part by mass or more and 1.0 part by mass or less. When the content of the silane coupling agent (C) is within the above range, the mechanical strength of the resin member 101 can be further improved while sufficiently covering the filler (B).
  • silane coupling agent (C) examples include epoxy groups such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • alkoxysilane compounds mercapto group-containing alkoxysilane compounds such as ⁇ -mercaptopropyltrimethoxysilane and ⁇ -mercaptopropyltriethoxysilane; ⁇ -ureidopropyltriethoxysilane, ⁇ -ureidopropyltrimethoxysilane, ⁇ - (2- Ureido group-containing alkoxysilane compounds such as ureidoethyl) aminopropyltrimethoxysilane; ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropylmethyldimethoxy Isocyanato group-containing alkoxysilane compounds such as silane, ⁇ -isocyanatopropylmethyldiethoxysilane, ⁇ -isocyanatopropylethyldime
  • the thermosetting resin composition (P) preferably contains a shrinkage inhibitor (D) from the viewpoint of suppressing thermal shrinkage of the resin member 101.
  • the filler (B) described above is excluded from the shrinkage inhibitor (D).
  • the content of the shrinkage inhibitor (D) is preferably 0.5% by mass or more and 10% by mass or less, and more preferably when the total solid content of the thermosetting resin composition (P) is 100% by mass. It is 1 mass% or more and 8 mass% or less.
  • the shrinkage inhibitor (D) is not particularly limited as long as it has a large thermal expansion coefficient and can suppress the thermal shrinkage of the resin member 101.
  • acrylonitrile / butadiene rubber, unmodified polyvinyl acetate, carboxylic acid-modified poly Elastomers such as vinyl acetate, polyvinyl butyral, natural rubber, isoprene rubber, styrene / butadiene rubber, butadiene rubber, chloroprene rubber, butyl rubber, ethylene / propylene rubber, acrylic rubber, styrene / isoprene rubber, urethane rubber, silicone rubber, fluorine rubber, etc.
  • These may be used alone or in combination of two or more.
  • the reason why the shrinkage can be suppressed is not necessarily clear, but it is considered that these compounds suppress the shrinkage by being incorporated into the crosslinked structure of the resin.
  • acrylonitrile / budadiene rubber, unmodified polyvinyl acetate, and carboxylic acid-modified polyvinyl acetate are preferable, and carboxylic acid-modified polyvinyl acetate is particularly preferable.
  • Carboxylic acid-modified polyvinyl acetate reacts with the thermosetting resin (A) such as phenol resin to reflect the characteristics of polyvinyl acetate more, so acrylonitrile / budadiene rubber, unmodified polyvinyl acetate, etc. It is considered that the resin member 101 has a superior heat shrinkage suppressing power compared to the above.
  • thermosetting resin composition P
  • thermosetting resin (A) filler (B), if necessary, silane coupling agent (C), shrinkage inhibitor (D), curing agent, curing aid, release agent, pigment, flame retardant
  • a weathering agent, an antioxidant, a plasticizer, a lubricant, a sliding agent, a foaming agent and the like are blended and mixed uniformly.
  • thermosetting resin composition (P) is obtained by granulating or pulverizing the obtained mixture.
  • the linear expansion coefficient ⁇ R in the range from 25 ° C. to the glass transition temperature of the resin member 101 is preferably 5 ppm / ° C. or more and 25 ppm / ° C. or less, more preferably 10 ppm / ° C. or more and 20 ppm / ° C. or less.
  • the reliability of the temperature cycle of the metal resin composite 100 can be further improved.
  • the linear expansion coefficient ⁇ R in the range from 25 ° C. to the glass transition temperature of the resin member 101 and the linear expansion coefficient ⁇ R1 in the flow direction (MD) and the direction perpendicular to the MD (
  • the absolute value of the difference ( ⁇ R1 ⁇ R2 ) from the linear expansion coefficient ⁇ R2 of TD) is preferably 10 ppm / ° C. or less, more preferably 8 ppm / ° C. or less. If the difference in the linear expansion coefficient is not more than the above upper limit value, distortion and warpage generated in the resin member 101 can be reduced, and as a result, the dimensional stability at a high temperature of the resulting metal resin composite 100 can be further improved. Can do.
  • the thickness of the resin member 101 is not particularly limited because it is appropriately set depending on the use of the metal resin composite 100, but is usually 0.05 mm or more, preferably 0.1 mm or more.
  • the upper limit value of the thickness of the resin member 101 is not particularly limited, but is, for example, 50 mm or less.
  • the metal resin composite 100 includes a resin member 101 and a stainless steel metal member 102 joined to the resin member 101.
  • the metal-resin composite 100 has a linear expansion coefficient ⁇ R in the range from 25 ° C. to the glass transition temperature of the resin member 101, and a line in the range from 25 ° C. of the stainless metal member 102 to the glass transition temperature of the resin member 101.
  • the absolute value of the difference from the expansion coefficient ⁇ M ( ⁇ R ⁇ M ) is preferably 15 ppm / ° C. or less, more preferably 10 ppm / ° C. or less, and further preferably 5 ppm / ° C. or less. If the difference in the linear expansion coefficient is less than or equal to the upper limit, thermal stress due to the difference in linear expansion that occurs when the metal resin composite 100 is exposed to a high temperature can be suppressed.
  • the bonding strength between the resin member 101 and the stainless steel metal member 102 can be maintained even at a high temperature. That is, if the difference in the linear expansion coefficient is not more than the upper limit value, the dimensional stability of the metal resin composite 100 at a high temperature can be further improved.
  • the linear expansion coefficient has anisotropy, an average value thereof is represented. For example, when the resin member 101 is in the form of a sheet, when the linear expansion coefficient in the flow direction (MD) is different from the linear expansion coefficient in the vertical direction (TD), the average value thereof is the linear expansion coefficient ⁇ of the resin member 101. R.
  • the metal resin composite 100 is not particularly limited, but it is preferable that the resin member 101 and the stainless steel metal member 102 are joined without an adhesive.
  • the resin member 101 and the stainless steel metal member 102 have excellent bonding strength even without an adhesive. Therefore, the manufacturing process of the metal resin composite 100 can be simplified.
  • the adhesive refers to an adhesive known in the technical field of metal resin composites, and examples thereof include an epoxy adhesive.
  • the total thickness of the metal resin composite 100 is not particularly limited because it is appropriately set depending on the use of the metal resin composite 100, but is usually 0.06 mm or more, preferably 0.2 mm or more. Although the upper limit of the thickness of the metal resin composite 100 is not particularly limited, for example, it is 100 mm or less.
  • a method for manufacturing the metal resin composite 100 will be described. Although it does not specifically limit as a manufacturing method of the metal resin composite 100, for example, the injection molding method, the transfer molding method, the compression molding method, the injection compression molding method etc. are mentioned. Of these, the injection molding method is particularly suitable.
  • the manufacturing method of the metal resin composite 100 includes, for example, the following steps. (1) Step of installing a stainless steel metal member 102 having a roughened layer 104 on at least a bonding surface 103 to be bonded to the resin member 101 in the mold 105 (2) A thermosetting resin composition ( P) is injected, and the thermosetting resin composition (P) is cured in a state where at least a part of the thermosetting resin composition (P) is in contact with the bonding surface 103, whereby the thermosetting resin composition ( Step of joining resin member 101 made of P) and stainless steel metal member 102
  • FIG. 4 is a cross-sectional view schematically showing an example of an apparatus for manufacturing the metal resin composite 100 according to the embodiment of the present invention.
  • a mold 105 is prepared, and the stainless steel metal member 102 is installed in the mold 105.
  • the thermosetting resin composition is formed in the mold 105 so that at least a part of the thermosetting resin composition (P) is in contact with the joining surface 103 of the stainless steel metal member 102.
  • the object (P) is injected.
  • thermosetting resin composition (P) is cured in a state where at least a part of the thermosetting resin composition (P) is in contact with the bonding surface 103. Thereafter, the metal resin composite 100 is taken out from the mold 105, and the metal resin composite 100 is obtained.
  • thermosetting resin composition (P) preferably has high fluidity in order to perform molding well. Therefore, the thermosetting resin composition (P) has a melt viscosity at 175 ° C. of preferably 10 Pa ⁇ s to 3000 Pa ⁇ s, and more preferably 30 Pa ⁇ s to 2000 Pa ⁇ s.
  • the melt viscosity at 175 ° C. can be measured by, for example, a thermal fluidity evaluation apparatus (flow tester) manufactured by Shimadzu Corporation.
  • the molding conditions of the metal resin composite 100 are not particularly limited because they vary depending on the molding method employed, but generally known molding conditions in the employed molding method can be employed.
  • molding conditions of a temperature of 160 to 180 ° C., a pressure of 10 to 30 MPa, and a curing time of 30 seconds to 5 minutes can be mentioned.
  • the metal resin composite 100 according to the present embodiment Since the metal resin composite 100 according to the present embodiment has high productivity and high degree of freedom in shape control, it can be developed for various uses. For example, it can be used for aircraft parts, automobile parts, electronic equipment parts, household appliance parts, industrial equipment parts, and the like. It is preferable that the metal resin composite body 100 according to the present embodiment is particularly used for automotive parts.
  • thermosetting resin composition (P1) The melt viscosity of the thermosetting resin composition (P1) at 175 ° C. was measured using a thermal fluid characteristic evaluation apparatus (Koka flow tester, CFT-500D).
  • Stainless steel sheet A (80 mm ⁇ 10 mm, thickness 1.0 mm, SUS304) was prepared as a stainless steel sheet that was not surface-treated.
  • the stainless steel sheet A was immersed and swung, and dissolved in the depth direction by 15 ⁇ m (calculated from the reduced weight of stainless steel). Subsequently, it washed with water and dried and the stainless steel sheet 1 was obtained.
  • the sample to be measured was vacuum-dried at 120 ° C. for 6 hours, and then the nitrogen adsorption / desorption amount at the liquid nitrogen temperature was measured using an automatic specific surface area / pore distribution measuring device (BELSORPmini II, manufactured by Nippon Bell Co., Ltd.).
  • BELSORPmini II automatic specific surface area / pore distribution measuring device
  • the actual surface area by the nitrogen adsorption BET method was calculated from the BET plot.
  • the specific surface area was calculated by dividing the actual surface area measured by the nitrogen adsorption BET method by the apparent surface area.
  • the specific surface area of the stainless steel sheet 1 was 250.
  • the glossiness of the surface of the stainless steel metal member is measured at a measurement angle of 60 according to ASTM-D523 using a digital gloss meter (20 °, 60 °) (GM-26, manufactured by Murakami Color Research Laboratory Co., Ltd.). Measured at °. The glossiness of the stainless steel sheet 1 was 10.
  • the surface of the stainless steel metal member was photographed with an electron microscope (SEM), and the structure of the roughened layer existing on the surface of the stainless steel metal member was observed. From the obtained SEM photograph, the thickness of the roughened layer, the cross-sectional shape of the concave portion, the average depth of the concave portion, and the average cross-sectional width of the opening were determined.
  • the thickness of the roughened layer of the stainless steel sheet 1 was 15 ⁇ m
  • the average depth of the recesses was 13 ⁇ m
  • the average cross-sectional width of the openings was 14 ⁇ m.
  • the cross section of the concave portion has a shape having a cross sectional width larger than the cross sectional width of the opening portion at least at a part between the opening portion and the bottom portion of the concave portion.
  • the metal resin composite 1 was produced using the obtained thermosetting resin composition (P1) and the stainless steel sheet 1. Specifically, it was produced by the following procedure. First, a stainless steel sheet 1 having a thickness of 1 mm is placed in a mold. Next, the thermosetting resin composition (P1) is heated so that the thickness after curing is 3 mm, and a predetermined amount is injected into the mold. Finally, by curing the thermosetting resin composition (P1) by compression molding, a metal resin composite 1 that is a two-layer sheet of a resin member sheet having a thickness of 3 mm and a stainless sheet 1 having a thickness of 1 mm was obtained ( (Length 80mm, width 10mm, thickness 4mm). This metal resin composite 1 was used as a test piece 1. The compression molding conditions were an effective pressure of 20 MPa, a mold temperature of 175 ° C., and a curing time of 3 minutes.
  • the bending strength of the obtained test piece 1 was measured in an atmosphere at 25 ° C. according to JIS K 6911. At this time, the test was performed by placing the stainless steel sheet 1 on the lower side.
  • the unit of bending strength is “MPa”.
  • Example 2 A metal resin composite 2 was produced in the same manner as in Example 1 except that the following thermosetting resin composition (P2) was used instead of the thermosetting resin composition (P1). This metal resin composite 2 was used as a test piece 2, and the same evaluation as in Example 1 was performed.
  • Example 3 A metal resin composite 3 was produced in the same manner as in Example 1 except that the following thermosetting resin composition (P3) was used instead of the thermosetting resin composition (P1). This metal resin composite 3 was used as a test piece 3 and evaluated in the same manner as in Example 1. 18.5% by weight of novolac-type phenolic resin (PR-51305, manufactured by Sumitomo Bakelite Co., Ltd.), 3.5% by weight of hexamethylenetetramine, glass fiber (CS3E479, manufactured by Nittobo Co., Ltd., average particle size: 11 ⁇ m, average major axis: 3mm, average aspect ratio: 270) 20.0% by mass, wollastonite (manufactured by NYCO Minerals, product name: NYAD325, average particle size: 10 ⁇ m) 30.0% by mass, fused silica (manufactured by ELKEM, product) Name: SIDISTAR, average particle size: 0.15 ⁇ m) is 20.0% by mass, carboxylic acid-modified poly
  • Example 4 A metal resin composite 4 was produced in the same manner as in Example 1 except that the following thermosetting resin composition (P4) was used instead of the thermosetting resin composition (P1). This metal resin composite 4 was used as a test piece 4 and evaluated in the same manner as in Example 1.
  • Resol type phenol resin Suditomo Bakelite, PR-513723
  • novolac type phenol resin PR-51305, manufactured by Sumitomo Bakelite
  • glass fiber S3E479, Nittobo
  • Manufactured average particle size: 11 ⁇ m, average major axis: 3 mm, average aspect ratio: 270
  • wollastonite manufactured by NYCO Minerals, product name: NYAD325, average particle size: 10 ⁇ m
  • Example 5 A metal resin composite 5 was produced in the same manner as in Example 1 except that the following thermosetting resin composition (P5) was used instead of the thermosetting resin composition (P1). The metal resin composite 5 was used as a test piece 5 and the same evaluation as in Example 1 was performed.
  • Example 6 A metal resin composite 6 was produced in the same manner as in Example 1 except that the following thermosetting resin composition (P6) was used instead of the thermosetting resin composition (P1). This metal resin composite 6 was used as a test piece 6 and evaluated in the same manner as in Example 1.
  • Example 7 A metal resin composite 7 was produced in the same manner as in Example 1 except that the following thermosetting resin composition (P7) was used instead of the thermosetting resin composition (P1). The metal resin composite 7 was used as a test piece 7, and the same evaluation as in Example 1 was performed.
  • Example 8 A metal resin composite 8 was produced in the same manner as in Example 1 except that the following stainless steel sheet 2 was used instead of the stainless steel sheet 1. This metal resin composite 8 was used as a test piece 8, and the same evaluation as in Example 1 was performed. An aqueous solution of sulfuric acid (50 mass%), cupric sulfate pentahydrate (3 mass%), potassium chloride (3 mass%), and thiosalicylic acid (0.0001 mass%) was prepared. In the obtained aqueous solution (30 ° C.), the stainless steel sheet A was immersed and rocked, and dissolved in the depth direction by 30 ⁇ m (calculated from the reduced weight of stainless steel). Subsequently, it washed with water and dried and the stainless steel sheet 2 was obtained.
  • the characteristics of the stainless steel sheet 2 were as follows. Ra: 2.8 ⁇ m Rz: 28.0 ⁇ m Specific surface area: 280 Glossiness: 8 Roughening layer thickness: 30 ⁇ m Average depth of recess: 28 ⁇ m Average cross-sectional width of the opening: 5 ⁇ m Linear expansion coefficient ⁇ M : 17 ppm / ° C.
  • the cross section of the concave portion has a shape having a cross sectional width larger than the cross sectional width of the opening portion at least at a part between the opening portion and the bottom portion of the concave portion.
  • Example 9 A metal resin composite 9 was produced in the same manner as in Example 1 except that the following stainless steel sheet 3 was used instead of the stainless steel sheet 1. This metal resin composite 9 was used as a test piece 9, and the same evaluation as in Example 1 was performed. An aqueous solution of sulfuric acid (50 mass%), cupric sulfate pentahydrate (3 mass%), potassium chloride (3 mass%), and thiosalicylic acid (0.0001 mass%) was prepared. In the obtained aqueous solution (30 ° C.), the stainless steel sheet A was immersed and swung, and dissolved in the depth direction by 4 ⁇ m (calculated from the reduced weight of stainless steel). Subsequently, it washed with water and dried and the stainless steel sheet 3 was obtained.
  • the characteristics of the stainless steel sheet 3 were as follows. Ra: 1.1 ⁇ m Rz: 4.0 ⁇ m Specific surface area: 165 Glossiness: 13 Roughening layer thickness: 4 ⁇ m Average depth of recess: 3.7 ⁇ m Average cross-sectional width of the opening: 3 ⁇ m Linear expansion coefficient ⁇ M : 17 ppm / ° C.
  • the cross section of the concave portion has a shape having a cross sectional width larger than the cross sectional width of the opening portion at least at a part between the opening portion and the bottom portion of the concave portion.
  • thermosetting resin composition P8
  • thermosetting resin composition P1
  • thermosetting resin composition P9
  • thermosetting resin composition P1
  • thermosetting resin composition P10
  • thermosetting resin composition P1
  • This metal resin composite 12 was used as a test piece 12, and the same evaluation as in Example 1 was performed.
  • novolac-type phenolic resin PR-51305, manufactured by Sumitomo Bakelite
  • hexamethylenetetramine, glass fiber CS3E479, manufactured by Nittobo Co., Ltd., average particle size: 11 ⁇ m, average major axis: 3mm, average aspect ratio: 270
  • wollastonite manufactured by NYCO Minerals, product name: NYAD325, average particle size: 10 ⁇ m
  • fused silica manufactured by ELKEM, product
  • SIDISTAR average particle size: 0.15 ⁇ m
  • carboxylic acid-modified polyvinyl acetate manufactured by Denki Kagaku Kogyo Co., Ltd., product name: Denka ASR CH-09
  • 10.5% by mass ⁇ -1.0% by mass of aminopropyltriethoxysilane (manufactured
  • Table 1 and Table 2 show the above evaluation results.
  • the metal resin composites 1 to 9 obtained in Examples 1 to 9 had a warpage change rate in the range of ⁇ 35% to 35%. Further, the metal resin composites 1 to 9 had a sufficient bending strength. The casings using such metal resin composites 1 to 9 did not show any abnormality in the joints, and were excellent in dimensional stability at high temperatures. On the other hand, the metal resin composites 10 to 12 obtained in Comparative Examples 1 to 3 had a warpage change rate outside the range of ⁇ 35% to 35%. The casings using such metal resin composites 10 to 12 had gaps at the joints and were inferior in dimensional stability at high temperatures.

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Abstract

L'invention concerne une composition de résine thermodurcissable (P) destinée à être utilisée pour former un élément en résine (101) dans un composite métal-résine (100) constitué de l'élément en résine (101) et d'un élément métallique en acier inoxydable (102) assemblé à l'élément en résine (101). La composition de résine thermodurcissable (P) comprend une résine thermodurcissable (A) et une charge (B). Le degré de gauchissement est compris entre -35 % et 35 %.
PCT/JP2014/081627 2013-12-20 2014-11-28 Composition de résine thermodurcissable et composite métal-résine WO2015093261A1 (fr)

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CN105178177A (zh) * 2015-08-07 2015-12-23 吴昊 一种公路桥梁自适应多向变位复合结构伸缩装置
JP2017165609A (ja) * 2016-03-15 2017-09-21 デンカ株式会社 六方晶窒化ホウ素の一次粒子凝集体、樹脂組成物及びその用途
WO2018152998A1 (fr) * 2017-02-23 2018-08-30 歌尔股份有限公司 Élément combiné en acier inoxydable et en plastique et procédé de traitement de celui-ci
WO2020010812A1 (fr) * 2018-07-12 2020-01-16 歌尔股份有限公司 Procédé de préparation d'une pièce composite en céramique-plastique
CN112477213A (zh) * 2020-11-11 2021-03-12 四川文诚管业有限公司 一种钢丝网骨架聚乙烯复合管生产工艺及其制备的复合管
JP7001874B1 (ja) * 2020-08-25 2022-01-20 ポリプラスチックス株式会社 樹脂成形品の弾性率の推定方法、樹脂成形品の応力推定方法、プログラム、コンピュータ可読記録媒体、樹脂成形品の弾性率の算定装置、樹脂成形品の製造方法、樹脂成形品の弾性率のデータ取得方法、樹脂成形品の形状最適化方法、樹脂成形品の変形予測方法、樹脂成形品の破壊寿命予測方法

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JPH0912840A (ja) * 1995-06-27 1997-01-14 Sumitomo Bakelite Co Ltd フェノール樹脂成形材料
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105178177A (zh) * 2015-08-07 2015-12-23 吴昊 一种公路桥梁自适应多向变位复合结构伸缩装置
JP2017165609A (ja) * 2016-03-15 2017-09-21 デンカ株式会社 六方晶窒化ホウ素の一次粒子凝集体、樹脂組成物及びその用途
WO2018152998A1 (fr) * 2017-02-23 2018-08-30 歌尔股份有限公司 Élément combiné en acier inoxydable et en plastique et procédé de traitement de celui-ci
WO2020010812A1 (fr) * 2018-07-12 2020-01-16 歌尔股份有限公司 Procédé de préparation d'une pièce composite en céramique-plastique
JP7001874B1 (ja) * 2020-08-25 2022-01-20 ポリプラスチックス株式会社 樹脂成形品の弾性率の推定方法、樹脂成形品の応力推定方法、プログラム、コンピュータ可読記録媒体、樹脂成形品の弾性率の算定装置、樹脂成形品の製造方法、樹脂成形品の弾性率のデータ取得方法、樹脂成形品の形状最適化方法、樹脂成形品の変形予測方法、樹脂成形品の破壊寿命予測方法
CN112477213A (zh) * 2020-11-11 2021-03-12 四川文诚管业有限公司 一种钢丝网骨架聚乙烯复合管生产工艺及其制备的复合管

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